Zero-dimensional organic-inorganic hybrid metal halide scintillator and preparation method and application thereof

Abstract

The invention discloses a zero-dimensional organic-inorganic hybrid metal halide scintillator and a preparation method and application thereof, and belongs to the technical field of luminescent materials. The chemical general formula of the zero-dimensional organic-inorganic hybrid metal halide scintillator is (A0. 5L0. 5O4Cl2) (TPP) 4Cl. 4MeOH, wherein both A and L in the formula are lanthanide ions. The invention further discloses a preparation method and application of the zero-dimensional organic-inorganic hybrid metal halide scintillator. The zero-dimensional organic-inorganic hybrid metal halide scintillator effectively weakens non-radiation energy transfer between luminescence centers, solves the problems of complex synthesis conditions, high cost, insufficient processability and poor X-ray absorption coefficient, energy resolution and luminescence efficiency of a traditional scintillator material, and has a wide application prospect.

Description

Technical Field

[0001] This invention belongs to the field of luminescent materials technology, specifically relating to a zero-dimensional organic-inorganic hybrid metal halide scintillator, its preparation method, and its application. Background Technology

[0002] Scintillators are optical materials that can convert high-energy ionizing radiation (such as X-rays) into visible light, playing an important role in fields such as medical diagnostics, non-destructive testing, safety inspection, scientific research, and environmental monitoring. Especially in the field of X-ray imaging, the performance of X-ray-excited scintillators directly determines the core indicators of detectors such as sensitivity, dose level, and resolution, and is a key factor affecting imaging quality and application effectiveness.

[0003] Current mainstream inorganic scintillators (such as CsI:Tl, LYSO:Ce, LuAG:Ce, Bi4Ge3O) 12 While inorganic scintillators (such as CdWO4) have been commercialized, they suffer from significant drawbacks: their synthesis requires extreme conditions, such as high temperature, high pressure, or inert gas protection, leading to high production costs and complex processes; simultaneously, some inorganic scintillators exhibit excessively long afterglow or slow luminescence decay, affecting the real-time performance of dynamic imaging. Organic scintillators, on the other hand, have attracted attention due to their mild synthesis conditions, highly modifiable chemical structures, and tunable luminescence performance. However, they still have significant shortcomings in X-ray absorption capacity and energy resolution, with insufficient absorption coefficients for high-energy X-rays; furthermore, the light yield of organic materials is generally lower than that of inorganic materials, resulting in poorer energy resolution and difficulty in meeting the requirements of high-precision detection.

[0004] Therefore, exploring novel scintillators that combine high efficiency in radiation emission, high stability, and good solution processability has become a core challenge in breaking through current technological bottlenecks and promoting the development of X-ray detection technology towards low dose, high resolution, and flexibility. Summary of the Invention

[0005] The problem to be solved by this invention is to provide a zero-dimensional organic-inorganic hybrid metal halide scintillator, its preparation method and application, so as to solve the problems of complex synthesis conditions, high cost, insufficient processability and poor X-ray absorption coefficient, energy resolution and luminous efficiency of existing scintillator materials.

[0006] The technical solution adopted to solve its technical problem is a zero-dimensional organic-inorganic hybrid metal halide scintillator, the general chemical formula of which is (A... 0.5 L 0.5 O4Cl2)(TPP)4Cl·4MeOH, where A and L are both lanthanide ions.

[0007] Preferably, the zero-dimensional organic-inorganic hybrid metal halide scintillator has the chemical formula (Tb0.5 Eu 0.5 O4Cl2)(TPP)4Cl·4MeOH.

[0008] More preferably, the zero-dimensional organic-inorganic hybrid metal halide scintillator is triclinic with space group [missing information]. P Cell parameters a = 19.3045 Å, b = 19.8064 Å, c = 20.1662 Å, α = 89.684°, β = 66.4537°, γ =85.477°, Z = 4.

[0009] This invention also provides a method for preparing the above-mentioned zero-dimensional organic-inorganic hybrid metal halide scintillator, comprising the following steps: The product is synthesized by dissolving cyanomethyltriphenylphosphine chloride, ACl3·6H2O and LCl3·6H2O in methanol and then using a solvothermal method.

[0010] A preferred method for preparing a zero-dimensional organic-inorganic hybrid metal halide scintillator includes the following steps: The product is synthesized by dissolving cyanomethyltriphenylphosphine chloride, TbCl3·6H2O and EuCl3·6H2O in methanol and then using a solvothermal method.

[0011] Preferably, the ratio of cyanomethyltriphenylphosphine chloride, ACl3·6H2O, LCl3·6H2O and methanol is (0.3~0.4) g:(0.05~0.1) g:(0.05~0.1) g:2 mL.

[0012] More preferably, the ratio of cyanomethyltriphenylphosphine chloride, TbCl3·6H2O, EuCl3·6H2O and methanol is (0.3~0.4) g:(0.05~0.1) g:(0.05~0.1) g:2 mL.

[0013] More preferably, the feed-to-liquid ratio of cyanomethyltriphenylphosphine chloride, ACl3·6H2O, LCl3·6H2O and methanol is 0.3377 g:0.0933 g:0.0916 g:2 mL.

[0014] More preferably, the feed-to-liquid ratio of cyanomethyltriphenylphosphine chloride, TbCl3·6H2O, EuCl3·6H2O and methanol is 0.3377 g:0.0933 g:0.0916 g:2 mL.

[0015] Preferably, the solvothermal method includes the following steps: carrying out the synthesis reaction at 95~105℃ for 4~6 days under sealed conditions to obtain the product.

[0016] More preferably, the synthesis reaction temperature is 100℃ and the time is 5 days.

[0017] This invention also provides the application of the above-mentioned zero-dimensional organic-inorganic hybrid metal halide scintillators in X-ray detection and imaging.

[0018] The present invention has the following beneficial effects: This invention synthesizes zero-dimensional organic-inorganic hybrid metal halide scintillators using a low-temperature solvothermal method, effectively solving the problems of harsh synthesis conditions, environmental unfriendliness, and poor processability associated with traditional inorganic scintillators. It also overcomes the issues of low X-ray absorption coefficient and insufficient energy resolution found in organic scintillators. Furthermore, the compound (Tb... 0.5 Eu 0.5 Tb in O4Cl2)(TPP)4Cl·4MeOH 3+ / Eu 3+ The ions are completely separated by the triphenylphosphine cation, and its unique zero-dimensional structure effectively suppresses non-radiative energy transfer between luminescent centers, thereby significantly improving the radiative luminescence efficiency. The light yield is as high as 46105 Ph / MeV, which is significantly better than commercially available LuAG:Ce scintillators. At the same time, the zero-dimensional organic-inorganic hybrid metal halide scintillator of the present invention also exhibits high stability and good solution processability, providing a certain research and development foundation for flexible X-ray imaging. Attached Figure Description

[0019] Figure 1 For (Tb) 0.5 Eu 0.5 Schematic diagram of the crystal structure of O4Cl2)(TPP)4Cl·4MeOH; Figure 2 For (Tb) 0.5 Eu 0.5 Powder X-ray diffraction pattern of O4Cl2)(TPP)4Cl·4MeOH; Figure 3 For (Tb) 0.5 Eu 0.5 Thermogravimetric analysis curve of O4Cl2)(TPP)4Cl·4MeOH; Figure 4 For (Tb) 0.5 Eu 0.5 Infrared spectrum of O4Cl2)(TPP)4Cl·4MeOH; Figure 5 For (Tb) 0.5 Eu 0.5UV-Vis absorption spectrum of O4Cl2)(TPP)4Cl·4MeOH; Figure 6 For (Tb) 0.5 Eu 0.5 Photoluminescence performance test diagrams of O4Cl2)(TPP)4Cl·4MeOH; where (a) is the excitation-emission spectrum; (b) is the CIE color coordinate diagram; (c) is the emission spectrum at different excitation wavelengths; and (d) is the CIE color coordinate diagram at different excitation wavelengths. Figure 7 For (Tb) 0.5 Eu 0.5 Light yield test graph of O4Cl2)(TPP)4Cl·4MeOH; where (a) is (Tb) 0.5 Eu 0.5 (a) Radiative emission spectra of O4Cl2)(TPP)4Cl·4MeOH and LuAG:Ce; (b) Radiative emission spectra of (Tb 0.5 Eu 0.5 Spectra of radiation emission of O4Cl2)(TPP)4Cl·4MeOH under different X-ray doses. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the invention; that is, the described embodiments are merely some embodiments of the invention, and not all embodiments.

[0021] Example 1 A zero-dimensional organic-inorganic hybrid metal halide scintillator with the chemical formula (Tb 0.5 Eu 0.5 O4Cl2)(TPP)4Cl·4MeOH;(Tb 0.5 Eu 0.5 O4Cl2)(TPP)4Cl·4MeOH belongs to the triclinic crystal system, space group [missing information]. P Cell parameters a =19.3045 Å, b = 19.8064 Å, c = 20.1662 Å, α = 89.684°, β = 66.4537°, γ =85.477°, Z = 4.

[0022] This embodiment also includes a method for preparing the above-mentioned zero-dimensional organic-inorganic hybrid metal halide scintillator, comprising the following steps: (1) Weigh 0.3377 g of cyanomethyltriphenylphosphine chloride, 0.0933 g of TbCl3·6H2O and 0.0916 g of EuCl3·6H2O, add 2 mL of methanol and mix well to obtain a mixed solution; (2) The mixed solution was sealed in a polytetrafluoroethylene liner and the synthesis reaction was carried out at 100°C for 5 days. Then, it was naturally cooled to room temperature, and the solvent was evaporated to obtain colorless and transparent (Tb) solution. 0.5 Eu 0.5 O4Cl2)(TPP)4Cl·4MeOH crystals.

[0023] Example 2 A zero-dimensional organic-inorganic hybrid metal halide scintillator with the chemical formula (Tb 0.5 Eu 0.5 O4Cl2)(TPP)4Cl·4MeOH.

[0024] This embodiment also includes a method for preparing the above-mentioned zero-dimensional organic-inorganic hybrid metal halide scintillator, comprising the following steps: (1) Weigh 0.3 g of cyanomethyltriphenylphosphine chloride, 0.05 g of TbCl3·6H2O and 0.05 g of EuCl3·6H2O, add 2 mL of methanol and mix well to obtain a mixed solution; (2) The mixed solution was sealed in a polytetrafluoroethylene liner and the synthesis reaction was carried out at 95°C for 6 days. Then, it was naturally cooled to room temperature, and the solvent was evaporated to obtain colorless and transparent (Tb) solution. 0.5 Eu 0.5 O4Cl2)(TPP)4Cl·4MeOH crystals.

[0025] Example 3 A zero-dimensional organic-inorganic hybrid metal halide scintillator with the chemical formula (Tb 0.5 Eu 0.5 O4Cl2)(TPP)4Cl·4MeOH.

[0026] This embodiment also includes a method for preparing the above-mentioned zero-dimensional organic-inorganic hybrid metal halide scintillator, comprising the following steps: (1) Weigh 0.4 g of cyanomethyltriphenylphosphine chloride, 0.1 g of TbCl3·6H2O and 0.1 g of EuCl3·6H2O, add 2 mL of methanol and mix well to obtain a mixed solution; (2) The mixed solution was sealed in a polytetrafluoroethylene liner and the synthesis reaction was carried out at 105°C for 4 days. Then, it was naturally cooled to room temperature, and the solvent was evaporated to obtain colorless and transparent (Tb) solution. 0.5 Eu 0.5O4Cl2)(TPP)4Cl·4MeOH crystals.

[0027] Experimental Example 1. Crystal structure analysis For (Tb) 0.5 Eu 0.5 The crystal structure of O4Cl2)(TPP)4Cl·4MeOH was analyzed, and the results are as follows: Figure 1 As shown.

[0028] from Figure 1 As can be seen, each Tb atom coordinates with 4 O atoms and 2 Cl atoms to form a [TbCl₂O₄] octahedron, and each Eu atom coordinates with 4 O atoms and 2 Cl atoms to form a [EuCl₂O₄] octahedron. Both types of octahedrons are connected to triphenylphosphine through shared oxygen atoms; at the same time, they are completely isolated by the wide-bandgap triphenylphosphine, thus forming a zero-dimensional crystal structure at the molecular level; free Cl atoms also exist in the crystal structure. - Ions and methanol molecules.

[0029] 2. PXRD diffraction analysis First, take the (Tb) from Example 1 0.5 Eu 0.5 O4Cl2)(TPP)4Cl·4MeOH crystals were ground into powder in a mortar, then a sample was prepared and tested using a powder X-ray diffractometer. The results are as follows: Figure 2 As shown.

[0030] from Figure 2 As can be seen from the example, (Tb) of Example 1 0.5 Eu 0.5 The positions of the PXRD diffraction peaks of O4Cl2)(TPP)4Cl·4MeOH are consistent with the fitted SCXRD data, indicating that the synthesized (Tb 0.5 Eu 0.5 O4Cl2)(TPP)4Cl·4MeOH is the pure phase.

[0031] 3. Thermogravimetric analysis A simultaneous thermal analyzer of model STA449F3 was used to analyze the (Tb) of Example 1. 0.5 Eu 0.5 Thermogravimetric analysis was performed on O4Cl2)(TPP)4Cl·4MeOH under the following conditions: N2 atmosphere, temperature range of 25~800℃, heating rate of 10℃ / min; the results are as follows. Figure 3 As shown.

[0032] from Figure 3 As can be seen from this, when the temperature range is between 40 and 100℃, (Tb 0.5 Eu 0.5The mass of O4Cl2)(TPP)4Cl·4MeOH decreases slightly due to the desorption of methanol (MeOH) molecules; however, when the heating temperature exceeds 200℃, the mass decreases again, at which point (Tb 0.5 Eu 0.5 O4Cl2)(TPP)4Cl·4MeOH begins to decompose.

[0033] 4. Infrared spectroscopy analysis The (Tb) of Example 1 was analyzed using a Nicoletis 10 Fourier transform infrared spectrometer. 0.5 Eu 0.5 Infrared spectroscopy analysis was performed on O4Cl2)(TPP)4Cl·4MeOH, with a spectral range of 4000–400 cm⁻¹. -1 The result is as follows Figure 4 As shown.

[0034] from Figure 4 It can be seen from this that 3500 cm -1 The nearby absorption peaks are due to the stretching vibrations of the OH bonds in the methanol molecule, 3000~2800 cm⁻¹. -1 The nearby absorption peaks are attributed to the stretching vibrations of the CH bond, 1680–1600 cm⁻¹. -1 The absorption peaks around 1400 cm⁻¹ belong to the stretching vibration of the C=C bond. -1 The absorption peaks around 1100 cm⁻¹ are due to the stretching vibration of the PO bond. -1 The absorption peaks near the 800 cm⁻¹ are due to the stretching vibrations of the CP bond; while those at 800 cm⁻¹ are due to the stretching vibrations of the CP bond. -1 The absorption peaks around 500 cm⁻¹ are due to the stretching vibrations of the Tb-Cl / Eu-Cl bonds. -1 The absorption peak at that point belongs to the stretching vibration of the Tb-O / Eu-O bond.

[0035] 5. Ultraviolet spectroscopy analysis Using PerkinElmer LAMBDA 750 UV vis NIR spectrometer for (Tb) in Example 1 0.5 Eu 0.5 The UV-Vis absorption spectra of O4Cl2)(TPP)4Cl·4MeOH were analyzed, with a test range of 200–800 nm; the results are as follows. Figure 5 As shown.

[0036] from Figure 5 As can be seen from the example, (Tb) of Example 1 0.5 Eu 0.5 The UV absorption edge of O4Cl2)(TPP)4Cl·4MeOH is located at 276 nm.

[0037] 6. Photoluminescence performance test The (Tb) of Example 1 was analyzed using an Edinburgh FS5 fluorescence spectrometer. 0.5 Eu 0.5 The photoluminescence properties of O4Cl2)(TPP)4Cl·4MeOH were tested, and the results are as follows: Figure 6 As shown.

[0038] from Figure 6 As can be seen from this, (Tb 0.5 Eu 0.5 O4Cl2)(TPP)4Cl·4MeOH exhibits broadband absorption in the 250–400 nm range, corresponding to Tb 3+ 4f 8 →4f 7 5d 1 Leap and Eu 3+ 4f 6 →4f 5 5d 1 Leap ( Figure 6 (a purple portion), under ultraviolet light excitation at 282 nm, the compound emits bright orange light, with the cluster peaks near 550 nm representing Tb. 3+ The 5D4-7F5 transition, and the cluster peaks near 611 nm originate from Eu. 3+ of 5 D0→ 7 F2 jump ( Figure 6 (a. Orange section). Figure 6 b shows that the CIE color coordinates of this compound are (0.48, 0.49).

[0039] In addition, for (Tb) 0.5 Eu 0.5 Emission spectra of O4Cl2)(TPP)4Cl·4MeOH were measured at different excitation wavelengths, ranging from 260 to 380 nm, with intervals of 10 nm. Figure 6 c shows that the intensity of the emission peak changes with the excitation wavelength; and the CIE chromaticity coordinates at different excitation wavelengths show that ( Figure 6 d), by changing the excitation wavelength, it is possible to control (Tb) 0.5 Eu 0.5 The emission color of O4Cl2)(TPP)4Cl·4MeOH was precisely controlled, effectively achieving the emission color transition from green light to yellow light and then to red light.

[0040] 7. Analysis of Photovoltaic Output Light yield (LY), as an important indicator, reflects the ability of a scintillator to convert high-energy ionizing radiation into visible light. To evaluate the invention (Tb... 0.5 Eu 0.5 The application potential of O4Cl2)(TPP)4Cl·4MeOH in the field of scintillators was investigated. Using the commercial scintillator LuAG:Ce (LY = 25000 photons / MeV) as a reference, the light yield was calculated by comparing radiation intensity. The results are as follows: Figure 7 As shown.

[0041] from Figure 7 From this, we can see that (Tb 0.5 Eu 0.5 The light yield of O4Cl2)(TPP)4Cl·4MeOH reached 46105 Ph / MeV, significantly higher than that of commercially available LuAG:Ce scintillators; furthermore, under different X-ray doses (Tb 0.5 Eu 0.5 The radiation emission spectrum of O4Cl2)(TPP)4Cl·4MeOH shows that (Tb 0.5 Eu 0.5 The intensity of radiation emission from O4Cl2)(TPP)4Cl·4MeOH increases with increasing X-ray dose.

[0042] The present invention has been described according to the above embodiments. It should be understood that the above embodiments do not limit the present invention in any way. All technical solutions obtained by equivalent substitution or equivalent transformation fall within the scope of the present invention.

Claims

1. A zero-dimensional organic-inorganic hybrid metal halide scintillator, characterized in that, The zero-dimensional organic-inorganic hybrid metal halide scintillator has the general chemical formula (A) 0.5 L 0.5 O4Cl2)(TPP)4Cl·4MeOH, where A and L are both lanthanide ions.

2. The zero-dimensional organic-inorganic hybrid metal halide scintillator as described in claim 1, characterized in that, The zero-dimensional organic-inorganic hybrid metal halide scintillator has the chemical formula (Tb 0.5 Eu 0.5 O4Cl2)(TPP)4Cl·4MeOH.

3. The zero-dimensional organic-inorganic hybrid metal halide scintillator as described in claim 2, characterized in that, The zero-dimensional organic-inorganic hybrid metal halide scintillator is triclinic with space group [space group number missing]. P Cell parameters a = 19.3045 Å, b = 19.8064 Å, c = 20.1662 Å, α = 89.684°, β = 66.4537°, γ = 85.477°, Z = 4.

4. The method for preparing the zero-dimensional organic-inorganic hybrid metal halide scintillator according to any one of claims 1 to 3, characterized in that, Includes the following steps: The product is synthesized by dissolving cyanomethyltriphenylphosphine chloride, ACl3·6H2O and LCl3·6H2O in methanol and then using a solvothermal method.

5. The method for preparing a zero-dimensional organic-inorganic hybrid metal halide scintillator as described in claim 4, characterized in that, The ratio of cyanomethyltriphenylphosphine chloride, ACl3·6H2O, LCl3·6H2O and methanol is (0.3~0.4) g:(0.05~0.1) g:(0.05~0.1) g:2 mL.

6. The method for preparing a zero-dimensional organic-inorganic hybrid metal halide scintillator as described in claim 5, characterized in that, The feed-to-liquid ratio of cyanomethyltriphenylphosphine chloride, ACl3·6H2O, LCl3·6H2O and methanol is 0.3377 g:0.0933 g:0.0916 g:2 mL.

7. The method for preparing a zero-dimensional organic-inorganic hybrid metal halide scintillator as described in claim 4, characterized in that, The solvothermal method includes the following steps: a synthesis reaction is carried out under sealed conditions at 95~105℃ for 4~6 days to obtain the product.

8. The method for preparing a zero-dimensional organic-inorganic hybrid metal halide scintillator as described in claim 7, characterized in that, The synthesis reaction was carried out at a temperature of 100°C for 5 days.

9. The application of the zero-dimensional organic-inorganic hybrid metal halide scintillator according to any one of claims 1 to 3 in X-ray detection and imaging.

Images