Method for preparing organic metal halide glass under assistance of fluxing agent and application

Abstract

The invention provides a method for preparing organic metal halide glass under the assistance of a fluxing agent, which comprises the following steps: synthesizing organic metal halide crystals by a temperature-controlled recrystallization, anti-solvent spin coating or solvent evaporation method, filtering and drying the crystals, mixing the crystals with the screened fluxing agent according to a specific ratio, and fully grinding into powder; pouring the powder into a quartz beaker, putting the quartz beaker into a muffle furnace, heating to a melting point, keeping the temperature for a period of time, pouring the powder on an aluminum plate after the powder is completely molten, and quickly cooling the temperature to room temperature to obtain the homogeneous and transparent organic metal halide glass, so that compared with an organic metal halide crystal material, the material can be quickly prepared in a large area; the organic metal halide compound has certain photoresponse and X-ray response characteristics, can be applied to the field of medical X-ray detection, is convenient and rapid, and can be suitable for different types of organic metal halides.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of semiconductor material preparation, and relates to a preparation method of an organic metal halide glass with photoelectric response and X-ray response characteristics, in particular to a method for preparing an organic metal halide glass assisted by a fluxing agent, and the method is suitable for manufacturing a medical X-ray detection device. BACKGROUND

[0002] Organic metal halide materials (such as perovskite materials) have many unique advantages, and have been widely studied in the field of optoelectronics in recent years, especially in the applications of solar cells, light-emitting diodes (LEDs), lasers and the like. Due to the very high photoelectric conversion efficiency in solar cells, the efficiency of perovskite solar cells has rapidly increased in recent years, and even approaches or exceeds the efficiency of silicon-based solar cells. By adjusting the band gap of the organic metal halide material, it can be applied to different optoelectronic applications. The band gap of the material is adjusted by adjusting the chemical composition and crystal structure of the material, so that it exhibits good light absorption characteristics in different spectral ranges. In terms of preparation process, the organic metal halide material is mostly prepared by solution method (such as spin coating method, spraying method, etc.). These methods are relatively simple and low in cost, and have greater economic advantages compared with the traditional preparation process of silicon-based materials. In addition, the organic metal halide material is not only widely used in solar cells, but also has great application potential in photodetectors, photoluminescence devices, lasers and other fields. Overall, the high efficiency, low cost and good adjustability of these materials make them have broad prospects in future optoelectronic applications.

[0003] Currently, the application form of organic metal halide materials is mainly single crystal and polycrystalline thin film, but both are hindered in application due to obvious defects: single crystal material has excellent performance, but its slow growth rate and difficulty in size control hinder its application prospects; the preparation cost of polycrystalline thin film is low, but its poor stability and processing difficulty hinder its application. In view of this predicament, the emergence of organic metal halide glass opens up a new direction for the application of the material. The literature (Akash Singh, Adv. Mater., 2020, 10.1002 / adma.202005868) describes the preparation of organic metal halide glass by melt quenching, which can be simply and reversibly converted between glassy and crystalline states, has unique photoelectric properties, and opens up new opportunities for applications including non-volatile memory, optical communication and neuromorphic computing; The literature (Chumei Ye, Chem. Sci., 2024, 10.1039.D4SC00905C) describes the preparation of two-dimensional organic-inorganic hybrid perovskite glass by mechanical chemical induction method, which is a fast, green and efficient glass preparation method. Amorphous phase is formed from crystalline phase within 10 minutes of ball milling, and its glass transition behavior is proved by thermal analysis technology.

[0004] Organic metal halide materials have a vast variety due to the tunable characteristics of organic and inorganic parts, and the development and application of the material is limited due to the unanalyzed melting mechanism. The literature (Wei Wang, J. Am. Chem. Soc., 2024, 10.1021 / jacs.4c00768) describes that by reasonably designing the structure of the material, it has a low homogenous melting temperature and a large thermal processing window, which reduces Tm and enhances the melting stability, and has broad application prospects in the fields of glass formation, preparation of high-quality thin films for photoelectric detection and manufacturing of flexible devices. However, the design and synthesis of materials are challenging, which limits the expansion of this method.

[0005] Currently, the preparation of organic metal halide glass by melt quenching and mechanical chemical induction method is limited to several specific materials, and the method of designing the structure of the material has certain difficulty, and these methods lack certain applicability. The excellent properties and broad application prospects of organic metal halide glass force the development of a simple and universal preparation method. SUMMARY

[0006] The present application is aimed at the above problems, and the purpose is to provide a method for preparing organic metal halide glass with fluxing agent, in order to reduce the melting point and processing difficulty of organic metal halide glass.

[0007] Another purpose of the present application is to explore the application of the organic metal halide glass prepared by the method in X-ray detection.

[0008] To achieve the above object, the technical scheme adopted by the present application is as follows:

[0009] The core idea of the present application is as follows: organic metal halide crystals are synthesized by temperature control recrystallization, anti-solvent spin coating or solvent evaporation method, the crystals are filtered and dried, then mixed with a selected fluxing agent in a specific proportion and fully ground into powder, the powder is poured into a quartz beaker and placed in a muffle furnace to be heated to the melting point and kept for a period of time, after the powder is completely melted, it is poured onto an aluminum plate, and the temperature is quickly reduced to room temperature to obtain homogeneous and transparent organic metal halide glass. Compared with organic metal halide crystal materials, this material can be prepared in large area and quickly, and has certain light response and X-ray response characteristics, and can be applied to the field of medical X-ray detection. The method is convenient and fast, and can be applied to different types of organic metal halides.

[0010] In the first aspect of the present application, a method for preparing organic metal halide glass with the aid of a fluxing agent is provided, and the main steps are as follows:

[0011] (1) Put organic amine and metal halide into an acidic solvent or organic solvent in a certain proportion, heat and stir for a period of time, slowly cool to precipitate organic metal halide crystals, and then filter and dry the product;

[0012] (2) Mix the organic metal halide crystals with the fluxing agent in a certain proportion and fully grind to obtain the raw material for preparing glass;

[0013] (3) Pour the powder into a quartz beaker and place it in a muffle furnace to heat to the melting point and keep for a period of time, then pour it onto a substrate to obtain the organic metal halide glass.

[0014] The preferred technical solutions of the above three steps are as follows:

[0015] In step (1):

[0016] (i) In terms of reactants, the organic amine is selected from any one of dimethylbiguanide, 4-(ethylaminomethyl)pyridine, (S)-(-)-1-(1-naphthyl)ethylamine, (R)-1-(1-naphthyl)ethylamine, butylamine, 5-aminoquinoline, quinoxaline, phenethylamine, 3-(2-aminoethyl)pyridine, 4-(2-aminoethyl)pyridine, 2-amino-1,3,4-thiadiazole, 3,5-diamino-1,2,4-triazole, 2,6-diaminopyridine, 4,6-diaminopyrimidine, 3,5-dimethyltriazole, 3-amino-5-methylpyrazole, 3,5-dimethyltriazole, 3-aminopyridazine, 4-hydroxypyridine, 3-aminopyridine, 2-aminopyrimidine, 2-aminoimidazole, 3-aminopyrazole, cyclohexylamine, and 4-aminomethylpiperidine;

[0017] The metal halide is selected from any one of lead bromide (PbBr2), lead iodide (PbI2), bismuth bromide (BiBr3), and bismuth iodide (BiI3).

[0018] The acidic solvent is selected from a hydrogen bromide or hydrogen iodide solution with a concentration of 48 wt%.

[0019] (ii) In terms of formulation composition, different organic amines are adapted to different metal halides, and the formulation ratio is also different, as follows: the ratio of metformin, 4-(ethylaminomethyl)pyridine, 5-aminoquinoline, quinoxaline, 3-(2-aminoethyl)pyridine, 4-(2-aminoethyl)pyridine, (S)-(-)-1-(1-naphthyl)ethylamine, (R)-1-(1-naphthyl)ethylamine, 2-amino-1,3,4-thiadiazole, 3,5-diamino-1,2,4-triazole, 2,6-diaminopyridine, 4,6-diaminopyrimidine, 3,5-dimethyltriazole, 3-amino-5-methylpyrazole, 3,5-dimethyltriazole, 3-aminopyridazine, 4-hydroxypyridine, 3-aminopyridine, 2-aminopyrimidine, 2-aminoimidazole, 3-aminopyrazole, and 4-aminomethylpiperidine to lead bromide is 1:1-2:3; the ratio of phenethylamine, butylamine, and cyclohexylamine to lead iodide is 2:1; and the ratio of metformin to bismuth bromide and bismuth iodide is 1:1.

[0020] (iii) In terms of reaction temperature, different organic amines are adapted to different metal halides, and the reaction temperature is different: the reaction temperature of metformin with lead bromide, lead iodide, bismuth bromide, and bismuth iodide is 120-170 °C; the reaction temperature of 4-(ethylaminomethyl)pyridine with lead bromide is 100-170 °C; the reaction temperature of (S)-(-)-1-(1-naphthyl)ethylamine, (R)-1-(1-naphthyl)ethylamine, 2-amino-1,3,4-thiadiazole, 3,5-diamino-1,2,4-triazole, 2,6-diaminopyridine, 4,6-diaminopyrimidine, 3,5-dimethyltriazole, 3-amino-5-methylpyrazole, 3,5-dimethyltriazole, 3-aminopyridazine, 4-hydroxypyridine, 3-aminopyridine, 2-aminopyrimidine, 2-aminoimidazole, 3-aminopyrazole, and 4-aminomethylpiperidine with lead bromide is 90-160 °C; the reaction temperature of butylamine with lead iodide is 110-160 °C;

[0021] (iv) In terms of reaction conditions, the preferred process conditions are as follows:

[0022] The stirring speed is 200-1000 rpm; the reaction time is 5-60 min; and the cooling rate after the reaction is completed is 2-20 °C / min.

[0023] When suction filtration is performed, the crystal is washed with n-hexane or diethyl ether to remove residual solvent.

[0024] The drying conditions are as follows: 12-48 h in a vacuum oven at 60 °C.

[0025] In step (2):

[0026] The flux is selected from lithium hydroxide, lithium carbonate, sodium hydroxide, sodium carbonate, potassium hydroxide or potassium carbonate;

[0027] The ratio of the organometallic halide to the flux is 50:1-2:1 (molar ratio), and the ratio between different organometallic halides and the flux varies, and is as follows: the ratio of (DGA)PbBr4 and (DGA)PbI4 to LiOH is both 50:1-5:2; the ratio of (DGA)2Bi2Br 10 4(H2O) and (DGA)2Bi2I 10 2(H2O) to LiOH is 50:1-5:2; the ratio of (4-EAMP)2Pb3Br 10 to LiOH is 50:1-5:2; the ratio of (R-NEA)2PbBr4 and (S-NEA)2PbBr4 to LiOH is both 20:1-5:1; the ratio of (BA)2PbI4 to LiOH is 20:1-10:3;

[0028] In step (3):

[0029] The reaction temperature is reduced compared to before doping: (DGA)PbBr4 before doping is 260 °C, and after doping is 190-250 °C; (4-EAMP)2Pb3Br 10 before doping is 240 °C, and after doping is 180-210 °C; (DGA)PbI4 after doping is 220-240 °C; (R-NEA)2PbBr4 and (S-NEA)2PbBr4 before doping is 200 °C; after doping is 150-190 °C; (BA)2PbI4 after doping is 210-260 °C; (DGA)2Bi2Br 10 4(H2O) and (DGA)2Bi2I 10 2(H2O) is 180-250 °C after doping, and is 250 °C before doping;

[0030] Further, the holding time is 5-60 min;

[0031] Further, the substrate can be an aluminum plate, glass or graphite.

[0032] In a second aspect of the present application, an organic metal halide glass prepared by the above method is provided. The melting point test results show that the melting point of the organic metal halide glass prepared by the present application is reduced by 25-29℃ compared with that before doping, which reduces the processing difficulty while completely not affecting the glassy structure and composition thereof; meanwhile, the transmittance, X-ray sensitivity and stability of the product are more excellent.

[0033] Therefore, in a third aspect of the present application, the application of the organic metal halide glass prepared by the method of the present application in X-ray detection is provided, and a corresponding X-ray detector prepared thereby is also provided.

[0034] Effects of the present application

[0035] The present application provides a flux-assisted method for preparing an organic metal halide glass, which has the characteristics of low-temperature rapid preparation of high-quality glass. Compared with the method of designing material structure, the addition of flux reduces the melting point of the organic metal halide material and increases the processing window of the material, so that the material originally needing to be processed at high temperature can be prepared at a lower temperature, thereby reducing the processing difficulty of the material, and the material prepared at a low temperature has higher transparency than that at a high temperature. The addition of flux not only reduces the melting point of the material, but also hinders the crystallization process of the melt, making it easier to become glassy, thereby providing a new idea for the preparation of organic metal halide glass.

[0036] The method for preparing an organic metal halide glass by doping with a flux is simple to operate, has low processing difficulty, and has certain applicability. The flux not only plays a role in (DGA)PbBr4, but also plays a role in S-NPB, R-NPB, (DGA)2Bi2Br 10 ·4(H2O), (DGA)2Bi2I 10 ·2(H2O) and (4-EAMP)2Pb3Br 10 The flux also plays a role in reducing the melting point of these materials. These materials can be prepared into glassy materials without adding flux, but it is difficult to obtain high-quality glass at a higher temperature, and the processing temperature window is also short. By this method, the processing difficulty of the material is reduced, and high-quality glassy material is obtained. The addition of flux to (DGA)PbI4 and (BA)2PbI4 can also obtain the corresponding glassy state. These two materials originally do not have the characteristics of being prepared into glass (melting point is higher than decomposition temperature), and will irreversibly decompose before being converted into a melt. BRIEF DESCRIPTION OF DRAWINGS

[0037] Figure 1 The figure shows the state comparison of the organic metal halide crystal doped with a flux and not doped with a flux of Example 1 of the present application when heated at 230℃ for one hour.

[0038] Figure 2 (DGA)2Bi2I 10 2(H2O), (DGA)2Bi2Br 10 4(H2O), (4-EAMP)2Pb3Br 10 S-NPB, R-NPB, (DGA)PbBr4 corresponding crystal powder before and after doping flux, respectively, corresponding to the horizontal coordinates in the figure DBI, DBB, EPB, SPB, RPB, DPB, w / flux represents doping flux, w / o flux represents undoped flux, the yellow interval indicates the size of the reduced temperature.

[0039] Figure 3 DPB, DBB, EPB, SPB, RPB sample after doping glass material 400-800 nm transmittance test.

[0040] Figure 4 DBI, DPB, DBB, EPB, SPB, RPB corresponding to doped and undoped glass material, w / flux represents doping flux, w / o flux represents undoped flux.

[0041] Figure 5 DBI, DPB, DBB, EPB, SPB, RPB corresponding material crystalline state and a-DBI-flux, a-DPB-flux, a-DBB-flux, a-EPB-flux, a-SPB-flux, a-RPB-flux corresponding to the XRD test of doped glass state, the prepared glass after doping shows typical amorphous diffraction peak, which proves the structure of its glass state.

[0042] Figure 6 (DGA)PbI4 and (BA)2PbI4 before and after doping decomposition temperature and melting point test, corresponding to the horizontal coordinates in the figure DPI and BPI, the inserted figure is the real object display of the corresponding powder after heating before and after doping.

[0043] Figure 7 (BA)2PbI4 and (DGA)PbI4 crystalline state and glass state XRD test, crystalline state corresponds to the name BPI and DPI in the figure, glass state corresponds to a-BPI-flux and a-DPI-flux in the figure. The prepared glass after doping shows typical amorphous diffraction peak, which proves the structure of its glass state.

[0044] Figure 8Liquid state NMR hydrogen spectra of the crystalline state before doping (BPI and DPI in the figure) and of the glassy state after doping (a-BPI-flux and a-DPI-flux in the figure) for (BA)2PbI4and (DGA)PbI4. The crystalline state and the glassy state have the same chemical composition, the ammonium group located in the low field in the glassy state shows a shift to the high field proving the effect of the flux.

[0045] Figure 9 Switching ratio of the (DGA)PbBr4glass X-ray detector as a function of the X-ray dose, X-ray dose of 4.24 μGy·s -1 -1.02 μGy·s -1 with a bias of 100 V.

[0046] Figure 10 Sensitivity of the detector as a function of the bias.

[0047] Figure 11 Stability test of the X-ray detector. DETAILED DESCRIPTION

[0048] The following examples further illustrate the application and are not to be construed as further limiting. The examples do not include a detailed description of conventional methods, which are well known to one of ordinary skill in the art and are described in many publications.

[0049] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. In addition, any method and material similar or equivalent to those described herein can be used in the practice of the present application, without limitation, to the particular methods and materials described herein.

[0050] Methods for experiments not specifically described in the following examples were generally performed according to conventional methods, or according to the manufacturer's instructions.

[0051] I. Representative Metal Halide Crystals and Glasses

[0052] Example 1: Synthesis of (DGA)PbBr4and Preparation of the Glass

[0053] Step 1 : Take 10 mmol (1.29 g) of metformin (>97%, Adamas-beta) and 10 mmol (3.67 g) of lead bromide (>99.99%, TCI) into a 50 ml beaker, add 35 ml of hydrobromic acid (48 wt% in H2O, >99.99%, Sigma Aldrich), place it on a 160 °C heating stir plate, stir the reaction at 500 rpm for 30 min, after the reaction is complete, slowly cool it to room temperature to precipitate colorless (DGA)PbBr4crystals. Use a Buchner funnel to filter the (DGA)PbBr4crystals, and dry the crystals in a constant temperature vacuum oven at 60 °C for 24 h.

[0054] Step 2: Take 5 mmol (3.29 g) of (DGA)PbBr4crystals and 2 mmol (0.0479 g) of lithium hydroxide powder into an agate mortar and mix and grind them thoroughly, and then place the completely ground powder into a 50 ml quartz beaker.

[0055] Step 3: Heat the muffle furnace to 230 °C, and after the temperature is stable, place the quartz beaker containing the powder into the muffle furnace for 15-20 min to fully melt the powder.

[0056] Step 4: Place a 10 x 10 cm aluminum plate with a thickness of 0.2 mm on a flat table, and after the powder is fully melted, quickly pour the melt onto the aluminum plate to spread it out and cool it to room temperature, and after the melt solidifies, the organometallic halide glass is obtained.

[0057] Step 5: Take 5 mmol (3.29 g) of (DGA)PbBr4crystals and place them into an agate mortar and grind them thoroughly, and then place the completely ground powder into a 50 ml quartz beaker.

[0058] Step 6: Heat the muffle furnace to 260 °C, and after the temperature is stable, place the quartz beaker containing the powder into the muffle furnace for 15-20 min to fully melt the powder.

[0059] The same method is used to prepare a comparative sample (without doping a flux), and transmittance tests are performed on the two samples.

[0060] Example 2: Synthesis of (DGA)2Bi2Br4(H2O) and glass preparation 10 4(H2O) and glass preparation

[0061] ​Step 1 : Take 10 mmol (1.29 g) of Metformin (>97%, Adamas-beta) and 10 mmol (4.49 g) of Bismuth Bromide (>99.99%, aladdin) in a 50 ml beaker, add 25 ml of Hydrobromic acid (48 wt% in H2O, >99.99%, Sigma Aldrich), place on a 150 °C heating stir plate, stir at 500 rpm for 30 min, after the reaction is complete, slowly cool to room temperature to precipitate light yellow (DGA)2Bi2Br 10 • 4(H2O) crystals. Use a Buchner funnel to perform suction filtration to obtain (DGA)2Bi2Br 10 • 4(H2O) crystals, place the crystals in a constant temperature vacuum oven at 60 °C and dry for 24 h.

[0062] Step 2: Take 2.5 mmol (3.878 g) of (DGA)2Bi2Br 10 • 4(H2O) crystals and 1 mmol (0.024 g) of lithium hydroxide powder into an agate mortar and mix well and grind, place the completely ground powder into a 50 ml quartz beaker.

[0063] Step 3: Heat the muffle furnace to 210 °C, after the temperature is stable, place the quartz beaker containing the powder into the muffle furnace and heat for 15-20 min to fully melt the powder.

[0064] Step 4: Place a 10 x 10 cm aluminum plate with a thickness of 0.2 mm on a flat table, after the powder is fully melted, quickly pour the melt onto the aluminum plate to allow it to spread out on its own and cool to room temperature, after the melt solidifies, the organometallic halide glass is obtained.

[0065] Step 5: Take 2.5 mmol (3.879 g) of (DGA)2Bi2Br 10 • 4(H2O) crystals into an agate mortar and grind to a uniform mixture with a particle size of ≤10 μm, place the completely ground powder into a 50 ml quartz beaker.

[0066] Step 6: Heat the muffle furnace to 250 °C, after the temperature is stable, place the quartz beaker containing the powder into the muffle furnace and heat for 15-20 min to fully melt the powder.

[0067] The same method is used to prepare a comparative sample (without doping flux), and transmittance tests are performed on both samples.

[0068] Example 3: Synthesis of (DGA)2Bi2I 10 2(H2O) and glass preparation

[0069] Step 1 : Take 10 mmol (1.29 g) of Metformin (>97%, Adamas-beta) and 10 mmol (5.897 g) of Bismuth Iodide (> 99.99%, aladdin) into a 50 ml beaker, add 30 ml of hydriodic acid (> 47 wt% in H2O, >99.99%, Macklin), place on a 150 °C heating stir plate, stir at 500 rpm for 30 min, after the reaction is completed, slowly cool to room temperature to precipitate light yellow (DGA)2Bi2Br 10 • 4(H2O) crystals. Use a Buchner funnel to obtain (DGA)2Bi2Br 10 • 4(H2O) crystals, place the crystals in a constant temperature vacuum oven at 60 °C and dry for 24 h.

[0070] Step 2: Take 2.5 mmol (4.963 g) of (DGA)2Bi2I 10 • 2(H2O) crystals and 1 mmol (0.024 g) of lithium hydroxide powder into an agate mortar and mix well and grind, put the ground powder into a 50 ml quartz beaker.

[0071] Step 3: Heat the muffle furnace to 210 °C, after the temperature is stable, place the quartz beaker containing the powder into the muffle furnace for 15-20 min to fully melt the powder.

[0072] Step 4: Place a 10 x 10 cm aluminum plate with a thickness of 0.2 mm on a flat table, after the powder is fully melted, quickly pour the melt onto the aluminum plate to spread it out and cool it to room temperature, after the melt solidifies, the organometallic halide glass is obtained.

[0073] Step 5: Take 2.5 mmol (4.963 g) of (DGA)2Bi2Br 10 • 4(H2O) crystals into an agate mortar and grind well, put the ground powder into a 50 ml quartz beaker.

[0074] Step 6: Heat the muffle furnace to 250 °C, after the temperature is stable, place the quartz beaker containing the powder into the muffle furnace for 15-20 min to fully melt the powder.

[0075] The same method is used to prepare a comparative sample (without doping flux), and transmittance tests are performed on both samples.

[0076] The synthesis of R-NPB, S-NPB, (4-EAMP)2Pb3Br10, (DGA)PbI4, (BA)2PbI4, and other organic metal halide materials can refer to the corresponding literature, and the preparation of the glass can be processed according to this step, and the doping amount and the reaction temperature in the muffle furnace are adjusted according to the characteristics of the material.

[0077] II. Experimental results

[0078] Figure 1 The state contrast of the organic metal halide crystal doped with a cosolvent and not doped with a cosolvent in Example 1 of the present application is shown after heating at 230°C for one hour. The results show that the solution state of the organic metal halide crystal solution after doping with a cosolvent is obviously more excellent, and the solution transparency, clarity, and color are significantly better than those of the crystal solution state without doping with a cosolvent.

[0079] Figure 2 The melting point tests of (DGA)2Bi2I10·2(H2O), (DGA)2Bi2Br10·4(H2O), (4-EAMP)2Pb3Br10, S-NPB, R-NPB, (DGA)PbBr4 corresponding crystal powders before and after doping with a flux are shown, respectively corresponding to the horizontal coordinates DBI, DBB, EPB, SPB, RPB, and DPB in the figure, w / flux represents doping with a flux, w / o flux represents not doping with a flux, and the yellow interval represents the size of the reduced temperature. The results show that compared with the initial melting point, the melting points of each crystal after doping are reduced by 25-59°C.

[0080] Figure 3 The 400-800 nm transmittance tests of the glass materials after doping of the DPB, DBB, EPB, SPB, and RPB samples are shown. The results show that compared with the initial sample, the transmittance is improved.

[0081] Figure 4 The physical displays of the DBI, DPB, DBB, EPB, SPB, and RPB corresponding doped and undoped glass materials are shown, w / flux represents doping with a flux, and w / o flux represents not doping with a flux. The results show that compared with the initial glass sample, the surface smoothness and transparency of the glass material prepared after doping with a cosolvent are improved.

[0082] Figure 5XRD tests of DBI, DPB, DBB, EPB, SPB, RPB corresponding to the crystalline state and a-DBI-flux, a-DPB-flux, a-DBB-flux, a-EPB-flux, a-SPB-flux, a-RPB-flux corresponding to the glass state after doping, the prepared glass after doping shows typical amorphous diffraction peaks, which proves the structure of the glass state.

[0083] Figure 6 Decomposition temperature and melting point tests of (DGA)PbI4 and (BA)2PbI4 before and after doping, corresponding to DPI and BPI in the figure, the insert is the real object display of the powder after heating before and after doping. Compared with the initial sample, the melting point after doping decreased by 21 °C and 77 °C.

[0084] Figure 7 XRD tests of (BA)2PbI4 and (DGA)PbI4 crystalline state and glass state, corresponding to the names BPI and DPI in the figure, and a-BPI-flux and a-DPI-flux in the figure. The glass state after doping shows typical amorphous diffraction peaks, which proves the structure of the glass state.

[0085] Figure 8 Liquid-state nuclear magnetic hydrogen spectrum tests of (BA)2PbI4 and (DGA)PbI4 before doping and glass state after doping, corresponding to the names BPI and DPI in the figure, and a-BPI-flux and a-DPI-flux in the figure. The crystalline state and the glass state have the same chemical composition, and the ammonium group in the glass state at the low field shows a displacement to the high field, which proves that the fluxing agent works.

[0086] Figure 9 The on-off ratio of the (DGA)PbBr4 glass-based X-ray detector, the X-ray dose is 4.24 μGy·s -1 -1.02 μGy·s -1 , the bias is 100 V, and the on-off ratio gradually decreases over time.

[0087] Figure 10 The sensitivity of the detector under different biases.

[0088] The sensitivity (S) of the X-ray detector is defined as the response capability to per unit area dose rate, which can be calculated using the following formula:

[0089] Where I p is the photocurrent, I d is the dark current, D is the dose rate, and A is the detection area.

[0090] The results show that the sensitivity of the detector is dependent on the bias voltage, the greater the bias voltage, the higher the sensitivity.

[0091] Figure 11 The stability of the X-ray detector was tested. The device was tested for one hour continuously under an electric field intensity of 500 V / mm and an irradiation dose of 4.24 μGy·s -1 The device showed excellent irradiation stability. -1

[0092] The unexplained part involved in the present application is the same as the prior art or is realized by using the prior art. The applicant declares that the present application is illustrated by the above-mentioned embodiments to explain the detailed method of the present application, but the present application is not limited to the above-mentioned detailed method, that is, it does not mean that the present application must rely on the above-mentioned detailed method to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific methods, etc. fall within the protection scope and disclosure scope of the present application.​

Claims

1. A method for flux-assisted preparation of organometal halide glasses, characterized in that, Includes the following steps: (1) Place the organic amine and the metal halide in an acidic solvent or organic solvent in a certain proportion, heat and stir for a period of time, slowly cool down to precipitate organometal halide crystals, filter the product and dry it. (2) Mix organometal halide crystals and flux in a certain proportion and grind them thoroughly to obtain raw materials for glass preparation; (3) Pour the powder into a quartz beaker and place it in a muffle furnace. Heat the beaker to the melting point and hold it for a period of time. After the powder has completely melted, pour it onto a substrate to obtain organometallic halide glass. In step (1), the metal halide is selected from any one of lead bromide, lead iodide, bismuth bromide, and bismuth iodide; the molar ratio between the organic amine and the metal halide is 2:3 to 2:1; the acidic solvent is selected from hydrogen bromide or hydrogen iodide solution; and the reaction temperature is 90 to 170°C. In step (2), the flux is selected from lithium hydroxide, lithium carbonate, sodium hydroxide, sodium carbonate, potassium hydroxide, or potassium carbonate; the molar ratio of organometallic halide to flux is 50:1-2:

1. In step (3), the heat preservation temperature is reduced by at least 20~30℃ compared to before the flux is doped.

2. The method for flux-assisted preparation of organometal halide glasses according to claim 1, characterized in that: in, In step (1), the organic amine is selected from any one of metformin, 4-(ethylaminomethyl)pyridine, (S)-(-)-1-(1-naphthyl)ethylamine, (R)-1-(1-naphthyl)ethylamine, butylamine, 5-aminoquinoline, quinoxaline, phenethylamine, 3-(2-aminoethyl)pyridine, 4-(2-aminoethyl)pyridine, 2-amino-1,3,4-thiadiazole, 3,5-diamino-1,2,4-triazole, 2,6-diaminopyridine, 4,6-diaminopyrimidine, 3,5-dimethyltriazole, 3-amino-5-methylpyrazole, 3,5-dimethyltriazole, 3-aminopyridazine, 4-hydroxypyridine, 3-aminopyridine, 2-aminopyrimidine, 2-aminoimidazole, 3-aminopyrazole, cyclohexylamine, and 4-aminomethylpiperidine.

3. The method for flux-assisted preparation of organometal halide glasses according to claim 2, characterized in that: in, Metformin, 4-(ethylaminomethyl)pyridine, 5-aminoquinoline, quinoxaline, 3-(2-aminoethyl)pyridine, 4-(2-aminoethyl)pyridine, (S)-(-)-1-(1-naphthyl)ethylamine, (R)-1-(1-naphthyl)ethylamine, 2-amino-1,3,4-thiadiazole, 3,5-diamino-1,2,4-triazole, 2,6-diaminopyridine, 4,6-diaminopyrimidine, 3, The ratio of 5-dimethyltriazole, 3-amino-5-methylpyrazole, 3,5-dimethyltriazole, 3-aminopyridazine, 4-hydroxypyridine, 3-aminopyridine, 2-aminopyrimidine, 2-aminoimidazole, 3-aminopyrazole, 4-aminomethylpiperidine to lead bromide is 1:1 to 2:3; the ratio of phenethylamine, butylamine, cyclohexylamine to lead iodide is 2:1; the ratio of metformin to bismuth bromide and bismuth iodide is 1:

1.

4. The method for flux-assisted preparation of organometal halide glasses according to claim 2, characterized in that: in, In step (1), the reaction temperature of metformin with lead bromide, lead iodide, bismuth bromide, and bismuth iodide is 120-170 °C; the reaction temperature of 4-(ethylaminomethyl)pyridine with lead bromide is 100-170 °C; and the reaction temperature of (S)-(-)-1-(1-naphthyl)ethylamine, (R)-1-(1-naphthyl)ethylamine, 2-amino-1,3,4-thiadiazole, 3,5-diamino-1,2,4-triazole, 2,6-diaminopyridine, 4,6-diaminopyrimidine, 3,5-dimethyltriazole, 3-amino-5-methylpyrazole, 3,5-dimethyltriazole, 3-aminopyridazine, 4-hydroxypyridine, 3-aminopyridine, 2-aminopyrimidine, 2-aminoimidazole, 3-aminopyrazole, and 4-aminomethylpiperidine with lead bromide is 90-160 °C. °C; the reaction temperature of butylamine with lead iodide is 110-160 °C.

5. The method for flux-assisted preparation of organometal halide glasses according to claim 2, characterized in that: in, In step (1), the stirring speed is 200-1000 rpm; the reaction time is 5-60 min; and the cooling rate after the reaction is completed is 2-20 ℃ / min. During vacuum filtration, the crystals are washed with n-hexane or diethyl ether to remove residual solvent; The drying conditions are as follows: place in a vacuum oven at 60℃ for 12-48 hours.

6. The method for flux-assisted preparation of organometal halide glasses according to claim 1, characterized in that: in, In step (2), the organometal halide crystals are selected from (DGA)PbBr4, (DGA)PbI4, and (DGA)2Bi2Br. 10 ·4(H2O), (DGA)2Bi2I 10 ·2(H2O), (4-EAMP)2Pb3Br 10 Any one of (R-NEA)2PbBr4, (S-NEA)2PbBr4, and (BA)2PbI4; The ratios of different organometallic halides to fluxes vary, as follows: the ratio of (DGA)PbBr4 and (DGA)PbI4 to LiOH is 50:1-5:2; (DGA)2Bi2Br 10 ·4(H2O) and (DGA)2Bi2I 10 The ratio of ·2(H2O) to LiOH is 50:1-5:2; (4-EAMP)2Pb3Br 10 The ratio of (R-NEA)2PbBr4 to LiOH is 50:1-5:2; the ratio of (R-NEA)2PbBr4 to LiOH is 20:1-5:1; the ratio of (BA)2PbI4 to LiOH is 20:1-10:

3.

7. The method for flux-assisted preparation of organometal halide glasses according to claim 6, characterized in that: in, In step (3), the reaction temperature after (DGA)PbBr4 doping is 190-250°C; (4-EAMP)2Pb3Br 10 The reaction temperature after doping is 180-210 °C; the reaction temperature after doping (DGA)PbI4 is 220-240 °C; the reaction temperature after doping (R-NEA)2PbBr4 and (S-NEA)2PbBr4 is 150-190 °C; the reaction temperature after doping (BA)2PbI4 is 210-260 °C; and the reaction temperature after doping (DGA)2Bi2Br4 is... 10 4(H2O) and (DGA)2Bi2I 10 The reaction temperature after doping with 2(H2O) is 180-250 °C; The heat preservation time is 5-60 minutes; The substrate is an aluminum plate, glass, or graphite plate.

8. An organometal halide glass, characterized in that, It is prepared by the method described in any one of claims 1 to 7.

9. The application of the metal halide glass film according to claim 8 in the preparation of X-ray detector devices.

10. An X-ray detection device, characterized in that, The organometal halide glass of claim 8.

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