Novel manganese-based multi-metal halide perovskite doped scintillation microcrystal and preparation method thereof

Abstract

The invention provides a novel manganese-based multi-element metal halide perovskite doped scintillation microcrystal and a preparation method thereof, the chemical formula of the novel manganese-based multi-element metal halide perovskite doped scintillation microcrystal is Cs3MnX5: A < n + >, A is one or more of Ti, Cr, Ni, Cu, Zn, Y, Zr, Ag, In, Sn, Sb and Bi, the doping amount of A is y, y is greater than or equal to 0 and less than or equal to 0.9, n is the valence state of A, n is greater than or equal to 1 and less than or equal to 5, and X is one or more halide ions of Cl <->, Br <-> and I <->. The preparation method comprises the following steps: adding CsX, MnX2, AXn and HX into an organic solvent, heating and stirring to obtain a precursor solution; injecting an anti-solvent into the precursor solution, carrying out suction filtration, and centrifuging to obtain scintillation microcrystals; and carrying out vacuum drying on the scintillation microcrystals, taking out the scintillation microcrystals after the scintillation microcrystals are completely dried, and carrying out ball milling to finally obtain scintillation microcrystal powder with uniform particle size distribution. The microcrystalline prepared by the invention has excellent environmental stability, and after being washed and purified by solvents such as n-butyl alcohol, isopropanol, n-hexane and the like, the scintillator microcrystalline is high in stability and free of phenomena such as halogen ion precipitation and oxidation.

Description

Technical Field

[0001] The present invention relates to the technical field of scintillator material preparation, and in particular to a novel manganese-based multinary metal halide perovskite-doped scintillator microcrystal and a preparation method thereof. Background Art

[0002] As the core component of radiation detectors, scintillator materials are responsible for converting high-energy radiation (such as X-rays, gamma rays, etc.) into visible light signals. They have been widely used in medical radiography, radiation exposure monitoring, industrial non-destructive testing, and travel safety inspections. Due to the need to have sufficient absorption capacity for high-energy radiation, scintillators usually have characteristics such as a large atomic number and a dense material structure. In addition, the light yield after the material absorbs radiation, the material's response speed to radiation, and the lifespan of the visible light emitted after excitation are also key indicators for measuring the quality of a scintillator material.

[0003] According to the constituent elements, common scintillator materials are mainly divided into organic scintillators and inorganic scintillators. Among them, organic scintillators have the advantages of simple preparation and adjustable light output wavelength; however, because their structure contains long-chain or planar organic structures, their material density is often low, resulting in unsatisfactory scintillation efficiency; in addition, the sites where organic structures exist make such materials susceptible to environmental factors, thereby reducing the service life of the materials. Relatively speaking, inorganic scintillators have a denser structure and better X-ray cutoff absorption capacity, thus having higher scintillation efficiency and more stable environmental tolerance; however, the preparation conditions of such materials are extremely harsh, generally requiring long-term high temperature and vacuum conditions, resulting in high costs; and the tunable performance of the obtained materials is poor, resulting in a relatively single light output wavelength, which is difficult to meet the needs of various application scenarios. The most widely commercialized cesium iodide doped with thallium (CsI:Tl) is a typical inorganic scintillator material with a high light yield, but it still has unavoidable defects such as high cost, highly toxic elements, and single emission.

[0004] In recent years, multi-metal halide perovskite materials have attracted widespread attention due to their advantages such as large X-ray attenuation coefficient, high bulk resistivity, and suitable band gap. The composition and structure of perovskite materials are tunable, and their luminescent color and decay time can be adjusted by adjusting the structural composition to match a variety of application scenarios. Combined with its all-inorganic and highly stable characteristics, halide perovskite materials combine the advantages of easy preparation and adjustability of common organic scintillators with high absorption and high conversion of inorganic scintillators, and are expected to become new scintillator materials with great commercial potential. However, common lead-based perovskites such as CsPbBr3 contain heavy metal lead, which is toxic to both organisms and the environment, limiting its further development.

[0005] Therefore, it is necessary to develop a heavy metal-free, easy-to-prepare, and tunable halide perovskite scintillator material. Summary of the invention

[0006] In order to overcome the deficiencies in the prior art, the present invention provides a novel manganese-based multinary metal halide perovskite doped scintillating microcrystal and a preparation method thereof.

[0007] To achieve the above object, the present invention provides a novel manganese-based multinary metal halide perovskite doped scintillating microcrystal, the chemical formula of which is Cs3MnX5:A n+ , where A is one or more of Ti, Cr, Ni, Cu, Zn, Y, Zr, Ag, In, Sn, Sb, and Bi, the doping amount of A is y, 0≤y≤0.9, n is the valence state of A, 1≤n≤4, and X is Cl - Br - ,I - One or more halogen ions.

[0008] Preferably, the novel manganese-based multinary metal halide perovskite doped scintillating microcrystals include Cs3MnI5, Cs3MnBr5, Cs3MnCl2I3, Cs3MnI5:0.3%Cu + 、Cs3MnI5:0.3%Ag + 、Cs3MnI5:0.3%Sn 2+ 、Cs3MnI5:0.3%Sb 3+ 、Cs3MnI5:0.1%Zr 4+ One or more of the .

[0009] The present invention also provides a method for preparing the novel manganese-based multinary metal halide perovskite-doped scintillating microcrystals, which comprises:

[0010] The main raw materials CsX, MnX2, dopant raw materials and HX are added to an organic solvent, heated and stirred until transparent and clear to obtain a precursor solution; the dopant raw materials include halide salts of the corresponding metals AX n 、Nitrate A(NO3) n 、Oxide AO n or acetate A(OAc) n One or more of the following;

[0011] Injecting the antisolvent into the precursor solution until no more crystals precipitate;

[0012] The microcrystals obtained were filtered and centrifuged to obtain scintillation microcrystals.

[0013] Preferably, the organic solvent includes one or more of dimethylformamide, dimethyl sulfoxide, dimethylacetamide, acetone, butanone, acetonitrile, methylpyrrolidine or butyrolactone; the anti-solvent includes one or more of alcohol solvents, ester solvents, ether solvents and alkane solvents.

[0014] Preferably, the alcohol solvent includes one or more of methanol, ethanol, isopropanol, and n-butanol; the ether solvent includes one or more of dimethyl ether, ethyl ether, and dipropyl ether; the alkane solvent includes one or more of n-hexane and cyclohexane; and the ester solvent includes one or more of methyl formate, isobutyl formate, methyl acetate, and ethyl acetate.

[0015] Preferably, the heating and stirring temperature is 50-150° C., the stirring and dissolving time is 2-8 h, and the stirring and dissolving rate is 200-600 rpm.

[0016] Preferably, the centrifugal speed is 6000-12000 rpm and the time is 1-3 min.

[0017] Preferably, the vacuum drying temperature is 60-100° C. and the time is 6-24 h.

[0018] Preferably, the scintillation microcrystals are vacuum dried, taken out and ball-milled after being completely dried, and finally scintillation microcrystal powder with uniform particle size distribution is obtained.

[0019] Preferably, the ball milling speed is 300-500 rpm, and the ball milling time is 15-30 min.

[0020] The beneficial effects of the present invention are as follows:

[0021] 2. The present invention uses manganese halide as the main material, and the main elements are non-toxic and harmless. Compared with traditional thallium-doped halide scintillators and common lead-based halide perovskites, it is more friendly to organisms and the environment;

[0022] 3. The present invention can use anti-solvent driven Cs3MnX5:A n+ The room temperature precipitation method of scintillation microcrystals is simple to operate, does not require long-term high temperature, high pressure, vacuum and other harsh conditions, has high yield, and is easy to mass produce;

[0023] 4. The present invention can adjust the luminescence peak of the scintillating microcrystals by controlling the type and ratio of doped ions, and can show bright blue, green, yellow and other luminescence to adapt to different application scenarios;

[0024] 5. The microcrystals prepared by the present invention have excellent environmental stability. After being washed and purified by solvents such as n-butanol, isopropanol, and n-hexane, the scintillator microcrystals have strong stability and are free of halogen ion precipitation and oxidation.

[0025] Compared with the traditional solid-phase doping which usually requires higher reaction temperature and pressure, the present invention can obtain doped microcrystals of multiple elements on the same main body at low temperature and normal pressure, and change the luminescence peak position and intrinsic color of the material. n The B-position element in the structure (either equivalent or asymmetrical), the essence of the reaction is the process of dopant replacing the main body, thereby forming a new luminescence center or distorting the original lattice, thus showing different ray response luminescence. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 Cs3MnX5:A was obtained by room temperature antisolvent method n+ Schematic diagram of the process of manganese-based halide perovskite scintillator;

[0027] Figure 2 is Cs3MnX5:A prepared in Example n+ Microcrystal images of three doped manganese-based halides and Cs3MnI5 undoped perovskite scintillators and luminescence images under ultraviolet light excitation;

[0028] Figure 3 is the XRD pattern of Cs3MnI5 microcrystals prepared in Example;

[0029] Table 1 shows the yield, luminescence peak position and normalized intensity of each example. DETAILED DESCRIPTION

[0030] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present application will be further described below in conjunction with specific embodiments.

[0031] Example 1

[0032] The preparation method of the undoped manganese-based halide perovskite scintillator microcrystalline powder with the chemical formula Cs3MnI5 comprises the following steps:

[0033] A mixed solution of 15 mmol CsI, 5 mmol MnI2, 50 mL DMF (dimethylformamide), and 50 μL HI was stirred and heated at 100 °C for 6 h until the solution was transparent and clear, then the heating was turned off and stirring was continued to room temperature; while the precursor solution was kept stirring, ethyl acetate (a total of 100 mL) was quickly injected into the solution until no more precipitate was precipitated.

[0034] The obtained mixture was transferred to a Buchner funnel for suction filtration, washed with ethyl acetate during the process, and then the precipitate was transferred to a 50mL centrifuge tube. An appropriate amount of n-butanol was added until the precipitate was just covered. The mixture was vibrated on a vibrator until it was evenly dispersed. Then centrifugation was started at a rate of 10,000 rpm for 90 seconds. After the centrifugation was completed, the supernatant was discarded, the precipitate was retained, and the centrifugation was repeated 3 times.

[0035] Finally, the sample was sealed with a sealing film and placed in a vacuum drying oven to remove the residual solvent at a drying temperature of 60°C for 24 hours. After the solvent evaporated completely, the lumpy precipitate was taken out and placed in a 50mL ball mill jar, the ball mill speed was set to 400rpm, and the precipitate was taken out after grinding for 30 minutes to obtain a uniformly distributed undoped manganese-based halide perovskite Cs3MnI5 scintillating microcrystalline powder.

[0036] Example 2

[0037] The preparation method of the undoped manganese-based halide perovskite scintillator microcrystalline powder with the chemical formula Cs3MnBr5 comprises the following steps:

[0038] A mixed solution of 15 mmol CsBr, 5 mmol MnBr2, 50 mL DMF (dimethylformamide), and 50 μL HBr was stirred and heated at 100 °C for 6 h until the solution was transparent and clear, then the heating was turned off and continued to stir until the solution reached room temperature. While the precursor solution was stirred, ethyl acetate (a total of 100 mL) was quickly injected into the solution until no more precipitation occurred.

[0039] The obtained mixture was transferred to a Buchner funnel for suction filtration, and washed with ethyl acetate during the process. The precipitate was then transferred to a 50 mL centrifuge tube, and an appropriate amount of n-butanol was added until the precipitate was just covered. The mixture was vibrated on a vibrator until it was evenly dispersed, and then centrifuged at a rate of 10,000 rpm for 90 seconds. After the centrifugation was completed, the supernatant was discarded, the precipitate was retained, and the centrifugation was repeated 3 times.

[0040] Finally, the sample was sealed with a sealing film and placed in a vacuum drying oven to remove the residual solvent at a drying temperature of 60°C for 24 hours. After the solvent evaporated completely, the lumpy precipitate was taken out and placed in a 50mL ball mill, the ball mill speed was set to 400rpm, and the precipitate was taken out after grinding for 30 minutes to obtain a uniformly distributed undoped manganese-based halide perovskite Cs3MnBr5 scintillating microcrystalline powder.

[0041] Example 3

[0042] The preparation method of the undoped manganese-based halide perovskite scintillator microcrystalline powder with the chemical formula of Cs3MnCl2I3 is as follows: a mixed solution of 15mmol CsI, 5mmol MnCl2, 50mL DMF (dimethylformamide), and 50μL HI is stirred and heated at 100°C for 6h until the solution is transparent and clear, then the heating is turned off and the stirring is continued to room temperature. While the precursor solution is kept stirred, ethyl acetate (a total of 100mL) is quickly injected into the solution until no more precipitation is precipitated.

[0043] The obtained mixture was transferred to a Buchner funnel for suction filtration, and washed with ethyl acetate during the process. The precipitate was then transferred to a 50 mL centrifuge tube, and an appropriate amount of n-butanol was added until the precipitate was just covered. The mixture was vibrated on a vibrator until it was evenly dispersed, and then centrifuged at a rate of 10,000 rpm for 90 seconds. After the centrifugation was completed, the supernatant was discarded, the precipitate was retained, and the centrifugation was repeated 3 times.

[0044] Finally, the sample was sealed with a sealing film and placed in a vacuum drying oven to remove the residual solvent at a drying temperature of 60°C for 24 hours. After the solvent evaporated completely, the lumpy precipitate was taken out and placed in a 50mL ball mill jar, the ball mill speed was set to 400rpm, and the precipitate was taken out after grinding for 30 minutes to obtain a uniformly distributed undoped manganese-based halide perovskite Cs3MnCl2I3 scintillating microcrystalline powder.

[0045] Example 4

[0046] The chemical formula is Cs3MnI5:0.3%Cu + The method for preparing copper-doped manganese-based halide perovskite scintillator microcrystalline powder comprises the following steps:

[0047] A mixed solution of 15 mmol CsI, 4.985 mmol MnI2, 0.03 mmol CuI, 50 mL DMF (dimethylformamide), and 50 μL HI was stirred and heated at 100 ° C for 6 h until the solution was transparent and clear, then the heating was turned off and continued to stir until room temperature. While the precursor solution was stirred, ethyl acetate (a total of 100 mL) was quickly injected into the solution until no more precipitation occurred.

[0048] The obtained mixture was transferred to a Buchner funnel for suction filtration, and washed with ethyl acetate during the process. The precipitate was then transferred to a 50 mL centrifuge tube, and an appropriate amount of n-butanol was added until the precipitate was just covered. The mixture was vibrated on a vibrator until it was evenly dispersed, and then centrifuged at a rate of 10,000 rpm for 90 seconds. After the centrifugation was completed, the supernatant was discarded, the precipitate was retained, and the centrifugation was repeated 3 times.

[0049] Finally, the sample was sealed with a sealing film and placed in a vacuum drying oven to remove the residual solvent. The drying temperature was 60°C and the drying time was 24 hours. After the solvent evaporated completely, the lumpy precipitate was taken out and placed in a 50mL ball mill. The ball mill speed was set to 400rpm. After grinding for 30 minutes, the sample was taken out to obtain a copper-doped manganese-based halide perovskite Cs3MnI5:0.3%Cu with uniform particle distribution. + Sparkling microcrystalline powder.

[0050] Example 5

[0051] Since silver ion halides and chalcogenides are difficult to dissolve or obtain, nitrate is used to prepare the chemical formula Cs3MnI5:0.3%Ag + The copper-doped manganese-based halide perovskite scintillator microcrystalline powder is prepared by the following steps:

[0052] A mixed solution of 15 mmol CsI, 4.985 mmol MnI2, 0.03 mmol AgNO3, 50 mL DMF (dimethylformamide), and 50 μL HI was stirred and heated at 100 °C for 6 h until the solution was transparent and clear, then the heating was turned off and continued to stir until room temperature. While the precursor solution was stirred, ethyl acetate (a total of 100 mL) was quickly injected into the solution until no more precipitation occurred.

[0053] The obtained mixture was transferred to a Buchner funnel for suction filtration, and washed with ethyl acetate during the process. The precipitate was then transferred to a 50 mL centrifuge tube, and an appropriate amount of n-butanol was added until the precipitate was just covered. The mixture was vibrated on a vibrator until it was evenly dispersed, and then centrifuged at a rate of 10,000 rpm for 90 seconds. After the centrifugation was completed, the supernatant was discarded, the precipitate was retained, and the centrifugation was repeated 3 times.

[0054] Finally, the sample was sealed with a sealing film and placed in a vacuum drying oven to remove the residual solvent. The drying temperature was 60°C and the drying time was 24 hours. After the solvent was completely evaporated, the lumpy precipitate was taken out and placed in a 50mL ball mill. The ball milling speed was set to 400rpm. After grinding for 30 minutes, the sample was taken out to obtain a copper-doped manganese-based halide perovskite Cs3MnI5:0.3%Ag with uniform particle distribution. + Sparkling microcrystalline powder.

[0055] Example 6

[0056] Acetate doping was used to prepare the chemical formula Cs3MnI5:0.3%Sn 2+ The copper-doped manganese-based halide perovskite scintillator microcrystalline powder is prepared by the following steps:

[0057] A mixed solution of 15 mmol CsI, 4.985 mmol MnI2, 0.015 mmol Sn(OAc)2, 50 mL DMF (dimethylformamide), and 50 μL HI was stirred and heated at 100 °C for 6 h until the solution was transparent and clear, then the heating was turned off and continued to stir until room temperature. While the precursor solution was stirred, ethyl acetate (a total of 100 mL) was quickly injected into the solution until no more precipitation occurred.

[0058] Sn(OAc)2+2H + →Sn 2+ +2HOAc

[0059] The obtained mixture was transferred to a Buchner funnel for suction filtration, and washed with ethyl acetate during the process. The precipitate was then transferred to a 50 mL centrifuge tube, and an appropriate amount of n-butanol was added until the precipitate was just covered. The mixture was vibrated on a vibrator until it was evenly dispersed, and then centrifuged at a rate of 10,000 rpm for 90 seconds. After the centrifugation was completed, the supernatant was discarded, the precipitate was retained, and the centrifugation was repeated 3 times.

[0060] Finally, the sample was sealed with a sealing film and placed in a vacuum drying oven to remove the residual solvent. The drying temperature was 60°C and the drying time was 24 hours. After the solvent evaporated completely, the lumpy precipitate was taken out and placed in a 50mL ball mill. The ball mill speed was set to 400rpm. After grinding for 30 minutes, the sample was taken out to obtain a copper-doped manganese-based halide perovskite Cs3MnI5:0.3%Sn with uniform particle distribution. 2+ Sparkling microcrystalline powder.

[0061] Example 7

[0062] The doping source with poor solubility is dissolved in a slightly excessive amount of the corresponding acid in advance to prepare the corresponding metal ions, and then mixed with the remaining raw materials to prepare a chemical formula of Cs3MnI5:0.3%Sb 3+ The specific steps are as follows:

[0063] 0.002mmol Sb2O3 was dissolved in 100μL HI and stirred until no precipitation occurred. Then the Sb solution, 15mmol CsI and 4.985mmol MnI2 were added to 50mL DMF (dimethylformamide), and stirred and heated at 100℃ for 6h until the solution was transparent and clear. Then the heating was turned off and the stirring continued to room temperature. While the precursor solution was stirred, ethyl acetate (a total of 100mL) was quickly injected into the solution until no more precipitation occurred.

[0064] Sb2O3+6H + →2Sb 3+ +3H2O

[0065] The obtained mixture was transferred to a Buchner funnel for suction filtration, and washed with ethyl acetate during the process. The precipitate was then transferred to a 50 mL centrifuge tube, and an appropriate amount of n-butanol was added until the precipitate was just covered. The mixture was vibrated on a vibrator until it was evenly dispersed, and then centrifuged at a rate of 10,000 rpm for 90 seconds. After the centrifugation was completed, the supernatant was discarded, the precipitate was retained, and the centrifugation was repeated 3 times.

[0066] Finally, the sample was sealed with a sealing film and placed in a vacuum drying oven to remove the residual solvent. The drying temperature was 60°C and the drying time was 24 hours. After the solvent evaporated completely, the lumpy precipitate was taken out and placed in a 50mL ball mill. The ball milling speed was set to 400rpm. After grinding for 30 minutes, the sample was taken out to obtain a copper-doped manganese-based halide perovskite Cs3MnI5:0.3%Sb with uniform particle distribution. 3+ Sparkling microcrystalline powder.

[0067] Example 8

[0068] The chemical formula is Cs3MnI5:0.1%Zr 4+ The method for preparing copper-doped manganese-based halide perovskite scintillator microcrystalline powder comprises the following steps:

[0069] A mixed solution of 15 mmol CsI, 4.995 mmol MnI2, 0.0025 mmol ZrCl4, 50 mL DMF (dimethylformamide), and 50 μL HI was stirred and heated at 100 °C for 6 h until the solution was transparent and clear, then the heating was turned off and continued to stir until room temperature. While the precursor solution was stirred, ethyl acetate (a total of 100 mL) was quickly injected into the solution until no more precipitation occurred.

[0070] The obtained mixture was transferred to a Buchner funnel for suction filtration, and washed with ethyl acetate during the process. The precipitate was then transferred to a 50 mL centrifuge tube, and an appropriate amount of n-butanol was added until the precipitate was just covered. The mixture was vibrated on a vibrator until it was evenly dispersed, and then centrifuged at a rate of 10,000 rpm for 90 seconds. After the centrifugation was completed, the supernatant was discarded, the precipitate was retained, and the centrifugation was repeated 3 times.

[0071] Finally, the sample was sealed with a sealing film and placed in a vacuum drying oven to remove the residual solvent. The drying temperature was 60°C and the drying time was 24 hours. After the solvent was completely evaporated, the lumpy precipitate was taken out and placed in a 50mL ball mill. The ball mill speed was set to 400rpm. After grinding for 30 minutes, the sample was taken out to obtain a copper-doped manganese-based halide perovskite Cs3MnI5:0.1%Zr with uniform particle distribution. 4+ Sparkling microcrystalline powder.

[0072] The difference of Example 8 is that mixed halogen doping is used, and the doping content is relatively low. Since the doping amount is small, the influence on the crystal structure of the microcrystalline body is negligible.

[0073] Example 9

[0074] The method for preparing an ester antisolvent of an undoped manganese-based halide perovskite scintillator microcrystalline powder with a chemical formula of Cs3MnI5 comprises the following steps:

[0075] A mixed solution of 15 mmol CsI, 5 mmol MnI2, 50 mL DMF (dimethylformamide), and 50 μL HI was stirred and heated at 100 °C for 6 h until the solution became transparent and clear, then the heating was turned off and stirring was continued to room temperature; while the precursor solution was kept stirring, n-butanol (a total of 100 mL) was quickly injected into the solution until no more precipitate was precipitated.

[0076] The obtained mixture was transferred to a Buchner funnel for suction filtration, washed with n-butanol during the process, and then the precipitate was transferred to a 50mL centrifuge tube, and an appropriate amount of n-butanol was added until the precipitate was just covered. The mixture was vibrated on a vibrator until it was evenly dispersed, and then centrifugation was started at a centrifugal speed of 10000rpm for 90s. After the centrifugation was completed, the supernatant was discarded, the precipitate was retained, and the centrifugation was repeated 3 times.

[0077] Finally, the sample was sealed with a sealing film and placed in a vacuum drying oven to remove the residual solvent at a drying temperature of 60°C for 24 hours. After the solvent evaporated completely, the lumpy precipitate was taken out and placed in a 50mL ball mill jar, the ball mill speed was set to 400rpm, and the precipitate was taken out after grinding for 30 minutes to obtain a uniformly distributed undoped manganese-based halide perovskite Cs3MnI5 scintillating microcrystalline powder.

[0078] Example 10

[0079] The ether antisolvent preparation method of the undoped manganese-based halide perovskite scintillator microcrystalline powder with the chemical formula Cs3MnI5 comprises the following steps:

[0080] A mixed solution of 15 mmol CsI, 5 mmol MnI2, 50 mL DMF (dimethylformamide), and 50 μL HI was stirred and heated at 100 °C for 6 h until the solution became transparent and clear, then the heating was turned off and stirring was continued to room temperature; while the precursor solution was kept stirring, dipropyl ether (a total of 100 mL) was quickly injected into the solution until no more precipitate was precipitated.

[0081] The obtained mixture was transferred to a Buchner funnel for suction filtration, washed with dipropyl ether during the process, and then the precipitate was transferred to a 50mL centrifuge tube. An appropriate amount of n-butanol was added until the precipitate was just covered. The mixture was vibrated on a vibrator until it was evenly dispersed. Then centrifugation was started at a rate of 10,000 rpm for 90 seconds. After the centrifugation was completed, the supernatant was discarded, the precipitate was retained, and the centrifugation was repeated 3 times.

[0082] Finally, the sample was sealed with a sealing film and placed in a vacuum drying oven to remove the residual solvent at a drying temperature of 60°C for 24 hours. After the solvent evaporated completely, the lumpy precipitate was taken out and placed in a 50mL ball mill jar, the ball mill speed was set to 400rpm, and the precipitate was taken out after grinding for 30 minutes to obtain a uniformly distributed undoped manganese-based halide perovskite Cs3MnI5 scintillating microcrystalline powder.

[0083] Embodiment 11

[0084] The method for preparing an alkane antisolvent of an undoped manganese-based halide perovskite scintillator microcrystalline powder with a chemical formula of Cs3MnI5 comprises the following steps:

[0085] A mixed solution of 15 mmol CsI, 5 mmol MnI2, 50 mL DMF (dimethylformamide), and 50 μL HI was stirred and heated at 100 °C for 6 h until the solution became transparent and clear, then the heating was turned off and stirring was continued to room temperature; while the precursor solution was kept stirring, n-hexane (a total of 100 mL) was quickly injected into the solution until no more precipitate was precipitated.

[0086] The obtained mixture was transferred to a Buchner funnel for suction filtration, washed with n-hexane during the process, and then the precipitate was transferred to a 50mL centrifuge tube, and an appropriate amount of n-butanol was added until the precipitate was just covered. The mixture was vibrated on a vibrator until it was evenly dispersed, and then centrifugation was started at a centrifugal speed of 10000rpm for 90s. After the centrifugation was completed, the supernatant was discarded, the precipitate was retained, and the centrifugation was repeated 3 times.

[0087] Finally, the sample was sealed with a sealing film and placed in a vacuum drying oven to remove the residual solvent at a drying temperature of 60°C for 24 hours. After the solvent evaporated completely, the lumpy precipitate was taken out and placed in a 50mL ball mill jar, the ball mill speed was set to 400rpm, and the precipitate was taken out after grinding for 30 minutes to obtain a uniformly distributed undoped manganese-based halide perovskite Cs3MnI5 scintillating microcrystalline powder.

[0088] Example 12

[0089] The dimethyl sulfoxide (DMSO) preparation method of undoped manganese-based halide perovskite scintillator microcrystalline powder with a chemical formula of Cs3MnI5 comprises the following steps:

[0090] A mixed solution of 15 mmol CsI, 5 mmol MnI2, 50 mL DMOS, and 50 μL HI was stirred and heated at 100 °C for 6 h until the solution became transparent and clear, then the heating was turned off and stirring was continued to room temperature; while the precursor solution was kept stirring, ethyl acetate (a total of 100 mL) was quickly injected into the solution until no more precipitate was precipitated.

[0091] The obtained mixture was transferred to a Buchner funnel for suction filtration, washed with ethyl acetate during the process, and then the precipitate was transferred to a 50mL centrifuge tube. An appropriate amount of n-butanol was added until the precipitate was just covered. The mixture was vibrated on a vibrator until it was evenly dispersed. Then centrifugation was started at a rate of 10,000 rpm for 90 seconds. After the centrifugation was completed, the supernatant was discarded, the precipitate was retained, and the centrifugation was repeated 3 times.

[0092] Finally, the sample was sealed with a sealing film and placed in a vacuum drying oven to remove the residual solvent at a drying temperature of 60°C for 24 hours. After the solvent evaporated completely, the lumpy precipitate was taken out and placed in a 50mL ball mill jar, the ball mill speed was set to 400rpm, and the precipitate was taken out after grinding for 30 minutes to obtain a uniformly distributed undoped manganese-based halide perovskite Cs3MnI5 scintillating microcrystalline powder.

[0093] Table 1

[0094]

[0095]

[0096] Table 2 Preparation methods of various embodiments

[0097]

[0098]

[0099] The reaction principle of the present invention is that the doping element partially replaces the main ABX n The B-position element in the structure (equivalent or heterovalent) is essentially a process in which the dopant replaces the main body, thereby forming a new luminescent center or causing the original lattice to distort, thereby showing different ray response luminescence, and obtaining the multi-element doping result on the same doping main body. Taking Example 1 as a representative, combined with the XRD pattern and the standard card ( Figure 2), it can be known that Cs3MnI5 crystals were successfully obtained, based on which the feasibility of this method is proved. On this basis, the results of the remaining embodiments are mainly determined by the changes in the luminescence peak position and the changes in the color of the product itself. The normalized luminescence intensity in Table 1 can more intuitively reflect the changes in luminescence intensity. Its calculation method is based on the luminescence peak position data of Example 1, and the luminescence intensity of the remaining embodiments is taken as its multiple as the result. Example 3 and Example 8 are two compounds of different forms. The Cl- in Example 3 forms a stable chemical structure with other elements. The elements exist in the crystal lattice and are a polyhalogen structure; Example 8 is a doping example, which is for doping of metal centers. The Cl- concentration does not exceed 0.1%. The doping element exists in the crystal in the form of non-chemical bonds, and will not cause distortion of the material lattice. It is not a Cl- non-luminescent center, so it has no effect on the luminescence performance of the material.

[0100] The present invention provides a novel manganese-based multinary metal halide perovskite doped scintillating microcrystal and a preparation method thereof, which is used to solve the problems of difficulty in preparing inorganic scintillators, toxic and harmful elements, and single luminescence. The invention comprises the following steps:

[0101] (1) The main raw materials CsX, MnX2 and the dopant raw materials (such as the halide of the corresponding metal AX) are mixed. n 、Nitrate A(NO3) n 、Oxide AO n or acetate A(OAc) n The precursor solution is prepared by heating and stirring until transparent and clear, and the stirring time is 2-8 hours and the stirring temperature is 50-150°C. The organic solvent is one or a mixed solvent of dimethylformamide (DMF), dimethyl sulfoxide (DMAC), dimethylacetamide, acetone, butanone, acetonitrile, methylpyrrolidine (NMP) or glucopyranoside (GBL). The molar ratio of CsX to MnX2 is 3:1, and AX is 0.05-4 mol / L. n The ratio of HI to MnX2 is y:(1-0.5ny), y is the A doping content, ranging from 0≤y≤0.9; the amount of HI used is 1 / 1000 to 5 / 1000 (volume fraction) of the organic solvent.

[0102] (2) The precursor solution is allowed to stand and cool to room temperature. At room temperature, the precursor solution is rapidly stirred, and then the anti-solvent is injected into the precursor solution with a syringe, and crystals are rapidly precipitated. The anti-solvent is continuously injected until no more crystals are precipitated, and then the excess clear liquid is removed by suction filtration. During the process, the anti-solvent is used for rinsing, and then the obtained microcrystals are centrifuged. Specifically, the obtained Cs3MnX5:A n+The anti-solvent is added to the scintillation microcrystal precipitate until the precipitate is just covered, and the precipitate is placed on an oscillator until mixed evenly, followed by centrifugation at a centrifugal rate of 6000-12000 rpm for 1-3 min, the supernatant is discarded and the precipitate is retained, and the steps of adding the anti-solvent and centrifuging are repeated for more than 3 times to obtain scintillation microcrystals. The anti-solvent is an alcohol solvent such as methanol, ethanol, isopropanol, and n-butanol, or an ester solvent such as methyl formate, isobutyl formate, methyl acetate, and ethyl acetate, or an ether solvent such as dimethyl ether and ethyl ether, or an alkane solvent such as n-hexane and cyclohexane, and the anti-solvent comprises one or a mixture of several of the solvents.

[0103] The obtained scintillation microcrystals were vacuum dried at a drying temperature of 60°C for 24 hours. After being completely dried, they were taken out and ball-milled for more than 2 hours. The ball milling jar size was 50 mL, the ball milling speed was 300-500 rpm, and the ball milling time was 30 minutes, and finally scintillation microcrystal powder with uniform particle size distribution was obtained.

[0104] In the above-mentioned step 1, the molar ratio of CsX to MnX2 is 3:1, and AX n The ratio to MnX2 is y:(1-0.5ny), y is the A doping content, ranging from 0≤y≤0.9, and n is the valence state of A.

[0105] A in the above-mentioned step 1 is Ti 4+ Cr 3+ 、Ni 3+ , Cu + , Cu 2+ 、Zn 2+ , Y 3+ 、Zr 4+ 、Ag + 、In 3+ Sn 2+ , Sb 3+ 、Bi 3+ Plasma, X is a single halogen or a mixed halogen.

[0106] The suction filtration element in step three described above can be 0.1-10 μm.

[0107] The volume of the ball mill in step 5 described above can be 25-50 mL.

[0108] The invention discloses a manganese-based halide perovskite microcrystalline scintillator, the chemical formula of which is Cs3MnX5:A n+ , the doping amount of A is y, 0≤y≤0.9. Where A is Ti 4+ Cr 3+ 、Ni 3+ , Cu + , Cu 2+ 、Zn 2+、Y3 + 、Zr 4+ 、Ag + 、In 3+ Sn 2+ , Sb 3+ 、Bi 3+ Plasma, X is Cl - Br - ,I - One or more mixed halogen ions.

[0109] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A novel manganese-based multinary metal halide perovskite doped scintillating microcrystal, characterized in that: The chemical formula is Cs3MnX5:A n+ , A is one or more of Ti, Cr, Ni, Cu, Zn, Y, Zr, Ag, In, Sn, Sb, Bi elements, wherein the doping amount of A is y, 0≤y≤0.9, n is the valence state of A, 1≤n≤4, and X is Cl - Br - ,I - One or more halogen ions.

2. The novel manganese-based multinary metal halide perovskite doped scintillating microcrystal according to claim 1, characterized in that: Including Cs3MnI5, Cs3MnBr5, Cs3MnCl2I3, Cs3MnI5:0.3%Cu + 、Cs3MnI5:0.3%Ag + 、Cs3MnI5:0.3%Sn 2 + 、Cs3MnI5:0.3%Sb 3+ 、Cs3MnI5:0.1%Zr 4+ One or more of the .

3. The method for preparing the novel manganese-based multinary metal halide perovskite doped scintillating microcrystals according to claim 1 or 2, characterized in that: The main raw materials CsX, MnX2, dopant raw materials and HX are added to an organic solvent, heated and stirred until transparent and clear to obtain a precursor solution; the dopant raw materials include halide salts of the corresponding metals AX n 、Nitrate A(NO3) n 、Oxide AO n or acetate A(OAc) n One or more of the following; Injecting the antisolvent into the precursor solution until no more crystals precipitate; The microcrystals obtained were filtered and centrifuged to obtain scintillation microcrystals.

4. The method according to claim 3, characterized in that: The organic solvent includes one or more of dimethylformamide, dimethyl sulfoxide, dimethylacetamide, acetone, butanone, acetonitrile, methylpyrrolidine or butyrolactone; the anti-solvent includes one or more of alcohol solvents, ester solvents, ether solvents and alkane solvents.

5. The method according to claim 4, characterized in that: The alcohol solvent includes one or more of methanol, ethanol, isopropanol, and n-butanol; the ether solvent includes one or more of dimethyl ether, ethyl ether, and dipropyl ether; the alkane solvent includes one or more of n-hexane and cyclohexane; and the ester solvent includes one or more of methyl formate, isobutyl formate, methyl acetate, and ethyl acetate.

6. The method according to claim 3, characterized in that: The heating and stirring temperature is 50-150° C., the stirring and dissolving time is 2-8 hours, and the stirring and dissolving rate is 200-600 rpm.

7. The method according to claim 3, characterized in that: The centrifugal speed is 6000-12000 rpm, and the time is 1-3 min.

8. The method according to claim 3, characterized in that: The vacuum drying is carried out at a temperature of 60-100° C. and for a time of 6-24 hours.

9. The method according to claim 3, characterized in that: The obtained scintillation microcrystals are vacuum dried, taken out and ball-milled after being completely dried, and finally scintillation microcrystal powder with uniform particle size distribution is obtained.

10. The method according to claim 9, characterized in that: The ball milling speed is 300-500 rpm, and the ball milling time is 15-30 min.

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