CN114195656B - Large-area high-transmittance metal halide scintillating ceramic and preparation method thereof - Google Patents

Large-area high-transmittance metal halide scintillating ceramic and preparation method thereof Download PDF

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CN114195656B
CN114195656B CN202111434405.2A CN202111434405A CN114195656B CN 114195656 B CN114195656 B CN 114195656B CN 202111434405 A CN202111434405 A CN 202111434405A CN 114195656 B CN114195656 B CN 114195656B
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夏志国
韩凯
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South China University of Technology SCUT
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Abstract

The invention belongs to the technical field of luminescent materials, and discloses a large-area high-transmittance metal halide scintillating ceramic and a preparation method thereof. The chemical composition formula of the hybridized metal halide is Or u M v X w . The invention provides a method for pressing powder into a large-area high-permeability ceramic block by a low-temperature cold sintering process. The metal halide ceramic exhibits excellent scintillation properties and temperature stability, such as a high energy absorption coefficient and a high light yield. The invention solves the key problems that the existing scintillation crystal is difficult to grow, has poor light transmittance and the like.

Description

Large-area high-transmittance metal halide scintillating ceramic and preparation method thereof
Technical Field
The invention relates to the field of luminescent materials, in particular to a large-area high-transmittance metal halide scintillating ceramic and a preparation method thereof.
Background
The scintillator is a medium material for converting high-energy X-rays or ions into ultraviolet-visible light, and has wide application in the fields of nuclear medicine imaging, safety inspection, space detection, high-energy physics and the like. However, the scintillation crystal at present has the common problems of low sensitivity, imaging artifact residues, complex preparation process, high cost and the like. In recent years, zero-dimensional metal halides have been promoted as one of the most competitive semiconductor materials in terms of scintillation by their excellent optical properties, such as large absorption coefficient, high external quantum efficiency, and broad stokes shift, as well as low-cost, large-scale, simple, easy-to-implement synthesis methods. In fact, metal halide scintillators suffer from stability problems such as susceptibility to moisture absorption, susceptibility to oxidation, and difficulty in preparing large-area high-permeability blocks. At present, for the preparation of large-area bulk materials of metal halides, the preparation of an organic composite film is mainly focused (Highly efficient eco-friendly X-ray scintillators based on an organic manganese halide. Nat. Commun.2020,11,4329), however, the non-uniformity and the non-suitability of the composite film seriously influence the transparency of the composite film, thereby impeding the application of the composite film in the field of X-ray imaging.
Therefore, finding a metal halide system suitable for scintillation, combining with advanced preparation technology, component and structure regulation and control strategies, further improving scintillation performance, large-area imaging and stability are the difficulties and hot spots in the current metal halide scintillation field. This study is of great scientific significance for the practical use of metal halides in the scintillation field.
Disclosure of Invention
In view of the above shortcomings and drawbacks of the prior art, it is an object of the present invention to develop a large area high permeability metal halide scintillating ceramic material. The material has excellent scintillation performance and temperature stability, such as high-energy radiation absorption coefficient, high light yield and the like, and solves the key problems that the existing scintillation crystal is difficult to grow, poor in light transmittance and the like.
The second purpose of the invention is to provide a preparation method of the large-area high-permeability metal halide scintillating ceramic. The preparation method is simple, easy to operate, low in equipment cost and pollution-free.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the invention provides a large-area high-permeability metal halide scintillating ceramic, the chemical composition formula of the hybridized metal halide is Or u M v X w 。
Wherein Or is one Or more of tetraphenyl phosphine bromide, triphenylphosphine, benzyl trimethyl halide, benzyl triethyl halide, benzyl tributyl halide and organic ligand of 1-methyl-1-ethyl pyrrolidine bromide;
m is one or more of Mn, zn, pb, sb and Bi;
x is one or more of Cl, br and I;
u, v, w represent the molar contents of Or, M, X, respectively, wherein 1 < u < 3,1 < v < 3, and 3 < w < 5.
The invention provides a preparation method of a large-area high-permeability metal halide scintillating ceramic, which comprises the following steps:
(1) Dissolving halide, oxide Or carbonate of metal M and organic ligand Or in the molar ratio of 1 (1-4) in solvent, heating and stirring to dissolve completely at 60-150 deg.c for 0.5-6 hr;
(2) Standing the solution dissolved in the step (1) for 12-24 hours under the action of an antisolvent, and separating out crystals or powder;
(3) Separating out the crystals or powder separated out in the step (2) through suction filtration, and then vacuum drying at 40-80 ℃ for 6-24 hours to obtain seed crystals or powder;
(4) Adding the powder obtained in the step (3) into a solution with the mass fraction of 10% -40%, wherein the solution is one or more of N, N-dimethylformamide, dimethyl sulfoxide and high-purity water, and fully and uniformly mixing to obtain powder;
(5) Adding seed crystals obtained in the step (3) into the powder obtained in the step (4), then adding the seed crystals into a die, pressing the seed crystals into ceramic sheets under the action of pressurizing and heating, and preserving heat to obtain the high-permeability metal halide ceramic.
Further, the solvent in the step (1) is one or more of N, N-dimethylformamide and dimethyl sulfoxide, and the molar volume ratio of the halide, the oxide or the carbonate of the metal M to the solvent is 1:2-1:5 mmol/mL.
Further, the antisolvent in the step (2) is one or more of acetone, ethanol and diethyl ether.
Further, in the ceramic pressing process in the step (5), the pressure of pressurizing and heating is 100-250 MPa, the temperature is 100-180 ℃, and the heat preservation time is 1-12 h.
The invention well combines the characteristics of novel low-temperature sintering technology (cold sintering) and low melting point of metal halide. The main function of the liquid phase solvent during sintering is to dissolve the powder surface, then the dissolved powder is reoriented to precipitate and crystallize under the action of seed crystal induction, resulting in single orientation of the ceramic, thus realizing the increase of transparency and large-area preparation. The high-permeability ceramic reduces light scattering and loss of radiant fluorescence in the ceramic, and realizes high-efficiency scintillation performance and high-resolution scintillation imaging.
The invention also provides an X-ray imaging device. The apparatus includes an X-ray tube, a scintillator, a Charge Coupled Device (CCD); the scintillator is the high-permeability metal halide ceramic obtained by the preparation method.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) The invention utilizes low-dimensional metal halide to realize high-efficiency photoluminescence and scintillation performance and better temperature stability, and prepares the synthetic solid solution by a simple solvent-antisolvent method;
(2) The large-area high-transmittance metal halide scintillating ceramic material prepared by the invention has light yield superior to that of a commercial scintillator and excellent stability;
(3) The large-area metal halide ceramic prepared by the invention can realize a wafer with the diameter of about 5cm by a simple process, which is far greater than the metal halide single crystal prepared by the solution method at present, and is beneficial to realizing large-area scintillation imaging;
(4) The large-area metal halide ceramic prepared by the invention has good light transmittance, and the transparent ceramic material can reduce light scattering in the imaging process, thereby being beneficial to realizing high-resolution scintillation imaging;
(5) The preparation process of the large-area high-permeability metal halide scintillating ceramic is easy to operate, good in repeatability, low in equipment cost and pollution-free, can generate huge social benefit and economic benefit, and is suitable for general popularization and use.
Drawings
FIG. 1 shows the results of examples 1-4 (C 24 H 20 P) 2 MnBr 4 Powder XRD diffractogram;
FIG. 2 shows the results of the preparation (C) of examples 1 to 4 24 H 20 P) 2 MnBr 4 Excitation and emission spectra of the crystal;
FIG. 3 shows the results of the preparation (C) of examples 1 to 4 24 H 20 P) 2 MnBr 4 Crystal and commercial CsI (Tl) and LuAG: ce crystal emission spectra under X-ray excitation and (C) 24 H 20 P) 2 MnBr 4 Fitting the detection limit of (2);
FIG. 4 is a sample of the product of example 9 (C 24 H 20 P) 2 MnBr 4 Schematic of the method of the ceramic;
FIG. 5 is a schematic view of the microstructure of the metal halide ceramics in different sintering modes;
FIG. 6 is a sample of the sample (C) prepared in example 9 24 H 20 P) 2 MnBr 4 Ceramics are schematically imaged in X-ray.
Detailed Description
The present invention is further illustrated in the accompanying drawings and detailed description which are to be understood as being merely illustrative of the invention and not limiting of its scope, and various modifications to the invention, which are equivalent to those skilled in the art, will fall within the scope of the invention as defined in the appended claims after reading the invention.
Example 1:
according to tetraphenylphosphine bromide and MnBr 2 Weighing 419mg and 214mg of samples according to the molar ratio of 1:1, pouring the samples into a beaker or a reaction kettle, adding 2mL of N, N-Dimethylacetamide (DMF) solution into the container, and heating and stirring the mixture at 120 ℃ for 2 hours to obtain a clear and uniform solution; placing the obtained solution in an atmosphere of diethyl ether serving as an antisolvent, and standing for 12h; after the reaction is finished, separating out precipitated crystals or powder by suction filtration; finally, vacuum drying the above crystals or powder at 80deg.C for 12 hr to obtain the final scintillator material (C 24 H 20 P) 2 MnBr 4 。
Example 2:
according to tetraphenylphosphine bromide and MnBr 2 The method comprises the steps of weighing 629mg and 214mg samples respectively according to a molar ratio of 1.5:1, pouring the samples into a beaker or a reaction kettle, adding 3mL of N, N-Dimethylacetamide (DMF) solution into the container, and heating and stirring the solution at 120 ℃ for 2 hours to obtain a clear and uniform solution; placing the obtained solution in an atmosphere of diethyl ether serving as an antisolvent, and standing for 18h; after the reaction is finished, separating out precipitated crystals or powder by suction filtration; finally, the above crystals or powder were vacuum-dried at 80℃for 16 hours to obtain the final scintillator material (C 24 H 20 P) 2 MnBr 4 。
Example 3:
according to tetraphenylphosphine bromide and MnBr 2 Samples of 838mg and 214mg were weighed at a molar ratio of 2:1, poured into a beaker or reaction kettle, and 3mL of N, N-dimethylacetamide was added to the vessel(DMF) solution, heating and stirring at 120 ℃ for 2 hours to obtain clear and uniform solution; placing the obtained solution in an atmosphere of diethyl ether serving as an antisolvent, and standing for 20h; after the reaction is finished, separating out precipitated crystals or powder by suction filtration; finally, the above crystals or powder were vacuum-dried at 80℃for 20 hours to obtain the final scintillator material (C 24 H 20 P) 2 MnBr 4 。
Example 4:
according to tetraphenylphosphine bromide and MnBr 2 Weighing 1257mg and 214mg of samples according to a molar ratio of 3:1, pouring the samples into a beaker or a reaction kettle, adding 4mL of N, N-Dimethylacetamide (DMF) solution into the container, and heating and stirring the solution at 120 ℃ for 6 hours to obtain a clear and uniform solution; placing the obtained solution in an atmosphere of diethyl ether serving as an antisolvent, and standing for 24 hours; after the reaction is finished, separating out precipitated crystals or powder by suction filtration; finally, the above crystals or powder were vacuum-dried at 80℃for 24 hours to obtain the final scintillator material (C 24 H 20 P) 2 MnBr 4 。
Example 5:
according to benzyltrimethylammonium bromide and MnBr 2 Respectively weighing 230mg and 214mg of samples according to the molar ratio of 1:1, pouring the samples into a beaker or a reaction kettle, adding 2mL of N, N-Dimethylacetamide (DMF) solution into the container, and heating and stirring the mixture at 100 ℃ for 2 hours to obtain a clear and uniform solution; placing the obtained solution in an atmosphere of diethyl ether serving as an antisolvent, and standing for 12h; after the reaction is finished, separating out precipitated crystals or powder by suction filtration; finally, vacuum drying the above crystals or powder at 80deg.C for 12 hr to obtain the final scintillator material (C 10 H 16 N) 2 MnBr 4 。
Example 6:
according to benzyltrimethylammonium bromide and MnBr 2 The molar ratio is 1.5:1, respectively weighing 345mg and 214mg of samples, pouring the samples into a beaker or a reaction kettle, adding 3mL of N, N-Dimethylacetamide (DMF) solution into the container, heating and stirring the mixture for 3 hours at 110 ℃ to obtain a clear and uniform solution; placing the obtained solution in an atmosphere of diethyl ether serving as an antisolvent, and standing for 12h; after the reaction is finished, the mixture is led toFiltering and separating out precipitated crystals or powder; finally, the above crystals or powder were vacuum-dried at 80℃for 16 hours to obtain the final scintillator material (C 10 H 16 N) 2 MnBr 4 。
Example 7:
according to benzyltrimethylammonium bromide and MnBr 2 Respectively weighing 460mg and 214mg of samples according to the molar ratio of 2:1, pouring the samples into a beaker or a reaction kettle, adding 3mL of N, N-Dimethylacetamide (DMF) solution into the container, and heating and stirring the mixture at 120 ℃ for 4 hours to obtain a clear and uniform solution; placing the obtained solution in an atmosphere of diethyl ether serving as an antisolvent, and standing for 12h; after the reaction is finished, separating out precipitated crystals or powder by suction filtration; finally, the above crystals or powder were vacuum-dried at 80℃for 20 hours to obtain the final scintillator material (C 10 H 16 N) 2 MnBr 4 。
Example 8:
according to benzyltrimethylammonium bromide and MnBr 2 Respectively weighing 690mg and 214mg of samples according to the molar ratio of 3:1, pouring the samples into a beaker or a reaction kettle, adding 4mL of N, N-Dimethylacetamide (DMF) solution into the container, and heating and stirring the mixture at 130 ℃ for 6 hours to obtain a clear and uniform solution; placing the obtained solution in an atmosphere of diethyl ether serving as an antisolvent, and standing for 12h; after the reaction is finished, separating out precipitated crystals or powder by suction filtration; finally, the above crystals or powder were vacuum-dried at 80℃for 24 hours to obtain the final scintillator material (C 10 H 16 N) 2 MnBr 4 。
Example 9
1g of the crystals and powder prepared in examples 1 to 4 were taken, and an N, N-Dimethylacetamide (DMF) solution of 20% by mass was added to mix well. Then adding the mixture into a stainless steel die, pressurizing to 200MPa under the action of a tablet press, and simultaneously raising the temperature to 150 ℃ and maintaining for 4 hours under the action of Wen Baoya; finally, when the reactants are naturally cooled to room temperature, the final scintillating ceramic (C) 24 H 20 P) 2 MnBr 4 . The obtained ceramic has a large area with a diameter of 3cm, and the large area is enough for scintillation imaging. And has high light transmittance (light transmittance higher than 60%) resolution.
Example 10
1g of the crystals and powder prepared in examples 5 to 8 were taken, and 15% by mass of N, N-Dimethylacetamide (DMF) solution was added and mixed well. Then adding the mixture into a stainless steel die, pressurizing to 250MPa under the action of a tablet press, and simultaneously raising the temperature to 170 ℃ and maintaining for 8 hours under the action of Wen Baoya; finally, when the reactants are naturally cooled to room temperature, the final scintillating ceramic (C) 10 H 16 N) 2 MnBr 4 . The resulting ceramic has a large area, up to 5cm in diameter, which is large enough for applications in scintigraphy. And has high light transmittance (light transmittance higher than 70%) resolution.
For the (C) prepared in examples 1-4 24 H 20 P) 2 MnBr 4 Crystals and powders, performing excitation and emission spectra, auxiliary emission spectra, and scintillation imaging assays.
FIG. 1 shows the results of examples 1-4 (C 24 H 20 P) 2 MnBr 4 Powder XRD diffractogram. Powder samples prepared with (C) 24 H 20 P) 2 MnBr 4 The results of single crystal diffraction were consistent, indicating that the purity of the phases was not heterogeneous. As can be seen from FIG. 1, the catalyst can be successfully prepared according to different raw material molar ratios (C 24 H 20 P) 2 MnBr 4 。
FIG. 2 shows the results of examples 1-4 (C 24 H 20 P) 2 MnBr 4 Excitation and emission spectra of the crystals. As can be seen from FIG. 2, (C) 24 H 20 P) 2 MnBr 4 The crystal has an optimal excitation peak at 365nm, an emission peak at 520nm and a half-width of 45nm. The luminescent mechanism of the material is typically four-coordinated Mn through a typical excitation spectrum and a narrow-band green light emission spectrum 2+ And (3) luminescence of ions.
FIG. 3 shows the results of examples 1-4 (C 24 H 20 P) 2 MnBr 4 Crystal and commercial CsI (Tl) and LuAG: ce crystal emission spectra under X-ray excitation and(C 24 H 20 P) 2 MnBr 4 is fit to the detection limit of (2). Wherein a in FIG. 3 is a graph showing the contrast of the fluorescence intensities of the three substances, and the light yield of the metal halide can be obtained by converting the fluorescence intensities of the radiation, which proves (C 24 H 20 P) 2 MnBr 4 The crystal has more efficient scintillation performance: the light yield of the material is calculated to reach 78000photons/MeV, which is far greater than that of the scintillation crystals CsI-Tl (58000 photons/MeV) and LuAG: ce (25000 photons/MeV) which are commercially used at present. And is represented by b (C in fig. 3 24 H 20 P) 2 MnBr 4 The detection limit fitting result of the material shows that the material realizes the ultra-low detection limit of 8.8nGy/s.
FIG. 4 is a sample of the product of example 9 (C 24 H 20 P) 2 MnBr 4 Schematic of the process for ceramics. The synthetic route of the metal halide ceramic is as follows: prepared (C) 24 H 20 P) 2 MnBr 4 Adding N, N-Dimethylacetamide (DMF) solution into the powder, and mixing to obtain (C) 24 H 20 P) 2 MnBr 4 Surface dissolution of the powder, reforming of the powder containing tetraphenylphosphine bromide and MnBr 2 Adding seed crystal, adding the seed crystal into a stainless steel die, pressurizing to 200MPa under the action of a tablet press, simultaneously raising the temperature to 150 ℃ for cold sintering, maintaining for 4 hours under the action of Wen Baoya, and finally polishing to obtain the high-permeability scintillation ceramic wafer with the diameter of 3cm when the reactant is naturally cooled to room temperature. This is far greater than the metal halide single crystals (typically less than 1 cm) currently prepared by solution methods, which is advantageous for achieving large area scintillation imaging. The ceramic has good light transmittance (the light transmittance is higher than 60%), and the transparent ceramic material can reduce light scattering in the imaging process, thereby being beneficial to realizing high-resolution scintillation imaging. The schematic diagram shows that the main function of the liquid phase solvent in the sintering process is to dissolve the powder surface, then the seed crystal is added to enable crystal grains to be deposited and rearranged uniformly according to the orientation of the seed crystal, and the preparation method can be used for effectively preparing high-permeability bulk ceramic and has excellent temperature stability.
FIG. 5 is goldA schematic of the microstructure of the various sintering modes of the halide ceramics is provided for illustrating the (C) produced in this example 9 24 H 20 P) 2 MnBr 4 The principle of high permeability of ceramics. A in fig. 5 is a conventional solid phase sintering method, and a ceramic material prepared by the method has a large number of pores and grain boundaries due to the volatile nature of metal halides and disordered grains, and the existence of the grain boundaries and the pores causes scattering of light and reduces transparency. B in fig. 5 is a conventional cold sintering method, although the low temperature liquid phase sintering characteristic of the method reduces sintering temperature, reduces pores in the material, and realizes a compact structure, disordered grains and grain boundaries still cause light scattering, and reduces transparency. C in fig. 5 is an experimental scheme of the present invention, in which light scattering factors (grain boundaries and pores) are reduced and high transparency is achieved by virtue of low temperature liquid phase sintering and seed crystal induced grain rearrangement. By comparing the grain orientation distribution structure and the light scattering result of the metal halide ceramics prepared by different preparation schemes, the preparation method of the invention realizes the microstructure with high orientation and low air holes, and the result is the main reason for realizing high permeability of the metal halide ceramics.
FIG. 6 is a sample of the product of example 9 (C 24 H 20 P) 2 MnBr 4 Ceramics are schematically imaged in X-ray. From fig. 6, by self-made imaging system: the X-ray source, the sample to be measured (e.g. ballpoint pen of FIG. 6), the high-transparency scintillating ceramic and the high-resolution CCD camera are sequentially arranged in a straight line, the outline of the ballpoint pen and the metal spring inside the ballpoint pen can be clearly seen, indicating that (C) 24 H 20 P) 2 MnBr 4 The ceramic material has large area, high permeability and scintillation property and can be well applied to scintillation imaging.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention are included in the protection scope of the present invention.

Claims (6)

1. The preparation method of the large-area high-permeability metal halide scintillating ceramic is characterized by comprising the following steps of:
(1) Dissolving halide, oxide Or carbonate of metal M and organic ligand Or in solvent, heating and stirring to dissolve completely;
(2) Standing the solution dissolved in the step (1) under the action of an antisolvent, and separating out crystals or powder;
(3) Separating out the crystals or powder separated out in the step (2) through suction filtration, and then carrying out vacuum drying to obtain seed crystals or powder;
(4) Adding a solution into the powder obtained in the step (3), and fully and uniformly mixing to obtain powder;
(5) Adding seed crystals obtained in the step (3) into the powder obtained in the step (4), then adding the seed crystals into a die, pressing the seed crystals into ceramic sheets under the action of pressurizing and heating, and preserving heat to obtain the high-permeability metal halide ceramic;
the solvent in the step (1) is one or more of N, N-dimethylformamide and dimethyl sulfoxide, and the molar volume ratio of the halide, the oxide or the carbonate of the metal M to the solvent is 1:2-1:5 mmol/mL;
the solution in the step (4) is one or more of N, N-dimethylformamide, dimethyl sulfoxide and high-purity water;
the pressure of the pressurizing and heating in the step (5) is 100-250 MPa, and the temperature of the pressurizing and heating is 100-180 ℃; the heat preservation time in the step (5) is 1-12 h;
the chemical composition formula of the metal halide ceramic is Or u M v X w Wherein Or is one Or more of tetraphenyl phosphine bromide, triphenylphosphine, benzyl trimethyl halide, benzyl triethyl halide, benzyl tributyl halide, and organic ligand of 1-methyl-1-ethyl pyrrolidine bromide; m is one or more of Mn, zn, pb, sb and Bi; x is one or more of Cl, br and I; u, v and w respectively represent the molar contents of Or, M and X, wherein u is more than 1 and less than 3, v is more than Or equal to 1 and less than 3, and w is more than 3 and less than 5.
2. The method for producing a large area high transmittance metal halide scintillating ceramic according to claim 1, wherein the molar ratio of the halide, oxide Or carbonate of the metal M to the organic ligand Or in the step (1) is 1 (1-4).
3. The method for preparing a large-area high-permeability metal halide scintillating ceramic according to claim 1, wherein the temperature of heating and stirring in the step (1) is 60-150 ℃, and the time of heating and stirring is 0.5-6 h.
4. The method for preparing a large-area high-permeability metal halide scintillating ceramic according to claim 1, wherein the antisolvent in the step (2) is one or more of acetone, ethanol and diethyl ether; and (3) standing for 12-24 hours.
5. The method for preparing a large-area high-permeability metal halide scintillating ceramic according to claim 1, wherein the temperature of the vacuum drying in the step (3) is 40-80 ℃, and the time of the vacuum drying is 6-24 h.
6. A large area high permeability metal halide scintillating ceramic made by the method of any one of claims 1-5.
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