Antimony (III)-based flexible scintillator film capable of being used for X-ray imaging and preparation method and application of antimony (III)-based flexible scintillator film

Abstract

The invention belongs to the field of photoelectric materials, and discloses an antimony (III)-based flexible scintillator film capable of being used for X-ray imaging and a preparation method and application thereof.The method comprises the following steps that A2 (CnH2n) and SbCl3 are weighed and added into a solvent, heating and stirring are conducted to enable reactants to be dissolved, then cooling, suction filtration, washing and drying are conducted, and a target scintillator single crystal is obtained; adding a polymer SEBS-g-MAH into a toluene solution, and heating and stirring until the solution is clear and transparent; the method comprises the following steps: grinding a target scintillator single crystal into powder, adding the powder into an SEBS-g-MAH / toluene solution, and stirring until the powder is uniformly dispersed; dispensing the obtained solution into a polytetrafluoroethylene mold, and volatilizing at normal temperature to obtain a film; the antimony (III)-based flexible scintillator film prepared by the invention has good mechanical properties, and can be repeatedly bent, stretched and compressed.

Description

Technical Field

[0001] The invention belongs to the field of optoelectronic materials, and in particular relates to an antimony (III)-based flexible scintillator film that can be used for X-ray imaging, and a preparation method and application thereof. Background Art

[0002] Scintillators can convert high-energy X-rays into low-energy ultraviolet / visible light. They are an important component of indirect X-ray detectors and can be widely used in many fields such as medical imaging, industrial inspection and scientific research. Metal halides have become a hot topic of scintillator research in recent years due to their solution processing characteristics, ideal X-ray absorption capacity and efficient and adjustable luminescence performance, especially Pb metal halides. However, the characteristic toxicity of Pb metal halide materials themselves is contrary to the current theme of environmental friendliness. Sb, which is in a diagonal position in the periodic table of Pb, has a similar, highly stereochemically active outer electron structure (ns 2 ), and its related halides usually exhibit efficient short-lived luminescence, and are considered to be an emerging candidate to replace Pb. At the same time, the Sb element has a relatively high atomic number, which is conducive to the efficient absorption of X-rays. In addition, antimony (III) halides also have the advantages of simple preparation and high stability. Therefore, antimony (III) halides are expected to be used as new scintillator materials for high-performance X-ray detectors.

[0003] Traditional X-ray detectors mainly use rigid flat-plate structures to obtain two-dimensional planar structural images of objects, but this cannot meet the urgent needs of X-ray imaging in various complex scenarios. For example, imaging of curved or irregular objects will cause image distortion. Flexible scintillator films with good ductility, stretchability, and easy bending properties can fit well on the surface of irregular or curved objects, thereby better restoring the original morphology of the object. Therefore, the development of new high-performance antimony (III)-based halide scintillators and the development of flexible films are of great significance to the development of X-ray imaging and detection. Summary of the invention

[0004] The purpose of the present invention is to solve the deficiencies in the prior art and to provide an antimony (III)-based flexible scintillator film that can be used for X-ray imaging, and a preparation method and application thereof.

[0005] In order to achieve the above object, the present invention is achieved through the following technical solutions:

[0006] In a first aspect, the present invention provides a method for preparing an antimony (III)-based flexible scintillator film that can be used for X-ray imaging, the method comprising the following steps:

[0007] Step (1): According to the molar ratio of A2(C n H 2n): SbCl3 = 1: 0.8-1.2, weigh A2 (C n H 2n ) and SbCl3 are added to a solvent, wherein A is a piperidinyl group and n is any integer from 1 to 9, and the reactants are heated to dissolve, and then cooled, filtered, washed and dried to obtain a target scintillator single crystal, whose molecular formula is [A2H2(C n H 2n )SbCl5]·0.5H2O;

[0008] Step (2): adding polymer SEBS-g-MAH to a toluene solution, heating and stirring until the solution is clear and transparent, to obtain a SEBS-g-MAH / toluene solution;

[0009] Step (3): Grind the target scintillator single crystal into powder, add it into SEBS-g-MAH / toluene solution, and stir until the powder is evenly dispersed, wherein the mass ratio of SEBS-g-MAH to scintillator is 1:0.5-0.75.

[0010] Step (4): drip the solution obtained in step (3) into a polytetrafluoroethylene mold and volatilize at room temperature to obtain a film.

[0011] Preferably, the heating temperature in step (1) is 80-120°C.

[0012] Preferably, the solvent in step (1) is hydrochloric acid or DMF.

[0013] Preferably, in step (1), the cooling rate is 5-10° C. every 30 minutes.

[0014] Preferably, the heating temperature in step (2) is 50-60°C.

[0015] Preferably, in step (3), the stirring time is 10-12 hours.

[0016] Preferably, in step (3), the room temperature volatilization temperature is 20-30°C and the time is 10-24h.

[0017] In a second aspect, the present invention provides an antimony (III)-based flexible scintillator film that can be used for X-ray imaging, which is prepared by the above method and has a chemical structure of [A2H2(C n H 2n )SbCl5]·0.5H2O@SGM.

[0018] Preferably, when n=3, the scintillator molecular formula is [(C 13 H 28 N2)SbCl5]·0.5H2O, molecular weight is 1040.76, crystal system is orthorhombic, space group is Fdd2, unit cell parameters are α=90, β=90, γ=90.

[0019] In a third aspect, the present invention provides the application of the antimony (III)-based flexible scintillator film that can be used for X-ray imaging in the fields of biomedical imaging and nondestructive testing of flexible devices.

[0020] The present invention has the following beneficial effects:

[0021] (1) The present invention designs and synthesizes a new antimony (III)-based scintillator, which is synthesized by the "cooling crystallization method" and can be produced and applied on a large scale at a low cost. Compared with lead halide perovskite nanocrystal scintillator, antimony (III)-based scintillator is environmentally friendly and is a potential alternative material to lead-based scintillator.

[0022] (2) The antimony (III)-based scintillator prepared by the present invention emits orange light in the solid state, with a quantum efficiency of up to 97.25%, a lifetime of microseconds, a large Stokes shift and a wide emission peak. Under X-ray irradiation, the antimony (III)-based scintillator emits orange light with a light yield of up to 32332 photons MeV -1 , surpassing the commercial scintillator BGO, demonstrating potential applications in X-ray detection and imaging.

[0023] (3) The antimony (III)-based scintillator flexible film prepared by the present invention has good mechanical properties and can be repeatedly bent, stretched and compressed. It can be applied to the field of X-ray planar and non-planar imaging, and promote the development of cutting-edge X-ray detectors. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 For Example 1 of the present invention [(C 13 H 28 N2)SbCl5]·0.5H2O synthesis route;

[0025] Figure 2 For Example 1 of the present invention [(C 13 H 28 N2)SbCl5]·0.5H2O single crystal structure;

[0026] Figure 3 For Example 1 of the present invention [(C 13 H 28 Powder X-ray diffraction pattern of N2)SbCl5]·0.5H2O;

[0027] Figure 4 For Example 1 of the present invention [(C 13 H 28Normalized UV-visible absorption spectrum of N2)SbCl5]·0.5H2O;

[0028] Figure 5 For Example 1 of the present invention [(C 13 H 28 Normalized solid-state stimulated emission spectrum of N2)SbCl5]·0.5H2O;

[0029] Figure 6 For Example 1 of the present invention [(C 13 H 28 Solid-state photoluminescence decay curve of N2)SbCl5]·0.5H2O;

[0030] Figure 7 For Example 1 of the present invention [(C 13 H 28 Photoluminescence quantum yield spectrum of N2)SbCl5]·0.5H2O;

[0031] Figure 8 For Example 1 of the present invention [(C 13 H 28 N2)SbCl5]·0.5H2O thermogravimetric analysis curve;

[0032] Fig. 9 For Example 1 of the present invention [(C 13 H 28 N2)SbCl5]·0.5H2O linear response spectrum to X-ray;

[0033] Fig.10 For Example 1 of the present invention [(C 13 H 28 N2)SbCl5]·0.5H2O detection limit spectrum;

[0034] Fig.11 For Example 1 of the present invention [(C 13 H 28 N2)SbCl5]·0.5H2O and BGO light production comparison chart;

[0035] Fig.12 For Example 1 of the present invention [(C 13 H 28 N2)SbCl5]·0.5H2O prepared flexible scintillator thin flexibility test;

[0036] Fig.13 For Example 1 of the present invention [(C 13 H 28 Planar and non-planar imaging of the flexible scintillator film prepared by N2)SbCl5]·0.5H2O. DETAILED DESCRIPTION

[0037] The present invention will be further described below in conjunction with the embodiments, but they are not intended to limit the present invention.

[0038] An antimony (III)-based flexible scintillator film that can be used for X-ray imaging; the chemical structural formulas of the scintillators are [A(C n H 2n )SbCl5]·H2O, wherein A is a piperidinyl group, and n is any integer from 1 to 9. A thermoplastic elastomer maleic anhydride grafted hydrogenated styrene-butadiene block copolymer (SEBS-g-MAH, SGM) is used as a matrix, and a scintillator is mixed with the matrix to prepare a film.

[0039] Embodiment 1: [(C 13 H 28 Preparation of flexible scintillator thin film using N2)SbCl5]·0.5H2O@SGM

[0040] [(C 13 H 28 Preparation of single crystal of N2)SbCl5]·0.5H2O: According to the molar ratio, C 13 H 26 N2: SbCl3 = 1: 1, weigh the raw materials and add them into hydrochloric acid solvent, heat to 110 ° C to dissolve the reactants, cool to room temperature at a rate of 5 ° C every 30 minutes, and finally obtain a single crystal of the target scintillator, filter it, wash it with anhydrous ether, and dry it. The synthetic route is as follows: Figure 1 shown.

[0041] [(C 13 H 28 Preparation of flexible scintillator film: Weigh 0.4g of SGM and add it to 4mL toluene solution, heat and stir at 60℃ until the solution is clear and transparent, grind the target scintillator single crystal into powder in a mortar, weigh 0.2g of scintillator powder and add it to the solution, stir with a magnetic stirrer for 12h until the powder is evenly dispersed. Take the above solution and drop it into a polytetrafluoroethylene mold, evaporate it at room temperature at 30℃ for 24h to obtain the target flexible film, which is recorded as CP2.

[0042] Embodiment 2:

[0043] [(C 13 H 28 Preparation of single crystal of N2)SbCl5]·0.5H2O: According to the molar ratio, C 13 H 26N2:SbCl3=1:0.8, weigh the raw materials and add them into hydrochloric acid solvent, heat to 80°C to dissolve the reactants, cool to room temperature at a rate of 5°C every 30 minutes, finally obtain a single crystal of the target scintillator, filter it, wash it with anhydrous ether, and dry it.

[0044] [(C 13 H 28 Preparation of N2)SbCl5]·0.5H2O@SGM flexible scintillator film: weigh 0.3g of SGM and add it to 3mL of toluene solution, heat and stir at 50℃ until the solution is clear and transparent, grind the target scintillator single crystal into powder in a mortar, weigh 0.18g of scintillator powder and add it to the solution, stir with a magnetic stirrer for 10h until the powder is evenly dispersed. Take the above solution and drop it into a polytetrafluoroethylene mold, evaporate it at room temperature 20℃ for 10h to obtain the target flexible film.

[0045] Embodiment 3:

[0046] [(C 13 H 28 Preparation of single crystal of N2)SbCl5]·0.5H2O: According to the molar ratio, C 13 H 26 N2:SbCl3=1:1.2, weigh the raw materials and add them into DMF, heat to 120°C to dissolve the reactants, cool to room temperature at a rate of 8°C per 30 minutes, finally obtain a single crystal of the target scintillator, filter it, wash it with anhydrous ether, and dry it.

[0047] [(C 13 H 28 Preparation of N2)SbCl5]·0.5H2O@SGM flexible scintillator film: weigh 0.5g of SGM and add it to 5mL toluene solution, heat and stir at 55℃ until the solution is clear and transparent, grind the target scintillator single crystal into powder in a mortar, weigh 0.35g of scintillator powder and add it to the solution, stir with a magnetic stirrer for 11h until the powder is evenly dispersed. Take the above solution and drop it into a polytetrafluoroethylene mold, evaporate it at room temperature 25℃ for 16h to obtain the target flexible film.

[0048] Experimental Example 1: Acquisition of SC-XRD and PXRD data

[0049] Example 1 prepared [(C 13 H 28 The SC-XRD data of N2)SbCl5]·0.5H2O@SGM were obtained on a BrukerSmart Apex CCD diffractometer. The solution is shown in Figure 2 As shown. The [(C 13 H 28The structure of the [(C N2)SbCl5]·0.5H2O crystal is orthorhombic, and the space group is Fdd2. 13 H 28 The P-XRD data of N2)SbCl5]·0.5H2O were obtained on a D8 Advance A25 diffractometer. The test results are shown in Figure 3 As shown, the diffraction peaks obtained experimentally are consistent with the theoretical values, proving that the purity of the crystal is very high.

[0050] Experimental Example 2: Measurement of UV-visible absorption, excitation emission spectrum and luminescence lifetime decay curve

[0051] UV-visible absorption spectroscopy was performed on a Shimadzu UV-3600. The test results are shown in Figure 4 As shown, the scintillator prepared in Example 1 has absorption in the range of 200-400nm. The excitation emission spectrum and the luminescence lifetime decay curve were measured on an Edinburgh FLS-980 spectrophotometer. The excitation emission spectrum used a 450W xenon lamp, the excitation spectrum ranged from 250nm-400nm, and the emission spectrum ranged from 450nm-800nm. The test results are shown in Figure 5 As shown in FIG. 1 , the excitation wavelength of the scintillator prepared in Example 1 is 366 nm, and the emission wavelength is 642 nm, indicating that the emission light of the crystal is orange. The luminescence lifetime decay curve test uses a 375 nm laser, and the test results are shown in FIG. Figure 6 As shown, the luminescence lifetime of the scintillator prepared in this example is 5.16 μs, which is shorter than many antimony (III)-based scintillators that have been reported.

[0052] Experimental Example 3: Test of Photoluminescence Quantum Yield

[0053] The photoluminescence quantum yield test was conducted using an integrating sphere mode under a 450W xenon lamp light source. The test results are shown in Figure 7 As shown, the photoluminescence quantum efficiency of the scintillator prepared in Example 1 is close to 100%, which is greater than that of many antimony (III)-based scintillators, indicating that the crystal has efficient light output.

[0054] Experimental Example 4: TGA Measurement

[0055] TGA measurement uses NETZSCH STA-2500 thermal analyzer. In 40mL / min nitrogen atmosphere, the heating rate is 10K / min, the heating range is RT-500℃, and the test results are as follows Figure 8 The decomposition temperature T of the scintillator prepared in Example 1 is d =255℃, indicating that the crystal has good thermal stability.

[0056] Experimental Example 5: Measurement of X-ray Linear Response and Detection Limit

[0057] The irradiation emission spectrum and detection limit were measured on an Edinburgh FLS-980 spectrophotometer. The irradiation intensity during the measurement was 0.578 μGy air ·s -1 -4.5μGy air ·s -1 , the test results are as follows Fig. 9 As shown, it shows that within a certain range, the X-ray irradiation intensity and dose rate have a certain linear relationship. Using 2 tungsten sheets and 4 copper sheets as attenuation sheets, when the signal-to-noise ratio is 3, the test results are as follows: Fig.10 As shown, the detection limit LoD obtained by the test is 74.30nGy air ·s -1 , which is much smaller than the medical diagnostic standard (5.5μGy air ·s -1 ), and has shown significant application potential in the field of medical testing.

[0058] Experimental Example 6: Measurement of Light Production

[0059] The light production was measured on an Edinburgh FLS-980 spectrophotometer. Using commercial BGO as a reference, a scintillator with a thickness of 100 μm was placed in the same position as BGO. The steady-state XEL spectrum was then integrated to obtain the corresponding photon counting results. It is known that the light production of BGO is 10,000 photons MeV -1 The light output of the scintillator is calculated by the following formulas (1) and (2): 32332 photons MeV -1 , the test results are as follows Fig.11 This shows that the scintillator prepared in Example 1 has a higher light yield, which makes it a strong candidate for the next generation of scintillators.

[0060]

[0061] Experimental Example 7: Imaging of Flexible Scintillator Films

[0062] The size of the flexible scintillator film prepared in Example 1 is 5×5 cm. It does not emit light under sunlight, but emits bright orange under ultraviolet and X-ray irradiation. It is a scintillator film made by doping antimony (III)-based scintillator with polymer SGM. The prepared film has certain flexibility and tensile properties and can be bent, compressed and stretched multiple times, such as Fig.12 and 13 shown.

[0063] Since different metals have different absorption of X-rays, the spatial saturation formed on the scintillator is different, thus forming optical imaging. Fig.13 It can be seen that under the irradiation of X-rays, the internal structures of conch and peanut can be clearly obtained. In addition, when the film and the object to be imaged are bent, the outline of the object to be imaged is also clearly visible under the irradiation of X-rays. The flexible scintillator film prepared in this example can realize planar imaging and non-planar imaging.

[0064] The above shows and describes the basic principles, main features and advantages of the present invention. However, the above is only a specific embodiment of the present invention, and the technical features of the present invention are not limited thereto. Any other implementation methods derived by any technician in the field without departing from the technical solution of the present invention should be included in the patent scope of the present invention.

Claims

1. A method for preparing an antimony (III)-based flexible scintillator film that can be used for X-ray imaging, characterized in that: The method comprises the following steps: Step (1): According to the molar ratio of A2(C n H 2n ): SbCl3 = 1: 0.8-1.2, weigh A2 (C n H 2n ) and SbCl3 are added to a solvent, wherein A is a piperidinyl group and n is any integer from 1 to 9, and the reactants are heated to dissolve, and then cooled, filtered, washed and dried to obtain a target scintillator single crystal, whose molecular formula is [A2H2(C n H 2n )SbCl5]·0.5H2O; Step (2): adding polymer SEBS-g-MAH to a toluene solution, heating and stirring until the solution is clear and transparent, to obtain a SEBS-g-MAH / toluene solution; Step (3): Grind the target scintillator single crystal into powder, add it into SEBS-g-MAH / toluene solution, and stir until the powder is evenly dispersed, wherein the mass ratio of SEBS-g-MAH to scintillator is 1:0.5-0.

75. Step (4): drip the solution obtained in step (3) into a polytetrafluoroethylene mold and volatilize at room temperature to obtain a film.

2. The method for preparing an antimony (III)-based flexible scintillator film that can be used for X-ray imaging according to claim 1, characterized in that: The heating temperature in step (1) is 80-120°C.

3. The method for preparing an antimony (III)-based flexible scintillator film that can be used for X-ray imaging according to claim 1, characterized in that: The solvent in step (1) is hydrochloric acid or DMF.

4. The method for preparing an antimony (III)-based flexible scintillator film for X-ray imaging according to claim 1, characterized in that: In step (1), the cooling rate is 5-10°C every 30 minutes.

5. The method for preparing an antimony (III)-based flexible scintillator film for X-ray imaging according to claim 1, characterized in that: The heating temperature in step (2) is 50-60°C.

6. The method for preparing an antimony (III)-based flexible scintillator film for X-ray imaging according to claim 1, characterized in that: In step (3), the stirring time is 10-12 hours.

7. The method for preparing an antimony (III)-based flexible scintillator film for X-ray imaging according to claim 1, characterized in that: In step (3), the room temperature volatilization temperature is 20-30°C and the time is 10-24h.

8. An antimony (III)-based flexible scintillator film that can be used for X-ray imaging, characterized in that: Prepared by the method according to any one of claims 1 to 7, the chemical structure is [A2H2(C n H 2n )SbCl5]·0.5H2O@SGM.

9. The antimony (III)-based flexible scintillator film for X-ray imaging according to claim 8, characterized in that: When n=3, the scintillator molecular formula is [(C 13 H 28 N2)SbCl5]·0.5H2O, molecular weight is 1040.76, crystal system is orthorhombic, space group is Fdd2, unit cell parameters are α=90, β=90, γ=90.

10. Use of the antimony (III)-based flexible scintillator film for X-ray imaging according to claim 8 in the fields of biomedical imaging and nondestructive testing of flexible devices.

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