An organic-inorganic manganese-based metal halide scintillator material containing diphenylphosphine

Abstract

The present invention discloses an organic-inorganic manganese-based metal halide scintillator material containing diphenylphosphine, its preparation method, and application, belonging to the technical field of luminescent materials. By adjusting the cationic structure of the metal-manganese organic hybrid scintillator, the present invention achieves X-ray luminescence of varying intensities and improves the scintillator's stability. The preparation method involves both liquid-phase diffusion and vapor-phase volatilization. The entire preparation process is mild, does not involve highly toxic or highly polluting organic reagents, and is low-cost, simple to operate, and environmentally friendly. The transparent film produced after simple treatment such as heating and melting can be used for X-ray imaging and detection, and has broad application prospects.

Description

Technical Field

[0001] The present invention belongs to the technical field of luminescent materials, and in particular relates to an organic-inorganic manganese-based metal halide scintillator material containing diphenylphosphine, a preparation method thereof, and an application thereof. Background Art

[0002] With the continuous advancement of science and technology, X-ray imaging detection technology has been widely used in medical imaging, industrial inspection, aerospace, and security fields. X-ray scintillators, as a class of materials that can convert high-energy X-rays into low-energy ultraviolet or visible light, play a vital role in this process. However, most of the commercial scintillator materials currently used are inorganic scintillator single crystals, which have problems such as high growth temperature, difficult processing, and high cost. In comparison, metal-organic hybrid scintillators have many advantages, including low cost, simple preparation, and stable luminescence. Their unique photophysical and chemical properties, especially the basic research on the controllable organic structure therein, provide more possibilities for further optimization of luminescence performance. This makes metal-organic hybrid materials one of the most anticipated candidate materials in the future development of scintillator materials.

[0003] As an emerging scintillator, metal halide materials exhibit excellent scintillation performance due to their high X-ray attenuation coefficient, high light yield and low X-ray detection limit. Among them, lead-free metal halides, such as Mn(Ⅱ)-based metal halides, have attracted much attention due to their environmental friendliness and ease of preparing large-area thin films. However, the currently known Mn(Ⅱ)-based metal halide materials are mainly based on the triphenylphosphine material system, which limits their flexibility in performance regulation and material design. Therefore, the present invention provides a manganese-based metal-organic hybrid scintillator material based on a diphenylphosphine structure. Compared with the existing triphenylphosphine system, the metal-organic hybrid scintillator material containing diphenylphosphine has a wider material design space and more flexible performance regulation method, which can improve its luminescence performance and stability, etc., and can bring new ideas and possibilities to the research and application of scintillator materials. Summary of the Invention

[0004] The present invention aims to provide a series of organic and inorganic manganese-based metal halide luminescent materials and scintillator materials containing diphenylphosphine. By adjusting the cationic structure, different intensities of X-ray radiation luminescence can be achieved and the scintillator stability can be improved. The method is simple and cost-effective to prepare. The resulting materials exhibit excellent X-ray excitation luminescence properties. Furthermore, through simple thin film preparation methods, high-resolution X-ray imaging can be achieved.

[0005] To achieve the above object, the present invention adopts the following technical solutions:

[0006] First, the present invention provides a class of organic and inorganic manganese-based metal halide luminescent materials and scintillator materials containing diphenylphosphine, the structural formula of which is shown in Formula I:

[0007]

[0008] In formula I, R1 and R2 are selected from alkyl groups containing 1 to 6 carbon atoms.

[0009] In a second aspect, the present invention further provides a method for synthesizing an organic-inorganic manganese-based metal halide crystalline material containing diphenylphosphine, comprising the following steps:

[0010] 1) R1, R2 diphenylphosphine bromide and manganese bromide (in a molar ratio of 2:1) are dissolved in an appropriate amount of solvent 1 (1-5 mL) (selected from one, two or more of dichloromethane, ethanol, methanol, and N,N-dimethylformamide, preferably ethanol or a mixture of dichloromethane and ethanol).

[0011] 2) Solvent 2 (1-5 mL) is added to the solution in step 1) or vapor-diffused until green crystals appear. Solvent 2 is selected from one or both of n-hexane, diethyl ether, and ethyl acetate, preferably diethyl ether.

[0012] In the step 1), R1 and R2 are selected from alkyl groups containing 1 to 6 carbon atoms.

[0013] In a third aspect, the present invention provides a method for preparing an organic-inorganic manganese-based metal halide scintillator glass material containing diphenylphosphine, comprising the following steps:

[0014] 1) Mix R1, R2 diphenylphosphine bromide and manganese bromide solid in a molar ratio of 2:1 and grind thoroughly.

[0015] 2) heating the powder obtained in step 1) or the crystalline material obtained in the above method until it melts.

[0016] 3) solidifying the molten product obtained in step 2) to obtain the scintillator glass material.

[0017] In the step 1), R1 and R2 are selected from alkyl groups containing 1 to 6 carbon atoms.

[0018] In a fourth aspect, the present invention provides a method for preparing a scintillating screen of the organic-inorganic manganese-based metal halide scintillator material containing diphenylphosphine, comprising the following steps:

[0019] The organic-inorganic manganese-based metal halide material containing diphenylphosphine is placed on quartz glass and heated to melt. After the melt has no bubbles, another quartz plate is taken to cover the melt. The temperature is then slowly lowered and the surface quartz plate is removed to obtain the scintillation screen.

[0020] In a fifth aspect, the present invention provides applications of the above-mentioned organic-inorganic manganese-based metal halide scintillator material containing diphenylphosphine in the field of X-ray imaging, such as medical imaging detection or industrial detection.

[0021] The crystals prepared according to the present invention are detected by a CCD single crystal X-ray diffractometer and are consistent with the target molecular structure, and the crystals have good quality and high yield.

[0022] The beneficial effects of the present invention are:

[0023] (1) The metal halides used in the present invention are inexpensive, non-toxic, and abundant on Earth, reducing production costs. The entire preparation process is mild and simple to operate, does not involve highly toxic or highly polluting organic reagents, and has a high yield, thus addressing to some extent the high cost and difficulty in preparing current X-ray scintillator materials.

[0024] (2) The series of manganese-based metal halide scintillators provided by the present invention have good scintillation performance, among which the detection limit of (DP33)2MnBr4 with better performance is determined to be 29.60nGy s -1 , is the standard dose rate required for X-ray medical diagnosis (5.5 μGyair s -1 ) is 1 / 186 of the original value.

[0025] (3) The present invention can achieve high-resolution X-ray imaging. Due to its good response to X-rays, the spatial resolution can reach 30 lp mm -1 @MTF=0.26. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is a crystal structure diagram of the manganese-based metal halide scintillator in formula I.

[0027] Figure 2 This is the XRD pattern of the manganese-based metal halide scintillator in formula I.

[0028] Figure 3 Graph showing the photoluminescence spectrum (PL) of the metal halide scintillator in formula I.

[0029] Figure 4 This is the radioluminescence spectrum (RL) diagram of the manganese-based metal halide scintillator in formula I.

[0030] Figure 5 It is a linear curve of the X-ray radiation intensity of the manganese-based metal halide scintillator in formula I versus the X-ray dose rate in a large range.

[0031] Figure 6 Images of (DP33)2MnBr4 under natural light and ultraviolet light.

[0032] Figure 7 This is the imaging and MTF curve of (DP33)2MnBr4 under X-ray irradiation after simple film formation. DETAILED DESCRIPTION

[0033] In order to make the contents of the present invention easier to understand, the technical solutions of the present invention are further described below in conjunction with specific implementation methods, but the present invention is not limited thereto.

[0034] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0035] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0036] The present invention can employ conventional techniques of organic chemistry within the skill of the art. In the following examples, efforts have been made to ensure the accuracy of the numbers used (including amounts, temperatures, reaction times, etc.), but some experimental errors and deviations should be taken into account. The temperatures used in the following examples (units are degrees Celsius) are expressed in ° C, and the pressures are at or near atmospheric pressure. All solvents were purchased as analytical grade, and all reagents were commercially available unless otherwise noted.

[0037] Example 1 (DP33) Synthesis of 2MnBr4 Crystals

[0038] The (DP33)2MnBr4 compound was prepared by dissolving dipropyldiphenylphosphine bromide and manganese bromide (1.0 mmol and 0.50 mmol) in a mixed solvent (2 mL) of ethanol and dichloromethane (1:1). Ether vapor was slowly diffused into the solution at room temperature until crystals precipitated. The product structure is shown below:

[0039]

[0040] Example 2 (DP14) Synthesis of 2MnBr4 Crystals

[0041] The (DP14)2MnBr4 compound was prepared by dissolving methylbutyldiphenylphosphonium bromide and manganese bromide (1.0 mmol and 0.50 mmol) in a mixed solvent (2 mL) of ethanol and dichloromethane (1:1). Ether vapor was slowly diffused into the solution at room temperature until crystals precipitated. The product structure is shown below:

[0042]

[0043] Example 3 (DP24) Synthesis of 2MnBr4 Crystals

[0044] The (DP24)2MnBr4 compound was prepared by dissolving ethylbutyldiphenylphosphonium bromide and manganese bromide (1.0 mmol and 0.50 mmol) in a mixed solvent (2 mL) of ethanol and dichloromethane (1:1). Ether vapor was slowly diffused into the solution at room temperature until crystals precipitated. The product structure is shown below:

[0045]

[0046] Example 4 (DP34) Synthesis of 2MnBr4 Crystals

[0047] The (DP34)2MnBr4 compound was prepared by dissolving propylbutyldiphenylphosphonium bromide and manganese bromide (1.0 mmol and 0.50 mmol) in a mixed solvent (3 mL) of ethanol and dichloromethane (2:1) in a 2:1 ratio. Ether vapor was slowly diffused into the solution at room temperature until crystals precipitated. The product structure is shown below:

[0048]

[0049] Example 5 (DP33) 2MnBr4 film imaging

[0050] (DP33)2MnBr4 has the best radiation performance and required dose rate, so the crystal sample obtained in Example 1 is placed on quartz glass and heated and melted in a vacuum box. The air bubbles are removed by vacuuming, and another quartz plate is used to cover the melt. The temperature is then lowered to obtain the scintillation screen.

[0051] Example 6 Experimental Analysis

[0052] The crystallographic data of the obtained compounds were collected by Rigaku-ACF11 equipped with a Rigaku Saturn CCD area detector (Bruker-SMART) and the X-ray source was pattern monochromatic Mo-Kα radiation. Working at 298K.

[0053] The photoluminescence spectra of the four crystals were measured at room temperature using an FLS980 fluorescence spectrometer.

[0054] The corresponding RL spectrum test was performed using a commercial miniature X-ray source combined with an Edinburgh FS5 fluorescence spectrophotometer (Edinburgh Instruments Ltd.). The X-ray source was a commercial miniature silver target X-ray tube (AMPEK, Inc.) with a maximum tube current / power output of 200 μA / 4 W.

[0055] X-ray images were taken with a Canon EOS 700D camera coupled to a commercial X-ray tube (tungsten target, Moxtek). The sample was placed 3 cm between the X-ray source and the scintillator film, and images were taken from behind the film. X-ray images were obtained using a line pair card as the imaging target.

[0056] Figure 1 and Figure 2 The crystal structures, simulated XRD patterns and measured XRD patterns of the manganese metal halide scintillators (DP14)2MnBr4, (DP24)2MnBr4, (DP33)2MnBr4 and (DP34)2MnBr4 in Formula I are compared. Figure 1 、 Figure 2 The obtained crystal structure is consistent with the measured XRD curve, indicating that the sample has good purity.

[0057] Figure 3 is the photoluminescence spectrum PL diagram of the manganese metal halide scintillator in formula I, Figure 4 This is the luminescence spectrum RL diagram of the manganese-based metal halide scintillator in formula I. Figure 3 and Figure 4 showed that the same radiative recombination pathway occurs under X-ray and UV excitation.

[0058] Figure 5 This is a linear curve of X-ray radiation intensity versus X-ray dose rate over a wide range. Through calculation and analysis, a series of detection limit values ​​for manganese-based metal halide scintillators can be obtained, with the lowest detection limit being 29.60 nGy s -1 , with a maximum of 35.16 nGy s -1 , respectively, are the standard dose rates for X-ray medical diagnostic applications (5.5 μGy air s -1 ) of 1 / 186 and 1 / 156.

[0059] Figure 6 Images of (DP33)2MnBr4 under natural light and ultraviolet light.

[0060] Figure 7 The imaging and MTF curve of (DP33)2MnBr4 under X-ray irradiation after simple film preparation show that it has good imaging ability. max and I min The spatial resolution of the image is quantified by the modulation transfer function (MTF), which can be obtained from the formula:

[0061]

[0062] Among them I min and Imax are the minimum and maximum values ​​of the function that quantifies the contrast. By obtaining 20.0 and 30.0 lp mm -1 I corresponding to spatial frequency max and I min The MTF values ​​corresponding to these two frequencies are analyzed and calculated to be 0.32±0.01 and 0.26±0.01.

[0063] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made according to the scope of the patent application of the present invention should fall within the scope of the present invention.

Claims

1. An organic-inorganic manganese-based metal halide scintillator material containing diphenylphosphine, characterized in that: Its chemical formula is as follows: Wherein, R1 and R2 are selected from alkyl groups containing 1 to 6 carbon atoms.

2. A method for preparing the organic-inorganic manganese-based metal halide scintillator material containing diphenylphosphine as claimed in claim 1, characterized in that: R1, R2 diphenylphosphine bromide and manganese bromide are dissolved in solvent 1, and solvent 2 is added dropwise or by vapor diffusion to obtain an organic-inorganic manganese-based metal halide scintillator crystal material containing diphenylphosphine; R1 and R2 are selected from alkyl groups containing 1-6 carbon atoms.

3. The method according to claim 2, wherein: The solvent 1 is at least one of dichloromethane, ethanol, methanol, and N,N-dimethylformamide; the solvent 2 is at least one of n-hexane, ether, and ethyl acetate.

4. A method for preparing the organic-inorganic manganese-based metal halide scintillator material containing diphenylphosphine as claimed in claim 1, characterized in that: R1, R2 diphenylphosphine bromide and manganese bromide solid are mixed and fully ground, heated to melt, and solidified to obtain an organic-inorganic manganese-based metal halide scintillator glass material containing diphenylphosphine; R1 and R2 are selected from alkyl groups containing 1 to 6 carbon atoms.

5. A method for preparing the organic-inorganic manganese-based metal halide scintillator material containing diphenylphosphine as claimed in claim 1, characterized in that: Dissolving R1, R2 diphenylphosphine bromide and manganese bromide in solvent 1, and adding solvent 2 by dropwise addition or vapor diffusion to obtain an organic-inorganic manganese-based metal halide scintillator crystal material containing diphenylphosphine; The organic and inorganic manganese-based metal halide scintillator glass material containing diphenylphosphine is obtained by heating until it melts and solidifies; wherein R1 and R2 are selected from alkyl groups containing 1 to 6 carbon atoms.

6. The method according to any one of claims 2, 4 and 5, characterized in that: The molar ratio of R1, R2 diphenylphosphine bromide and manganese bromide is 2:

1.

7. A use of the organic-inorganic manganese-based metal halide scintillator material containing diphenylphosphine as claimed in claim 1, characterized in that: Used to prepare X-ray imaging and detection materials.

8. The use according to claim 7, characterized in that: The scintillator material is used to prepare a scintillating screen.

9. The use according to claim 7, characterized in that: The preparation method of the scintillator screen is as follows: placing the organic-inorganic manganese-based metal halide scintillator material containing diphenylphosphine on quartz glass and heating and melting it; after the melt has no bubbles, taking another quartz plate to cover the melt; then slowly cooling it; removing the surface quartz plate to obtain the scintillator screen.

10. A use of the organic-inorganic manganese-based metal halide scintillator material containing diphenylphosphine as claimed in claim 1, characterized in that: The scintillator material is used to prepare the light-emitting layer material of a doped or non-doped OLED device.

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