Preparation of Mn-based organic-inorganic hybrid perovskite scintillator and application of Mn-based organic-inorganic hybrid perovskite scintillator in in-vivo 3D dosimeter

Abstract

The invention discloses preparation of a Mn-based organic-inorganic hybrid perovskite scintillator and application of the Mn-based organic-inorganic hybrid perovskite scintillator in an in-vivo 3D dosimeter, and belongs to the technical field of radiation detection materials and biomedical engineering. The Mn-based organic-inorganic hybrid perovskite scintillator is prepared from the following raw materials: an organic ligand (allyl triphenyl phosphonium bromide, (3, 3-dimethyl allyl) triphenyl phosphonium bromide, propyl triphenyl phosphonium bromide or (4-bromobutyl) triphenyl phosphonium bromide), a manganese source and a solvent (ethyl acetate). Ethyl acetate is used as a solvent, so that the reaction time is saved, and meanwhile, the yield of the product is improved. According to the invention, the material with good crystallinity and stability and excellent radiation response characteristic is prepared by selecting the types of the organic ligand and the manganese source and adjusting the proportion of the organic ligand and the manganese source. The obtained material can be used for preparing a 3D dosimeter, and the Mn-based perovskite scintillator is combined with X-ray detection, so that the development of the Mn-based perovskite scintillator in the field of combination of high-performance X-ray detection and the 3D dosimeter is effectively promoted.

Description

Technical Field

[0001] The present invention belongs to the technical fields of radiation detection materials and biomedical engineering, and more specifically relates to the preparation of Mn-based organic-inorganic hybrid perovskite scintillators and their application as in-vivo 3D dosimeters. Background Art

[0002] X-ray detection refers to a technical process of using detection equipment to detect, record, and analyze the presence, intensity, energy distribution, or other related characteristics of X-rays. X-ray detection has extensive applications in fields such as medical diagnosis and security inspection. Traditional inorganic semiconductor materials (such as silicon, cadmium telluride, etc.) as the core materials of X-ray detectors, although having high detection efficiency and energy resolution, have complex preparation processes, high costs, and obvious technical bottlenecks in the manufacture of large-area detectors. In addition, the environmental stability and processability of these materials are also difficult to meet the requirements of some practical applications.

[0003] In recent years, organic-inorganic hybrid perovskite materials have become important candidate materials in the field of X-ray detection due to their excellent optoelectronic properties, low-cost preparation processes, and good processability. However, current research on perovskite materials mostly focuses on lead-based perovskites. Although these materials exhibit good performance, their practical applications are greatly limited due to the toxicity problem of lead.

[0004] To address this issue, the development of a new type of lead-free or low-toxic hybrid perovskite material has become a current research hotspot. Among them, manganese (Mn)-based organic-inorganic hybrid perovskites have gradually attracted people's attention due to their potential environmental friendliness and excellent optoelectronic properties. Existing research has shown that manganese-based perovskites exhibit great potential in energy band regulation, luminescence performance, and stability. However, the current systematic research on manganese-based perovskites and the development of related applications are still in the initial stage, especially the application research in the field of combining high-performance X-ray detection with 3D dosimeters is still blank. Moreover, the currently commonly used manganese-based perovskites have poor stability, which limits their application in the field of X-ray detection.

[0005] Therefore, how to design and prepare an Mn-based organic-inorganic hybrid perovskite material with excellent performance, environmental friendliness, and high stability, and apply it to the field of combining high-performance X-ray detection with 3D dosimeters has become a technical problem that urgently needs to be solved. Summary of the Invention

[0006] The objective of the present invention is to provide a preparation method of Mn-based organic-inorganic hybrid perovskite scintillator and its application as an in-vivo 3D dosimeter, so as to solve the problems existing in the above-mentioned prior art, improve the stability of the Mn-based organic-inorganic hybrid perovskite scintillator, and at the same time promote the application research of the Mn-based organic-inorganic hybrid perovskite scintillator in the field of combination of high-performance X-ray detection and 3D dosimeter.

[0007] To achieve the above objective, the present invention provides the following solutions:

[0008] One of the technical solutions of the present invention: Provide a preparation method of a Mn-based organic-inorganic hybrid perovskite scintillator, including the following steps:

[0009] Dissolve the organic ligand and the manganese source in a solvent respectively to obtain a ligand solution and a manganese source solution; add the ligand solution to the manganese source solution for reaction to obtain the Mn-based organic-inorganic hybrid perovskite scintillator;

[0010] The organic ligand includes allyl triphenylphosphonium bromide, (3,3-dimethylallyl) triphenylphosphonium bromide, propyl triphenylphosphonium bromide or (4-bromobutyl) triphenylphosphonium bromide;

[0011] The solvent includes ethyl acetate.

[0012] The selected organic ligands of the present invention, namely allyl triphenylphosphonium bromide, (3,3-dimethylallyl) triphenylphosphonium bromide, propyl triphenylphosphonium bromide or (4-bromobutyl) triphenylphosphonium bromide, have the characteristics of low raw material cost, low toxicity and high stability when exposed to air.

[0013] The present invention uses ethyl acetate as the solvent. Compared with other solvents such as ethanol, ethyl acetate evaporates faster and it is easier to obtain powdery products, saving reaction time; in addition, by choosing ethyl acetate as the solvent, ethyl acetate has a lower polarity and weaker hydrogen bond force. This property enables the perovskite precursor to have a faster crystallization rate in ethyl acetate, which is beneficial to the rapid formation of perovskite crystals, thereby improving the yield of the Mn-based organic-inorganic hybrid perovskite scintillator.

[0014] Preferably, the manganese source includes manganese bromide and / or manganese chloride.

[0015] Preferably, the molar ratio of the organic ligand to the manganese source is 1-2:1.

[0016] The present invention prepares a Mn-based organic-inorganic hybrid perovskite scintillator using an organic ligand that can be effectively doped with Mn and play a synergistic role. The crystal structure of the organic-inorganic hybrid perovskite follows the general formula ABX3 of the perovskite structure. By adjusting the type and dosage of the organic ligand to form stronger chemical bonds or more stable interactions, such as hydrogen bonds and van der Waals forces, with the inorganic part, the stability of the overall perovskite structure can be enhanced, and the deformation and degradation of the structure can be reduced. Further, by adjusting the ratio of the organic ligand to the manganese source, the obtained material has both good crystallinity and stability and excellent radiation response characteristics.

[0017] Preferably, the reaction time ≥ 2 h.

[0018] Technical solution two of the present invention: Provide the Mn-based organic-inorganic hybrid perovskite scintillator prepared by the preparation method described above.

[0019] Technical solution three of the present invention: Provide the application of the Mn-based organic-inorganic hybrid perovskite scintillator in the preparation of a 3D dosimeter.

[0020] The present invention uses the prepared powdered Mn-based organic-inorganic hybrid perovskite scintillator to prepare a 3D dosimeter, and provides a solution for a miniaturized 3D dosimeter that integrates the powdered Mn-based organic-inorganic hybrid perovskite scintillator with a signal transmission and processing module.

[0021] Technical solution four of the present invention: Provide a 3D dosimeter, which includes a main control chip, a Bluetooth chip, a photoelectric sensor, a scintillator element containing the Mn-based organic-inorganic hybrid perovskite scintillator, a temperature sensor, and a battery.

[0022] The 3D dosimeter provided by the present invention is combined with X-ray detection. In the 3D dosimeter based on the main control chip, the photoelectric sensor is used to detect the light intensity and convert it into an electrical signal; the temperature sensor detects the internal temperature in real time; the Bluetooth chip transmits the signal to the outside; it reaches the state where the light signal detected by the scintillator can accurately invert the three-dimensional radiation dose distribution in the body, promoting the application research of the Mn-based organic-inorganic hybrid perovskite scintillator in the field of the combination of high-performance X-ray detection and 3D dosimeters.

[0023] The present invention discloses the following technical effects:

[0024] 1. By selecting the types and adjusting the ratios of the organic ligand and the manganese source, the present invention finds an organic ligand that can be effectively doped with Mn and play a synergistic role, ensuring that the obtained material has both good crystallinity and stability and excellent radiation response characteristics.

[0025] 2. The powdered Mn-based organic-inorganic hybrid perovskite scintillator prepared in the present invention is used to prepare a 3D dosimeter. The provided 3D dosimeter is combined with X-ray detection. Based on multiple factors such as the attenuation characteristics of radiation in biological tissues, the luminescence characteristics of the Mn-based organic-inorganic hybrid perovskite scintillator, and the geometric distribution of the X-ray detector, the state is achieved where the optical signal detected by the scintillator can accurately invert the three-dimensional radiation dose distribution in the body, promoting the application research of the Mn-based organic-inorganic hybrid perovskite scintillator in the field of the combination of high-performance X-ray detection and 3D dosimeters. Description of the Drawings

[0026] Figure 1 FIG. is a physical diagram of the Mn-based organic-inorganic hybrid perovskite scintillators prepared in Examples 1 to 4. Among them, from left to right are Example 1, Example 2, Example 3, and Example 4 in sequence;

[0027] Figure 2 FIG. is a fluorescence emission spectrum diagram of the Mn-based organic-inorganic hybrid perovskite scintillators prepared in Examples 1 to 4 with the slit kept consistent (0.27 nm) and the excitation wavelength of 362 nm;

[0028] Figure 3 FIG. is a fluorescence emission spectrum diagram of the Mn-based organic-inorganic hybrid perovskite scintillators prepared in Example 4 and Comparative Examples 3 to 4 with the slit kept consistent (0.27 nm) and the excitation wavelength of 362 nm;

[0029] Figure 4 FIG. is a fluorescence emission spectrum diagram of the Mn-based organic-inorganic hybrid perovskite scintillators prepared in Example 4 and Comparative Examples 1 to 2 with the slit kept consistent (0.27 nm) and the excitation wavelength of 362 nm;

[0030] Figure 5 FIG. is a comparison diagram of the emission spectra of the Mn-based organic-inorganic hybrid perovskite scintillators prepared in Examples 1 to 4 and commercially available CsI under the excitation of an X-ray source (50 kV, 50 μA);

[0031] Figure 6 FIG. is a test result diagram of the X-ray sensitivity of the Mn-based organic-inorganic hybrid perovskite scintillator prepared in Example 4;

[0032] Figure 7 FIG. is a structural schematic diagram of the 3D dosimeter. Among them, the fluorescent material is a scintillator element containing the Mn-based organic-inorganic hybrid perovskite scintillator. Detailed Embodiments

[0033] The various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics, and implementation schemes of the present invention.

[0034] It should be understood that the terms used in the present invention are only for describing specific embodiments and are not intended to limit the present invention. Additionally, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0035] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0036] Without departing from the scope or spirit of the present invention, various improvements and changes can be made to the specific embodiments of the present invention specification, which are obvious to those skilled in the art. Other embodiments obtained from the specification of the present invention are obvious to those skilled in the art. The specification and examples of the present invention are merely exemplary.

[0037] Regarding the use of "comprising", "including", "having", "containing", etc. herein, they are all open-ended terms, meaning including but not limited to.

[0038] The raw materials used in the examples, comparative examples and performance tests of the present invention are described as follows:

[0039] The allyltriphenylphosphonium bromide, (3,3-dimethylallyl)triphenylphosphonium bromide, propyltriphenylphosphonium bromide and (4-bromobutyl)triphenylphosphonium bromide used were purchased from Aladdin, and the CAS numbers are: 1560-54-9, 1530-34-3, 6228-47-3 and 7333-63-3 respectively.

[0040] The MnBr2 used was purchased from Aladdin, and the CAS number is: 13446-03-2.

[0041] The ethyl acetate used was purchased from Aladdin, and the CAS number is: 141-78-6.

[0042] The commercially available CsI used was purchased from Shanghai Shuojie Crystal Materials Co., Ltd.

[0043] All other raw materials used are commercially available products unless otherwise specified.

[0044] Unless otherwise specified, the room temperature involved in the present invention is calculated as 25 ± 5 °C.

[0045] Example 1

[0046] This example provides a preparation method of an Mn-based organic-inorganic hybrid perovskite scintillator, and the steps are as follows:

[0047] S1. Dissolve 1.533 g of allyl triphenylphosphonium bromide and 0.43 g of MnBr2 in 5 mL of ethyl acetate respectively to obtain an allyl triphenylphosphonium bromide precursor solution and an MnBr2 solution;

[0048] S2. Inject the allyl triphenylphosphonium bromide precursor solution into the MnBr2 solution, and stir and react at room temperature for 2 h to make it evenly mixed;

[0049] S3. Pour the solution obtained in S2 onto filter paper, and obtain the Mn-based organic-inorganic hybrid perovskite scintillator after filtration and natural evaporation to dryness, denoted as (C 21 H 20 P)2MnBr4.

[0050] Example 2

[0051] This example provides a preparation method of an Mn-based organic-inorganic hybrid perovskite scintillator, and the steps are as follows:

[0052] S1. Dissolve 1.645 g of (3,3-dimethylallyl) triphenylphosphonium bromide and 0.43 g of MnBr2 in 5 mL of ethyl acetate respectively to obtain a (3,3-dimethylallyl) triphenylphosphonium bromide precursor solution and an MnBr2 solution;

[0053] S2. Inject the (3,3-dimethylallyl) triphenylphosphonium bromide precursor solution into the MnBr2 solution, and stir and react at room temperature for 2 h to make it evenly mixed;

[0054] S3. Pour the solution obtained in S2 onto filter paper, and obtain the Mn-based organic-inorganic hybrid perovskite scintillator after filtration and natural evaporation to dryness, denoted as (C 23 H 24 P)2MnBr4.

[0055] Example 3

[0056] This example provides a preparation method of an Mn-based organic-inorganic hybrid perovskite scintillator, and the steps are as follows:

[0057] S1. Dissolve 1.541 g of propyl triphenylphosphonium bromide and 0.43 g of MnBr2 in 5 mL of ethyl acetate respectively to obtain a propyl triphenylphosphonium bromide precursor solution and an MnBr2 solution;

[0058] S2. Inject the propyltriphenylphosphonium bromide precursor solution into the MnBr2 solution and stir the reaction at room temperature for 2 h to make it evenly mixed;

[0059] S3. Pour the solution obtained in S2 onto filter paper, filter and naturally evaporate to dryness to obtain the Mn-based organic-inorganic hybrid perovskite scintillator, denoted as (C 21 H 22 P)2MnBr4.

[0060] Example 4

[0061] This example provides a method for preparing a Mn-based organic-inorganic hybrid perovskite scintillator, and the steps are as follows:

[0062] S1. Disperse 0.96 g of (4-bromobutyl)triphenylphosphonium bromide and 0.43 g of MnBr2 in 5 mL of ethyl acetate respectively to obtain the (4-bromobutyl)triphenylphosphonium bromide precursor solution and the MnBr2 solution;

[0063] S2. Inject the (4-bromobutyl)triphenylphosphonium bromide precursor solution into the MnBr2 solution and stir the reaction at room temperature for 2 h to make it evenly mixed;

[0064] S3. Pour the solution obtained in S2 onto filter paper, filter and naturally evaporate to dryness to obtain the Mn-based organic-inorganic hybrid perovskite scintillator, denoted as (C 22 H 23 P)2MnBr4.

[0065] Figure 1 FIG. is a physical diagram of the Mn-based organic-inorganic hybrid perovskite scintillators prepared in Examples 1 to 4, where from left to right are Example 1, Example 2, Example 3 and Example 4 in sequence.

[0066] Comparative Example 1

[0067] The difference from Example 4 is that "ethyl acetate" is replaced with an equal amount of "absolute ethanol", and the others are the same as Example 4.

[0068] Specifically:

[0069] S1. Disperse 0.96 g of (4-bromobutyl)triphenylphosphonium bromide and 0.43 g of MnBr2 in 5 mL of absolute ethanol respectively to obtain the (4-bromobutyl)triphenylphosphonium bromide precursor solution and the MnBr2 solution;

[0070] S2. Inject the (4-bromobutyl)triphenylphosphonium bromide precursor solution into the MnBr2 solution and stir the reaction at room temperature for 2 h to make it evenly mixed;

[0071] S3. Pour the solution obtained in S2 onto a filter paper, and after filtration and natural evaporation to dryness, the Mn-based organic-inorganic hybrid perovskite scintillator is obtained.

[0072] Comparative Example 2

[0073] The difference from Example 4 is that "ethyl acetate" is replaced with an equal amount of "DMF", and the others are the same as in Example 4.

[0074] Specifically:

[0075] S1. Disperse 0.96 g of (4-bromobutyl)triphenylphosphonium bromide and 0.43 g of MnBr2 in 5 mL of DMF respectively to obtain a (4-bromobutyl)triphenylphosphonium bromide precursor solution and a MnBr2 solution;

[0076] S2. Inject the (4-bromobutyl)triphenylphosphonium bromide precursor solution into the MnBr2 solution, stir and react at room temperature for 2 h to make it uniformly mixed;

[0077] S3. Pour the solution obtained in S2 onto a filter paper, and after filtration and natural evaporation to dryness, the Mn-based organic-inorganic hybrid perovskite scintillator is obtained.

[0078] Comparative Example 3

[0079] The difference from Example 4 is that the molar ratio of (4-bromobutyl)triphenylphosphonium bromide to MnBr2 is adjusted from 1:1 to 2.2:1, and the others are the same as in Example 4.

[0080] Specifically:

[0081] S1. Disperse 2.11 g of (4-bromobutyl)triphenylphosphonium bromide and 0.43 g of MnBr2 in 5 mL of ethyl acetate respectively to obtain a (4-bromobutyl)triphenylphosphonium bromide precursor solution and a MnBr2 solution;

[0082] S2. Inject the (4-bromobutyl)triphenylphosphonium bromide precursor solution into the MnBr2 solution, stir and react at room temperature for 2 h to make it uniformly mixed;

[0083] S3. Pour the solution obtained in S2 onto a filter paper, and after filtration and natural evaporation to dryness, the Mn-based organic-inorganic hybrid perovskite scintillator is obtained, denoted as (C 22 H 23 P)2MnBr4.

[0084] Comparative Example 4

[0085] The difference from Example 4 is that the molar ratio of (4-bromobutyl)triphenylphosphonium bromide to MnBr2 is adjusted from 1:1 to 0.9:1, and the others are the same as in Example 4.

[0086] Specifically:

[0087] S1. Disperse 0.86 g of (4-bromobutyl)triphenylphosphonium bromide and 0.43 g of MnBr₂ in 5 mL of ethyl acetate respectively to obtain a (4-bromobutyl)triphenylphosphonium bromide precursor solution and an MnBr₂ solution;

[0088] S2. Inject the (4-bromobutyl)triphenylphosphonium bromide precursor solution into the MnBr₂ solution, stir and react at room temperature for 2 h to make them mix evenly;

[0089] S3. Pour the solution obtained in S2 onto filter paper, filter and evaporate it naturally to obtain an Mn-based organic-inorganic hybrid perovskite scintillator, denoted as (C 22 H 23 P)₂MnBr₄.

[0090] Performance detection:

[0091] 1. Perform fluorescence spectrum detection on the Mn-based organic-inorganic hybrid perovskite scintillators prepared in Examples 1-4 and Comparative Examples 1-4.

[0092] Detection method: Steady-state fluorescence spectrum detection, and the results are as Figures 2 to 4 shown.

[0093] Figure 2 is the fluorescence emission spectrum of the Mn-based organic-inorganic hybrid perovskite scintillators prepared in Examples 1-4 with the slit kept consistent (0.27 nm) and the excitation wavelength of 362 nm; Figure 3 is the fluorescence emission spectrum of the Mn-based organic-inorganic hybrid perovskite scintillators prepared in Example 4 and Comparative Examples 3-4 with the slit kept consistent (0.27 nm) and the excitation wavelength of 362 nm; Figure 4 is the fluorescence emission spectrum of the Mn-based organic-inorganic hybrid perovskite scintillators prepared in Example 4 and Comparative Examples 1-2 with the slit kept consistent (0.27 nm) and the excitation wavelength of 362 nm. Figure 2 It shows that the materials prepared with allyltriphenylphosphonium bromide, (3,3-dimethylallyl)triphenylphosphonium bromide or (4-bromobutyl)triphenylphosphonium bromide as organic ligands have higher fluorescence intensity. Figure 3 It indicates that the materials prepared with the molar ratio of organic ligand to manganese source of 2:1 and 2.2:1 have higher fluorescence intensity, indicating that the radiation recombination efficiency of the materials is high at this ratio, the non-radiative recombination process is relatively less, and the luminescence performance of the materials is good. While the fluorescence intensity of the materials prepared with the molar ratio of organic ligand to manganese source of 0.9:1 is relatively low, because there are more defects or impurities in the materials at this ratio, acting as non-radiative recombination centers, reducing the luminescence efficiency; Figure 4It is shown that the polarity of the solvent has an important influence on the emission spectrum of perovskite. The polarity of absolute ethanol is relatively moderate, and its interaction with perovskite can make the energy level structure of perovskite in a more suitable state, which is conducive to electron transition and luminescence. The polarity of DMF is relatively high, which will cause great changes in the energy levels of perovskite, resulting in a decrease in the intensity of the emission spectrum. The polarity of ethyl acetate is between the two, so the luminescence intensity is also in the middle. Among the three, ethyl acetate is easy to prepare, has a fast crystallization rate, and can improve the yield.

[0094] 2. Compare the emission spectra of the Mn-based organic-inorganic hybrid perovskite scintillators prepared in Examples 1 to 4 and commercially available CsI under the excitation of an X-ray source (50 kV, 50 μA). The results are as Figure 5 shown.

[0095] Figure 5 Figure 9 is a comparison chart of the emission spectra of the Mn-based organic-inorganic hybrid perovskite scintillators prepared in Examples 1 to 4 and commercially available CsI under the excitation of an X-ray source (50 kV, 50 μA). It can be Figure 5 seen that the intensities of the four scintillators under X-ray excitation are all greater than that of commercially available CsI.

[0096] 3. Test the X-ray sensitivity of the Mn-based organic-inorganic hybrid perovskite scintillator prepared in Example 4.

[0097] Test method: X-ray fluorescence spectrometry. The results are as Figure 6 shown.

[0098] Figure 6 Figure 23 is a test result chart of the X-ray sensitivity of the Mn-based organic-inorganic hybrid perovskite scintillator prepared in Example 4. It can be Figure 6 seen that the detection limit of this scintillator can reach 27.4 nGy / s, with a low radiation detection limit and high sensitivity.

[0099] 4. Prepare a 3D dosimeter using the Mn-based organic-inorganic hybrid perovskite scintillator prepared in Example 4.

[0100] Preparation method:

[0101] Preparation of the scintillator element (7 mm high, 6.5 mm in diameter): Put the synthesized powder into a beaker, melt it using a heating jacket at 150 °C, pour it into a customized mold, cool it and take it out to obtain the scintillator element. Assembly of the 3D dosimeter: Assemble the STM32 microcontroller, Bluetooth chip, photoelectric sensor, scintillator element (7 mm high, 6.5 mm in diameter), temperature sensor and battery according to the Figure 7 shown structure to obtain the 3D dosimeter.

[0102] The above 3D dosimeter is used to monitor the three-dimensional radiation dose distribution in a specific part of a living body (such as tumor tissue) during radiotherapy. The monitoring method includes implanting or injecting the 3D dosimeter into a predetermined monitoring site before treatment, collecting radiation dose data in real time during treatment and transmitting it to an external terminal for processing and display, and subsequently adjusting the radiotherapy plan (such as adjusting parameters such as the intensity, angle, and irradiation time of the radiation source) according to the dose distribution information.

[0103] The various embodiments in this specification are described in a progressive manner. Each embodiment focuses on the differences from other embodiments. For the same and similar parts among the various embodiments, reference can be made to each other.

[0104] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be obvious to those skilled in the art. The general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to these embodiments shown herein, but rather will be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a Mn-based organic-inorganic hybrid perovskite scintillator, characterized in that: The steps include: Dissolving an organic ligand and a manganese source in a solvent respectively to obtain a ligand solution and a manganese source solution; adding the ligand solution to the manganese source solution for reaction to obtain the Mn-based organic-inorganic hybrid perovskite scintillator; The organic ligand includes allyl triphenyl phosphonium bromide, (3,3-dimethylallyl) triphenyl phosphonium bromide, propyl triphenyl phosphonium bromide or (4-bromobutyl) triphenyl phosphonium bromide; The solvent included ethyl acetate.

2. The preparation method according to claim 1, characterized in that: The manganese source includes manganese bromide and / or manganese chloride.

3. The preparation method according to claim 1, characterized in that: The molar ratio of the organic ligand to the manganese source is 1 to 2:

1.

4. The preparation method according to claim 1, characterized in that: The reaction time is ≥2h.

5. A Mn-based organic-inorganic hybrid perovskite scintillator prepared by the preparation method according to any one of claims 1 to 4.

6. Use of the Mn-based organic-inorganic hybrid perovskite scintillator according to claim 5 in the preparation of a 3D dosimeter.

7. A 3D dosimeter, characterized in that: The 3D dosimeter comprises a main control chip, a Bluetooth chip, a photoelectric sensor, a scintillator element comprising the Mn-based organic-inorganic hybrid perovskite scintillator according to claim 6, a temperature sensor and a battery.

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