Lead-free organic-inorganic hybrid manganese halide crystal, preparation method thereof and application of lead-free organic-inorganic hybrid manganese halide crystal in X-ray imaging

Abstract

The invention belongs to the field of X-ray imaging application, and relates to a lead-free organic-inorganic hybrid manganese halide crystal, a preparation method thereof and application of the lead-free organic-inorganic hybrid manganese halide crystal in X-ray imaging. According to the technical scheme disclosed by the invention, the lead-free organic-inorganic hybridized manganese halide single crystal material is prepared by taking chloromethyl triphenyl phosphorus and manganese halide as raw materials, N, N-dimethylformamide (DMF) and dihalomethane as solvents and diethyl ether as an anti-solvent, and the prepared crystal material is high in photoluminescence quantum yield, high in yield, high in yield, high in yield and high in yield and can be used for preparing the lead-free organic-inorganic hybridized manganese halide single crystal material. The crystal material is further prepared into the scintillator array through a solution method, the optical crosstalk influence is effectively reduced, and the scintillator array has high resolution when being applied to X-ray imaging. The preparation method is simple, low in cost and suitable for industrial production.

Description

Technical Field

[0001] The invention belongs to the field of X-ray imaging applications, and in particular relates to a lead-free organic-inorganic hybrid manganese halide crystal material and a preparation method thereof and X-ray imaging applications. Background Art

[0002] In recent years, organic-inorganic hybrid metal halides have been widely used in the field of X-ray imaging due to their good stability, high absorption coefficient and other advantages. However, their application is limited because most materials contain toxic elements such as lead. This has prompted researchers to explore low-toxic organic-inorganic hybrid metal halides. Among a series of hybrid metal halides, Mn-based hybrid metals exhibit excellent optical stability, excellent photoluminescence quantum yield (PLQY), high scintillation rate, negligible self-absorption effect, extremely low detection limit, environmentally friendly characteristics and a radius similar to that of Pb ions. This makes it a candidate material that can replace the toxic Pb element.

[0003] Hybrid metal halides are constantly being developed, and organic-inorganic hybrid halide scintillators are widely used in the field of X-ray imaging. The high-temperature melting method has irreplaceable advantages in the preparation of certain high-performance scintillators, but its process becomes complicated due to harsh operating conditions, cumbersome steps, and extremely high equipment requirements. Although the thermal evaporation method is used to make a structural array scintillator screen with good transmission performance, its preparation operation is complicated and there are varying degrees of adhesion between the crystal columns, resulting in lateral light crosstalk and reduced resolution. Although the scintillator prepared by grinding the material and combining it with PDMS has a simple preparation process and low cost, the film made of powder cannot ensure that the material powder is fully and evenly mixed in the PDMS matrix, resulting in unevenness and defects in the internal structure of the film, leading to light scattering.

[0004] Therefore, it is necessary to conduct in-depth research on manganese-based organic-inorganic hybrid halide materials. On the basis of optimizing the preparation process, it is possible to achieve higher quality images when the materials are used in X-ray imaging and reduce harm to the human body. Summary of the invention

[0005] In order to solve the problems of harsh operating conditions and optical crosstalk in the prior art, one of the purposes of the present invention is to disclose a lead-free organic-inorganic hybrid manganese halide crystal, which has a high photoluminescence quantum yield; the second purpose of the present invention is to disclose a preparation method of the lead-free organic-inorganic hybrid manganese halide crystal, which has the characteristics of simplicity, easy operation and low cost; the third purpose of the present invention is to disclose the application of the lead-free organic-inorganic hybrid manganese halide crystal in X-ray imaging, and a scintillator array with isolated small holes is prepared by immersing the crystal in a silicon wafer with a pixel structure, which can effectively reduce the influence of optical crosstalk and has good resolution when used in X-ray imaging.

[0006] To achieve the above purpose, the specific technical solution of the present invention is:

[0007] 1. A lead-free organic-inorganic hybrid manganese halide crystal, wherein the chemical formula of the lead-free organic-inorganic hybrid manganese halide crystal is (C 19 H 17 ClP)2MnX4, X is at least one of Cl, Br, and I.

[0008] 2. The method for preparing the lead-free organic-inorganic hybrid manganese halide crystal comprises the following steps:

[0009] (1) Chloromethyl triphenylphosphine, MnX2, N,N-dimethylformamide and CH4X2 are placed in a wide-mouthed glass bottle with a magnetic rotor, sealed, heat treated, stirred and mixed to obtain a clear and transparent solution;

[0010] (2) After the solution is clarified, the rotor is removed, and the wide-mouthed glass bottle is placed in a jar containing ether anti-solvent and sealed. The bottle is left to stand until crystals precipitate in the bottle. The crystals are repeatedly washed with ether to obtain (C 19 H 17 ClP)2MnX4 crystal.

[0011] Preferably, in step (1) of the above-mentioned method for preparing lead-free organic-inorganic hybrid manganese halide crystals, the mass volume ratio of chloromethyltriphenylphosphine, MnX2, N,N-dimethylformamide, CH4X2 and diethyl ether is 0.6944:0.1258:1-2:1-2:10-15 (g:g:ml:ml:ml).

[0012] Preferably, the heat treatment temperature in step (1) is 60°C.

[0013] Preferably, the stirring speed in step (1) is 200 to 300 r / min and the stirring time is 30 to 40 min.

[0014] Preferably, the sealed environment in step (2) is room temperature, and the static reaction time is 24 to 36 hours.

[0015] Preferably, in step (1), X in MnX2 and CH4X2 is at least one of Cl, Br and I.

[0016] Further preferably, the method for preparing lead-free organic-inorganic hybrid manganese halide crystals is characterized by comprising the following steps:

[0017] (1) 2 mmol of chloromethyl triphenylphosphine and 1 mmol of MnCl2 were placed in a wide-mouthed glass bottle with a magnetic rotor, and then 1 ml of N,N-dimethylformamide and 1 ml of CH4Cl2 were added. The bottle was sealed and placed on a heating table at 60°C for heating while continuously stirring until a clear transparent solution was formed;

[0018] (2) After the solution is clarified, remove the sealing plug, take out the rotor, put it into a jar with ether anti-solvent and seal it, let it stand until crystals precipitate, and repeatedly wash the crystals with ether several times to obtain (C 19 H 17 ClP)2MnCl4 single crystal.

[0019] 3. The application of the lead-free organic-inorganic hybrid manganese halide crystal in X-ray imaging comprises the following steps:

[0020] (1) 19 H 17 ClP)2MnX4 single crystal is ground into powder, and (C 19 H 17 ClP)2MnX4 single crystal powder, fluororubber and acetone are mixed and ground and stirred for 2-3 days to obtain (C 19 H 17 ClP)2MnX4 supersaturated solution;

[0021] (2) Apply the supersaturated solution to a silicon wafer with uniform pore size, and place the silicon wafer in a vacuum filter for vacuum treatment, so that (C 19 H 17 ClP)2MnX4 particles enter the silicon wafer holes, and repeat the coating and vacuuming operations to make the crystal powder particles fill the entire silicon wafer, and finally obtain (C 19 H 17 ClP)2MnX4 array scintillator;

[0022] (3) The obtained (C 19 H 17 ClP)2MnX4 array scintillator is used in X-ray imaging.

[0023] Preferably, the application of the lead-free organic-inorganic hybrid manganese halide in X-ray imaging, step (1) (C 19 H 17 The mass volume ratio of ClP2MnCl4 small single crystal powder, fluororubber and acetone is 500:150-200:15, mg:mg:ml.

[0024] The beneficial effects of the present invention are:

[0025] (1) The technical solution disclosed in the present invention uses chloromethyl triphenylphosphine and manganese halide as raw materials, N,N-dimethylformamide (DMF) and dihalomethane as solvents, and ether as anti-solvent to prepare a lead-free organic-inorganic hybrid manganese halide single crystal material. The prepared lead-free organic-inorganic hybrid manganese halide crystal material (with (C 19 H 17 Taking ClP)2MnCl4 crystal as an example, the photoluminescence quantum yield of the crystal is as high as 96.63%. Under X-ray radiation, the crystal has 53159.6 photon MeV -1 High light output and 182.5nGy air s -1 Low detection limit.

[0026] (2) A scintillator array with isolated small holes was prepared by immersing a mixed solution of lead-free organic-inorganic hybrid manganese halide single crystal powder, fluororubber and acetone into a silicon wafer with a pixel structure using a solution method, which effectively reduced the influence of light crosstalk. The obtained scintillator array (with (C 19 H 17 ClP)2MnCl4 as an example) has a high resolution of 23.9lp / mm.

[0027] (3) Using the lead-free organic-inorganic hybrid manganese halide crystal material of the present invention (with (C 19 H 17 The application of the scintillator array prepared by using ClP2MnCl4 crystal as an example in X-ray imaging technology has the following characteristics: the detection limit is low, which will greatly reduce the harm to the human body, and the resolution is high, and high-quality imaging images can be obtained when shooting X-rays, which can effectively improve the efficiency of medical and industrial detection. In addition, the preparation method of the present invention is simple, low-cost and suitable for industrial production.

[0028] Other advantages, objectives and features of the present invention will be described in the following description to some extent, and to some extent, will be obvious to those skilled in the art based on the following examination and study, or can be taught from the practice of the present invention. The objectives and other advantages of the present invention can be realized and obtained through the following description. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention will be described in detail below in conjunction with the accompanying drawings, wherein:

[0030] Figure 1 (C) prepared in Example 1 19 H 17 Schematic diagram of the synthesis process of ClP)2MnCl4 single crystal;

[0031] Figure 2(C) prepared in Example 1 19 H 17 ClP)2MnCl4 single crystal molecular structure diagram;

[0032] Figure 3 (C) prepared in Example 1 19 H 17 Photos of ClP)2MnCl4 single crystal under sunlight and UV light (365nm);

[0033] Figure 4 (C) prepared in Example 1 19 H 17 ClP)2MnCl4 single crystal X-ray powder diffraction pattern;

[0034] Figure 5 (C) prepared in Example 1 19 H 17 ClP)2MnCl4 single crystal excitation spectrum (PLE) and emission spectrum (PL) diagram;

[0035] Figure 6 (C) prepared in Example 1 19 H 17 Photoluminescence quantum yield (PLQY) diagram of ClP2MnCl4 single crystal;

[0036] Figure 7 For Example 1 (C 19 H 17 Comparison of the light yield of ClP)2MnCl4 single crystal and commercial LuAG:Ce;

[0037] Figure 8 (C) prepared in Example 1 19 H 17 The fitting curve of the minimum detection limit of ClP)2MnCl4 single crystal;

[0038] Fig. 9 (C) prepared in Example 1 19 H 17 The change curve of ClP)2MnCl4 single crystal after irradiation at 50kV and 500μA for 1h;

[0039] Fig.10 (C) prepared in Example 2 19 H 17 ClP)2MnCl4 scintillator array production flow chart and (C 19 H 17 ClP)2MnCl4 array under natural light and ultraviolet light;

[0040] Fig.11 (C) prepared in Example 219 H 17 Modulation transfer function curve of ClP)2MnCl4 array scintillator;

[0041] Fig.12 is prepared by Example 2 (C 19 H 17 ClP)2MnCl4 array scintillator, showing dried fish and partial magnification under natural light and X-ray. The partial magnification can show high-quality X-ray images of dried fish, and the fish bones, heart, and eyeballs inside the dried fish are clearly displayed. DETAILED DESCRIPTION

[0042] The following describes the embodiments of the present invention by specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that the illustrations provided in the following embodiments only illustrate the basic concept of the present invention in a schematic manner, and the following embodiments and features in the embodiments can be combined with each other without conflict.

[0043] Among them, the drawings are only used for illustrative explanations, and they only represent schematic diagrams rather than actual pictures, and should not be understood as limitations on the present invention. In order to better illustrate the embodiments of the present invention, some parts of the drawings may be omitted, enlarged or reduced, and do not represent the size of actual products. For those skilled in the art, it is understandable that some well-known structures and their descriptions in the drawings may be omitted.

[0044] Example 1

[0045] An organic-inorganic hybrid manganese halide crystal material (C 19 H 17 ClP)2MnCl4, the schematic diagram of its preparation process is as follows Figure 1 The specific preparation method is as follows:

[0046] 2mmol chloromethyl triphenylphosphine (C 19 H 17Cl2P 694.44mg) and 1mmol manganese chloride (MnCl2 125.84mg) are placed in a wide-mouth glass bottle with a magnetic rotor, and then 1ml N,N-dimethylformamide (DMF) and 1ml dichloromethane (DCM) solvent are added. After the bottle is sealed, it is placed on a 60°C heating table for heating and continuously stirred (200rpm) until a clear transparent solution is formed (about 30min). After the solution is clarified, the sealing plug is removed, the rotor is taken out and placed in a jar with 10ml ether (Et2O) anti-solvent and sealed. After standing overnight (24h), crystals precipitate in the vial. Repeatedly wash with ether 3 times to obtain (C 19 H 17 ClP)2MnCl4 single crystal.

[0047] The above-prepared (C 19 H 17 The molecular structure of ClP)2MnCl4 single crystal is shown in the figure Figure 2 As shown, (C 19 H 17 The photos of ClP)2MnCl4 single crystal under sunlight and ultraviolet light (365nm) are as follows Figure 3 shown.

[0048] Single crystal performance test

[0049] The organic-inorganic hybrid manganese halide crystal material (C 19 H 17 ClP)2MnCl4 is subjected to the following operations: (1) X-ray powder diffraction (XRD) is used for detection, and the obtained X-ray powder diffraction pattern is as follows: Figure 4 As shown. Figure 4 It can be seen that ((C 19 H 17 The XRD of the crystal of ClP)2MnCl4 is consistent with the XRD (Simulation) simulated after single crystal analysis, proving that the preparation method of Example 1 of the present invention can indeed prepare (C 19 H 17 (2) The single crystal structure of (C1P)2MnCl4 prepared in Example 1 was measured by a steady-state fluorescence spectrometer. 19 H 17 The single crystal of ClP)2MnCl4 was tested to obtain the emission spectrum (PLE) with 286, 357, 432, 447nm as the excitation wavelength and the excitation spectrum (PL) with 517nm as the emission wavelength, as shown in Figure 5 As shown. Figure 5 From the emission spectrum (PL) curve (Emission), it can be seen that the organic-inorganic hybrid manganese halide crystal material (C19 H 17 When the crystal of ClP)2MnCl4 is excited at 286, 357, 432, and 447nm, the emission peak is at 517nm; Figure 5 From the PLE curve (Excitation), it can be seen that when the emission is at 517nm, the excitation peaks are located at 286, 357, 432, and 447nm. 19 H 17 The photoluminescence quantum yield (PLQY) of ClP)2MnCl4 crystal is 96.63%. Figure 6 (3) The (C) prepared in Example 1 was analyzed by Maya2000 Pro spectrometer. 19 H 17 The single crystal of ClP)2MnCl4 was tested for radiative luminescence spectrum, and the light yield was compared with that of commercial LuAG:Ce (C 19 H 17 The light yield of ClP)2MnCl4 crystal is 53159.6photons MeV -1 ,like Figure 7 As shown. We also obtained (C 19 H 17 ClP)2MnCl4 crystal minimum detection limit fitting curve, such as Figure 8 As shown, it can be seen that (C 19 H 17 The detection limit of ClP)2MnCl4 crystals is 182.5nGy s -1 At the same time, if Fig. 9 , (C 19 H 17 The change curve of ClP)2MnCl4 crystal after irradiation with 50kV and 500μA for 1h shows that the crystal remains stable under long-term radiation.

[0050] Application Example 1

[0051] (C 19 H 17 The application of ClP)2MnCl4 crystal in X-ray imaging includes the following steps:

[0052] (1) Preparation of scintillator array: refer to Fig.10 As shown, 150 mg of fluororubber was dissolved in 15 ml of acetone (AC) solution; 500 mg of the synthesized (C 19 H 17ClP)2MnCl4 crystals were placed in an agate mortar for grinding. The crystals were ground into sufficiently fine powder and added to the above solution for further grinding, so that the prepared gel solution and crystals were mixed as fully as possible and the powder particles were as uniform and fine as possible; the solution was transferred to a glass bottle for ultrasonic vibration and mixing, and a rotor was added to stir the mixed solution for 2 days to obtain (C 19 H 17 ClP)2MnCl4 supersaturated solution, the solution was taken out with a rubber-tipped dropper and evenly applied to a silicon wafer with a pore size of 50μm, and then the silicon wafer was placed in a vacuum filter for 20 minutes to make the smaller (C 19 H 17 ClP)2MnCl4 particles enter the silicon wafer holes, repeat the operation three times to make the smaller powder particles fill the entire silicon wafer as much as possible, and finally obtain (C 19 H 17 ClP)2MnCl4 array scintillator;

[0053] (2) The array scintillator is irradiated with X-rays, and the results are as follows Fig.10 As shown in the last figure. The blade is irradiated with X-rays by the scintillator prepared in Example 2, and (C 19 H 17 The resolution of ClP)2MnCl4 array scintillator is 23.9lp / mm. Fig.11 As shown in (C 19 H 17 Modulation transfer function curve of ClP)2MnCl4 array scintillator. Fig.12 It can be seen that under natural light, only the appearance of the dried fish can be seen, and its internal structure cannot be obtained, but under X-ray irradiation, the internal structure of the dried fish can be clearly seen, including fish bones, heart, eyeballs, etc. This is also consistent with the actual internal structure of the dried fish.

[0054] Example 2

[0055] An organic-inorganic hybrid manganese halide crystal material (C 19 H 17 ClP)2MnCl4 crystals, the schematic diagram of its preparation process is as follows Figure 1 The specific preparation method is as follows:

[0056] 4mmol chloromethyl triphenylphosphine (C 19 H 17Cl2P 1388.88mg) and 2mmol manganese chloride (MnCl2251.68mg) are placed in a wide-mouth glass bottle with a magnetic rotor, and then 2ml N,N-dimethylformamide (DMF) and 2ml dimethyl sulfoxide (DMSO) solvent are added. After the bottle is sealed, it is placed on an 80°C heating table for heating and continuously stirred (300rpm) until a clear transparent solution is formed (about 30min). After the solution is clarified, the sealing plug is removed, the rotor is taken out and placed in a jar with 15ml ether (Et2O) anti-solvent and sealed. After standing overnight (36h), crystals precipitate in the vial. Repeatedly wash with ether 4 times to obtain (C 19 H 17 ClP)2MnCl4 single crystal.

[0057] Single crystal performance test

[0058] The organic-inorganic hybrid manganese halide crystal material (C 19 H 17 The corresponding performance tests were carried out on the organic-inorganic hybrid manganese halide crystal material (C 19 H 17 The crystal properties of (C1P)2MnCl4 are similar. This shows that the method of the present invention can prepare (C 19 H 17 ClP)2MnCl2 single crystal has the characteristics of stability and good luminescence.

[0059] Application Example 2

[0060] (C 19 H 17 The application of ClP)2MnCl4 crystal in X-ray imaging includes the following steps:

[0061] (1) Preparation of scintillator array: refer to Fig.10 As shown, 200 mg of fluororubber was dissolved in 15 ml of acetone (AC) solution; 500 mg of the synthesized (C 19 H 17 ClP)2MnCl4 crystals were placed in an agate mortar for grinding. The crystals were ground into sufficiently fine powder and added to the above solution for further grinding, so that the prepared gel solution and crystals were mixed as fully as possible and the powder particles were as uniform and fine as possible; the solution was transferred to a glass bottle for ultrasonic shaking and mixing, and a rotor was added to stir the mixed solution for 3 days to obtain (C 19 H 17 ClP)2MnCl4 supersaturated solution, the solution was taken out with a rubber-tipped dropper and evenly applied to a silicon wafer with a pore size of 50μm, and then the silicon wafer was placed in a vacuum filter for 30 minutes to make the smaller (C19 H 17 ClP)2MnCl4 particles enter the silicon wafer holes, repeat the operation three times to make the smaller powder particles fill the entire silicon wafer as much as possible, and finally obtain (C 19 H 17 ClP)2MnCl4 array scintillator;

[0062] (2) The array scintillator is irradiated with X-rays, and the (C 19 H 17 The resolution of the ClP)2MnCl4 array scintillator is similar to that of Application Example 1.

[0063] The above embodiments illustrate that the X-ray imaging scintillator prepared by the present invention emits green light under the excitation light of 365nm ultraviolet wavelength, and the finally obtained scintillator has the characteristics of stability, high resolution and good luminescence.

[0064] 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 it. 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 purpose and scope of the technical solution, which should be included in the scope of the claims of the present invention.

Claims

1. A lead-free organic-inorganic hybrid manganese halide crystal, characterized in that: The chemical formula of the lead-free organic-inorganic hybrid manganese halide crystal is (C 19 H 17 ClP)2MnX4, X is at least one of Cl, Br, and I.

2. The method for preparing the lead-free organic-inorganic hybrid manganese halide crystal according to claim 1, characterized in that: The steps include: (1) Chloromethyl triphenylphosphine, MnX2, N,N-dimethylformamide and CH4X2 are placed in a wide-mouthed glass bottle with a magnetic rotor, sealed, heat treated, stirred and mixed to obtain a clear and transparent solution; (2) After the solution is clarified, the rotor is removed, and the wide-mouthed glass bottle is placed in a jar containing ether anti-solvent and sealed. The bottle is left to stand until crystals precipitate in the bottle. The crystals are repeatedly washed with ether to obtain (C 19 H 17 ClP)2MnX4 crystal.

3. The method for preparing the lead-free organic-inorganic hybrid manganese halide crystal according to claim 2, characterized in that: The mass volume ratio of chloromethyltriphenylphosphine, MnX2, N,N-dimethylformamide, CH4X2 and ether in step (1) is 0.6944:0.1258:1-2:1-2:10-15, g:g:ml:ml:ml.

4. The method for preparing the lead-free organic-inorganic hybrid manganese halide crystal material according to claim 2, characterized in that: The heat treatment temperature in step (1) is 60°C.

5. The method for preparing the lead-free organic-inorganic hybrid manganese halide crystal material according to claim 2, characterized in that: The stirring speed of step (1) is 200-300 r / min and the stirring time is 30-40 min.

6. The method for preparing the lead-free organic-inorganic hybrid manganese halide crystal material according to claim 2, characterized in that: The sealing environment in step (2) is room temperature, and the static reaction time is 24 to 36 hours.

7. The method for preparing the lead-free organic-inorganic hybrid manganese halide crystal material according to claim 2, characterized in that: In step (1), X in MnX2 and CH4X2 is at least one of Cl, Br and I.

8. The method for preparing the lead-free organic-inorganic hybrid manganese halide crystal according to claim 2, characterized in that: The steps include: (1) 2 mmol of chloromethyl triphenylphosphine and 1 mmol of MnCl2 were placed in a wide-mouthed glass bottle with a magnetic rotor, and then 1 ml of N,N-dimethylformamide and 1 ml of dichloromethane were added. The bottle was sealed and placed on a heating table at 60°C for heating while continuously stirring until a clear transparent solution was formed; (2) After the solution is clarified, remove the sealing plug, take out the rotor, put it into a jar with ether anti-solvent and seal it, let it stand until crystals precipitate, and repeatedly wash the crystals with ether several times to obtain (C 19 H 17 ClP)2MnCl4 single crystal.

9. Application of lead-free organic-inorganic hybrid manganese halide crystals in X-ray imaging, characterized in that: The steps include: (1) 19 H 17 ClP)2MnX4 single crystal is ground into powder, and (C 19 H 17 ClP)2MnX4 single crystal powder, fluororubber and acetone are mixed and ground and stirred for 2-3 days to obtain (C 19 H 17 ClP)2MnX4 supersaturated solution; (2) Apply the supersaturated solution to a silicon wafer with uniform pore size, and place the silicon wafer in a vacuum filter for vacuum treatment, so that (C 19 H 17 ClP)2MnX4 particles enter the silicon wafer holes, and repeat the coating and vacuuming operations to make the crystal powder particles fill the entire silicon wafer, and finally obtain (C 19 H 17 ClP)2MnX4 array scintillator; (3) The obtained (C 19 H 17 ClP)2MnX4 array scintillator is used in X-ray imaging.

10. The use of the lead-free organic-inorganic hybrid manganese halide in X-ray imaging according to claim 9, characterized in that: Step (1) (C 19 H 17 The mass volume ratio of ClP2MnCl4 small single crystal powder, fluororubber and acetone is 500:150-200:15, mg:mg:ml.

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