Cuprous iodide complex scintillator, method of making and use in x-ray imaging

Abstract

The application discloses a cuprous iodide complex scintillator, a preparation method thereof and application of the cuprous iodide complex scintillator in X-ray imaging, and belongs to the technical field of luminescent materials. + [Cu2I3L1L2] ‑ Wherein, L1=TMTP, L2=P^N; the cuprous iodide complex single crystal is obtained by a solution diffusion combined solvent evaporation method from cuprous iodide, tris (o-methylphenyl) phosphine and diphenyl-2-pyridine phosphine ligands in an acetonitrile solution. The cuprous iodide complex microcrystal is obtained by growth under the limited action of a polyvinylpyrrolidone surfactant; the cuprous iodide complex microcrystal is used as a scintillator, a scintillator thin film is obtained through a microelectronic printing doctor blade coating technology, and the scintillator thin film can clearly image the internal structure of a real object under X-ray irradiation.

Description

Technical Field

[0001] This invention belongs to the field of luminescent materials technology, specifically a cuprous iodide complex scintillator, its preparation method, and its application in X-ray imaging. Background Technology

[0002] X-ray imaging scintillators convert high-energy radiation into low-energy ultraviolet-visible light, which is particularly important in various applications, including medical diagnostics, industrial flaw detection, nuclear power plants, and space exploration. Achieving a simultaneous improvement in the light yield, stability, environmental friendliness, and uniformity and flexibility of the scintillator screen is a significant challenge in this research field. Therefore, developing novel, high-performance X-ray imaging scintillators has immense scientific and practical value.

[0003] Traditional inorganic scintillators, such as CsI:TI, LuAG:Ce, CdWO4, and YAG:Ce, possess excellent energy resolution and high photoluminescence yield, but their preparation processes are complex, requiring high synthesis temperatures and vacuum conditions, making them neither convenient nor environmentally friendly. Organic scintillators offer the advantages of scalability and solution-processability, allowing for fabrication at room temperature using simple procedures. However, their low X-ray attenuation capability severely limits their development and future commercialization due to limited effective atomic numbers, insufficient exciton utilization, and nonradiative relaxation. Lead halide perovskites composed of heavy elements such as Cs, Pb, Br, and I exhibit excellent performance due to their efficient atomic number composition, high absorption coefficient, and high photoluminescence quantum yield. However, unavoidable self-absorption effects, low stability, and lead toxicity further hinder their practical applications.

[0004] Cuprous halide complexes combine the advantages of diverse electronic properties of coordination metal centers, tunable structure of cuprous halide clusters, and modifiability of organic ligand molecules, making them highly promising for the development of novel high-performance scintillators. In addition, the natural abundance and low toxicity of copper make copper-based compounds more attractive from both an economic and environmental perspective.

[0005] Common neutral cuprous halide complexes can form various charge-neutral inorganic clusters Cu through coordination bonds between Cu(I) and organic ligands. m X m It can be a zero-dimensional (0D) molecular cluster, a one-dimensional (1D) chain, or a two-dimensional (2D) layer, and has achieved a high photoluminescence quantum efficiency (PLQY), but regardless of Cu m X m Regardless of the type of inorganic modules (e.g., molecular clusters, chains, or layers) or the dimensionality of the overall structure, their solubility and solution processability are poor, which greatly limits their practical application in large-scale production. Furthermore, ionic cuprous halide complexes, generally composed of [Cu...],... m X n] -n+m Negatively charged inorganic clusters and L n-m Composed of organic cations, containing only ionic bonds. Due to their pure ionic structure, their stability is generally higher than that of neutral cuprous halide complexes, but their optical emission is weaker, exhibiting lower internal quantum efficiency (IQYs). The AIO (all-on-one) structure can be viewed as a combination of the first two structures, generally including cationic ligands with free P, N, or S binding sites. The cationic nature of the ligands ensures the formation of ionic compounds with anionic inorganic modules, while the free binding sites allow them to directly coordinate with Cu atoms to form coordinate or conjugated bonds. Combining ionic and coordinate bonds into the same structure produces stable cuprous halide scintillators with excellent performance.

[0006] Currently, the luminescence of cuprous halide complex scintillators under X-rays is mostly concentrated in the green and yellow light bands, with few reports on deep blue luminescent cuprous halide complex scintillators. Using Cu-I components and nitrogen-containing heterocyclic compounds as inorganic cores and organic ligands, respectively, radiative luminescence tuning across the entire visible light region was achieved through reactions with a series of pyridine diffracted organic ligands. The optimal emission peaks for CuI(4-me-py) and CuI(3-Br-py) were 433 nm and 453 nm, respectively, but their photoluminescence quantum efficiencies (PLQY) were only 38.3% and 5.7%, respectively. This poor optical performance hinders their application in deep blue luminescent scintillators.

[0007] In addition, most cuprous halide complex scintillators are used in bulk single crystal form after grinding, and the particle size is relatively large. Due to problems such as poor dispersibility, lack of suitable solvents, and low equivalent density of scintillator materials, it is difficult to prepare uniform, transparent and particle-free thin films. Their light scattering will lead to reduced resolution and affect imaging quality. Summary of the Invention

[0008] Purpose of the invention: This invention addresses the problem of low photoluminescence quantum efficiency of cuprous halide complex scintillators that emit deep blue light in the prior art, and provides a cuprous iodide complex scintillator, its preparation method, and its application in X-ray imaging. This invention uses cuprous iodide complex microcrystals as scintillators, and obtains scintillator films through microelectronic printing and coating technology, achieving highly efficient deep blue emission under X-ray irradiation, which can clearly image the internal structure of various objects.

[0009] The technical solution adopted in this invention is as follows:

[0010] In a first aspect, the present invention provides a cuprous iodide complex scintillator, specifically an AIO (all-in-one) cuprous iodide complex scintillator material with the chemical formula [CuL1(CH3CN)3]. + [Cu₂I₃L₁L₂]- The organic ligand components are L1 and L2, where L1 is tris(o-methylphenyl)phosphine (TMTP) and L2 is diphenyl-2-pyridinium phosphine (P^N), and the inorganic component is cuprous iodide.

[0011] Secondly, the present invention provides a method for preparing a single crystal of a cuprous iodide complex scintillator, wherein the single crystal of the cuprous iodide complex scintillator is obtained by crystallizing cuprous iodide, tris(o-methylphenyl)phosphine, and diphenyl-2-pyridinium phosphine in an acetonitrile solution via solution diffusion and solvent evaporation; specifically including the following steps:

[0012] Step 1: At room temperature, dissolve cuprous iodide in acetonitrile to prepare a cuprous iodide acetonitrile solution; wherein the concentration of cuprous iodide is 0.05-0.1 mmol / mL;

[0013] Step 2: Dissolve tris(o-methylphenyl)phosphine and diphenyl-2-pyridinium phosphine in acetonitrile to prepare a mixed ligand solution; in the mixed ligand solution, the concentration of tris(o-methylphenyl)phosphine is 0.0125–0.028 mmol / mL, and the concentration of diphenyl-2-pyridinium phosphine is 0.00625–0.014 mmol / mL;

[0014] Step 3: Place a layer of acetonitrile solution on top of the completely dissolved cuprous iodide acetonitrile solution, and then slowly add the mixed ligand solution to the cuprous iodide acetonitrile solution to prepare a mixed solution; the molar ratio of cuprous iodide to tris(o-methylphenyl)phosphine and diphenyl-2-pyridinephosphine ligands is 3:2:1;

[0015] Step 4: Seal the opening with aluminum foil and poke small holes in the aluminum foil with a needle. Use diffusion and volatilization methods to crystallize the resulting crystal, which is a cuprous iodide complex scintillator single crystal.

[0016] Thirdly, to further improve the resolution of scintillators for X-ray imaging, this invention provides a method for preparing cuprous iodide complex scintillator microcrystals. The cuprous iodide complex microcrystals are obtained by growing cuprous iodide, tris(o-methylphenyl)phosphine, and diphenyl-2-pyridinephosphine ligands under the confinement effect of a polyvinylpyrrolidone surfactant. The specific steps are as follows:

[0017] At room temperature, polyvinylpyrrolidone is dissolved in acetonitrile to prepare a PVP acetonitrile solution, and tris(o-methylphenyl)phosphine and diphenyl-2-pyridinium phosphine are dissolved in the PVP acetonitrile solution; the concentration of polyvinylpyrrolidone in the PVP acetonitrile solution is 5-20 mg / ml;

[0018] Cuprous iodide was then added, and after 12–16 hours of stirring at room temperature until the reaction was complete, the microcrystals were collected by centrifugation at 8000–12000 rpm and washed multiple times with acetonitrile solution to finally obtain cuprous iodide complex scintillator microcrystals; wherein the molar ratio of cuprous iodide to tris(o-methylphenyl)phosphine and diphenyl-2-pyridinephosphine ligands was 3:2:1.

[0019] Fourthly, the present invention provides a method for preparing a cuprous iodide complex scintillator film, wherein the scintillator film is obtained by a coating method using cuprous iodide complex scintillator microcrystals; the specific steps are as follows:

[0020] S1. Add polyvinyl alcohol (PVA) to water and stir to dissolve at 90°C to prepare a PVA aqueous solution with a concentration of 60-180 mg / mL;

[0021] S2. Add cuprous iodide complex scintillator microcrystals to acetonitrile solution to prepare a solution;

[0022] S3. Add the solution from S2 to an aqueous solution of polyvinyl alcohol (PVA), wherein the mass ratio of the cuprous iodide complex scintillator microcrystals to polyvinyl alcohol is 1:2.25-6.75, to prepare scintillator ink;

[0023] S4. Apply the scintillator ink to the substrate material by a scraping method to obtain a scintillator coating. After drying at room temperature, scrape it off to obtain a scintillator film.

[0024] In a preferred embodiment, during the coating process in S4, the scintillator coating can be prepared by coating the glass substrate using microelectronic printing. The specific steps of S4 when coating using microelectronic printing are as follows: inject scintillator ink into the ink sac of the microelectronic printer, print the ink onto the glass substrate by the pressure of the pump to obtain the scintillator coating, and then scrape it off after it dries naturally at room temperature to obtain a scintillator film.

[0025] Fifthly, the present invention provides an application of a scintillator thin film in X-ray imaging. The X-ray imaging application uses a constructed X-ray imaging platform, with the scintillator thin film as a substrate, and the object is placed on top of the film. X-rays irradiate the surface of the film, are reflected by a prism, and are then captured by a camera to obtain the entire X-ray image.

[0026] Beneficial effects:

[0027] 1) The novel AIO (all-in-one) structured cuprous iodide complex scintillator [CuL1(CH3CN)3] provided by this invention + [Cu₂I₃L₁L₂] -(L1=TMTP,L2=P^N), which has a novel structure that contains both ionic and coordinate bonds.

[0028] 2) This invention provides a method for preparing single crystals and microcrystals of cuprous iodide complex scintillators. The preparation is simple through solution mixing, resulting in excellent luminescence performance. It achieves highly efficient deep blue luminescence under X-ray irradiation, with a photoluminescence quantum efficiency (PLQY) of 92.4%. This facilitates the design of novel cuprous halide complex scintillator structures and the realization of higher scintillation performance.

[0029] 3) This invention provides a method for preparing scintillator films using cuprous iodide complex microcrystals, overcoming the shortcomings of traditional cuprous iodide complex crystal preparation methods, such as large particle size and uneven dispersion. The cuprous iodide complex microcrystals prepared by this invention have uniform size and a lamellar morphology that ensures tight stacking between the microcrystal scintillators, ultimately forming a particle-free, uniform, and translucent scintillator film, thus achieving a film thickness of 14 lp mm. -1 High spatial resolution. Attached Figure Description

[0030] Figure 1 [CuL1(CH3CN)3] + [Cu₂I₃L₁L₂] - Structure diagram of a crystal (L1 = TMTP, L2 = P^N);

[0031] Figure 2 [CuL1(CH3CN)3] in Example 1 + [Cu₂I₃L₁L₂] - (L1=TMTP,L2=P^N) Actual and simulated XRD patterns of powder crystals;

[0032] Figure 3 [CuL1(CH3CN)3] in Example 1 + [Cu₂I₃L₁L₂] - Excitation and emission spectra of the crystal (L1 = TMTP, L2 = P^N);

[0033] Figure 4 [CuL1(CH3CN)3] in Example 1 + [Cu₂I₃L₁L₂] - (L1=TMTP,L2=P^N) Lifetime decay curve of the crystal;

[0034] Figure 5 The [CuL1(CH3CN)3] prepared in Example 1 + [Cu₂I₃L₁L₂] -Photogenicity of crystals (L1 = TMTP, L2 = P^N);

[0035] Figure 6 The [CuL1(CH3CN)3] prepared in Example 1 + [Cu₂I₃L₁L₂] - (L1 = TMTP, L2 = P^N) Photoluminescence quantum efficiency of the crystal;

[0036] Figure 7 The [CuL1(CH3CN)3] prepared in Example 1 + [Cu₂I₃L₁L₂] - Radiation stability spectrum of crystals (L1 = TMTP, L2 = P^N).

[0037] Figure 8 The [CuL1(CH3CN)3] prepared in Example 6 + [Cu₂I₃L₁L₂] - (L1=TMTP,L2=P^N) Powder XRD pattern, SEM image and high-resolution TEM image of PVP microcrystals; where (a) is the XRD pattern, (b) is the SEM image and (c) is the high-resolution TEM image.

[0038] Figure 9 The [CuL1(CH3CN)3] prepared in Example 6 + [Cu₂I₃L₁L₂] - (L1 = TMTP, L2 = P^N) X-ray resolution test results of microcrystalline scintillator thin films;

[0039] Figure 10 The [CuL1(CH3CN)3] prepared in Example 6 + [Cu₂I₃L₁L₂] - (L1=TMTP,L2=P^N) X-ray imaging images of microcrystalline scintillator thin films; (a) is chip 1, the left image is chip 1 under normal sunlight; (b) is chip 2, the left image is chip 2 under normal sunlight.

[0040] Figure 11 The structural formulas are those of tris(o-methylphenyl)phosphine TMTP and diphenyl-2-pyridinium phosphine P^N. Detailed Implementation

[0041] The technical solution of the present invention will be described in detail below, but the scope of protection of the present invention is not limited to the embodiments described. In the following embodiments, the raw materials and reagents were directly purchased as commercial chemical reagents without further purification.

[0042] Tris(o-methylphenyl)phosphine: Amex.

[0043] Diphenyl-2-pyridinephosphine: Amex.

[0044] Cuprous iodide: Adamas-beta.

[0045] Polyvinylpyrrolidone: Aladdin K88-96.

[0046] Polyvinyl alcohol: McLean 1799.

[0047] Acetonitrile: Sinopharm AR.

[0048] Equipment model and manufacturer:

[0049] X-ray tube system: Mini-X2, Amptek; Mini-X2 is an X-ray tube system that includes an X-ray tube, power supply, control electronics, and USB communication with a computer. Amptek is the company name.

[0050] Microelectronic printer: Prtronic Scientific3 microelectronic printer from Mifang Technology.

[0051] Example 1

[0052] Example 1 provides a process for preparing an AIO (all-in-one) type cuprous iodide complex scintillator single crystal, specifically a [CuL1(CH3CN)3]... + [Cu₂I₃L₁L₂] - The specific synthesis process of the crystal (L1 = TMTP, L2 = P^N).

[0053] The specific synthesis process is as follows: In a 20 ml glass bottle, CuI (0.3 mmol, 57.0 mg) was completely dissolved in 3 ml of acetonitrile to prepare a CuI acetonitrile solution. In a 10 ml glass bottle, tris(o-methylphenyl)phosphine™TP (0.2 mmol, 60.4 mg) and diphenyl-2-pyridinium phosphine P^N (0.1 mmol, 26.4 mg) were completely dissolved in 7 ml of acetonitrile to prepare a ligand acetonitrile solution. Another 7 ml of acetonitrile was added dropwise to the top of the prepared CuI acetonitrile solution. The ligand acetonitrile solution was then slowly added dropwise to the CuI acetonitrile solution. The glass bottle was sealed tightly with aluminum foil, and a hole was made in the aluminum foil using a needle. After standing for 1–2 days, the crystals obtained by solution diffusion and evaporation were the cuprous iodide complex scintillator. The structural formulas of tris(o-methylphenyl)phosphine™TP and diphenyl-2-pyridinium phosphine P^N are shown below. Figure 11 As shown.

[0054] Example 2

[0055] Example 2 also provides a process for preparing an AIO (all-in-one) type cuprous iodide complex scintillator single crystal, namely [CuL1(CH3CN)3]. + [Cu₂I₃L₁L₂] - The specific synthesis process of (L1 = TMTP, L2 = P^N) crystals. The difference from Example 1 is that CuI (0.3 mmol, 57 mg) was completely dissolved in 4 ml of acetonitrile to prepare a CuI acetonitrile solution, and tris(o-methylphenyl)phosphine TMTP (0.2 mmol, 60.4 mg) and diphenyl-2-pyridinium phosphine (0.1 mmol, 26.4 mg) P^N were completely dissolved in 10 ml of acetonitrile to prepare a ligand acetonitrile solution.

[0056] Example 3

[0057] Example 3 also provides a process for preparing an AIO (all-in-one) type cuprous iodide complex scintillator single crystal, namely [CuL1(CH3CN)3]. + [Cu₂I₃L₁L₂] - The specific synthesis process of (L1 = TMTP, L2 = P^N) crystals. The difference from Example 1 is that CuI (0.3 mmol, 57 mg) was completely dissolved in 6 ml of acetonitrile to prepare a CuI acetonitrile solution, and tris(o-methylphenyl)phosphine TMTP (0.2 mmol, 60.4 mg) and diphenyl-2-pyridinium phosphine (0.1 mmol, 26.4 mg) P^N were completely dissolved in 16 ml of acetonitrile to prepare a ligand acetonitrile solution.

[0058] In Examples 1, 2, and 3 above, [CuL1(CH3CN)3] can be prepared by using different solution concentrations while maintaining the same ratio of CuI to tris(o-methylphenyl)phosphine TMTP and diphenyl-2-pyridinium phosphine P^N of 3:2:1. + [Cu₂I₃L₁L₂] - (L1 = TMTP, L2 = P^N) crystal, i.e. cuprous iodide complex scintillator single crystal; the results of Examples 2 and 3 are the same as those of Example 1, and the prepared crystals have the same color, shape, size, yield and purity.

[0059] The product [CuL1(CH3CN)3] prepared in Example 1 + [Cu₂I₃L₁L₂] - A crystal with L1 = TMTP and L2 = P^N was tested, and the results are as follows:

[0060] Figure 2 The product [CuL1(CH3CN)3] prepared in Example 1+ [Cu₂I₃L₁L₂] - The actual and simulated XRD patterns of the powder crystals (L1 = TMTP, L2 = P^N) were compared. The comparison revealed consistent peak positions at all angles and the absence of extraneous peaks, indicating that the synthesized [CuL1(CH3CN)3]... + [Cu₂I₃L₁L₂] - The crystal structure (L1 = TMTP, L2 = P^N) is consistent with the test results and has high purity with no other impurities.

[0061] Figure 3 The product [CuL1(CH3CN)3] prepared in Example 1 + [Cu₂I₃L₁L₂] - Excitation and emission spectra of the crystal (L1=TMTP,L2=P^N) were obtained. The instrument used for the ultraviolet emission spectrum test was an Edinburgh FLS980 transient spectrometer, and the test parameters were as follows: measurement range: 380-700nm, excitation: 334nm, emission: 450nm, slit: 1.0. Figure 3 This indicates that under optimal excitation by a 334nm xenon lamp light source, [CuL1(CH3CN)3] in Example 1... + [Cu₂I₃L₁L₂] - The emission spectrum of the (L1=TMTP,L2=P^N) crystal ranges from 380nm to 700nm, with the optimal emission peak at 450nm, exhibiting blue light emission.

[0062] Figure 4 The product [CuL1(CH3CN)3] prepared in Example 1 + [Cu₂I₃L₁L₂] - (L1 = TMTP, L2 = P^N) Crystal lifetime decay curve; the lifetime decay curve was obtained by testing with the 375nm laser on the Edinburgh FLS980 transient spectrometer and fitting the curve using the instrument's built-in fitting method; the results show that [CuL1(CH3CN)3] in Example 1... + [Cu₂I₃L₁L₂] - The time required for the fluorescence intensity of the (L1=TMTP,L2=P^N) crystal to drop to 1 / e of the maximum fluorescence intensity at excitation is 2.3 microseconds.

[0063] Figure 5 The product [CuL1(CH3CN)3] prepared in Example 1 + [Cu₂I₃L₁L₂] -Photogenesis of (L1 = TMTP, L2 = P^N) crystals. Photogenesis data acquisition method: Under the same test conditions, using X-rays as the excitation source, the same volume of standard reference BGO and [CuL1(CH3CN)3 prepared in Example 1 were tested. + [Cu₂I₃L₁L₂] - The X-ray emission spectrum of the crystal (L1 = TMTP, L2 = P^N) was obtained, and the photon yield was calculated by integration and formula. By comparing it with the commercial standard scintillator sample BGO (photon yield under X-rays of 10000 photons / MeV), the X-ray photon yield was calculated to be 23974 ± 1198 photons / MeV, indicating that it has excellent scintillator performance.

[0064] Figure 6 The product [CuL1(CH3CN)3] prepared in Example 1 + [Cu₂I₃L₁L₂] - The photoluminescence quantum efficiency (PLQY) of the crystal (L1 = TMTP, L2 = P^N) was measured using an Edinburgh FLS980 transient spectrometer and integrating sphere. The photoluminescence quantum efficiency was obtained by comparing the result with a standard white board and integrating the results using the instrument's built-in integration method. This yielded the product [CuL1(CH3CN)3] prepared in Example 1. + [Cu₂I₃L₁L₂] - The photoluminescence quantum efficiency of the (L1=TMTP,L2=P^N) crystal is 92.4%, which is close to 100%, indicating that it has excellent photoluminescence ability.

[0065] Figure 7 The product [CuL1(CH3CN)3] prepared in Example 1 + [Cu₂I₃L₁L₂] - Radiation stability spectrum of the crystal (L1 = TMTP, L2 = P^N). By continuously irradiating the above scintillator material with a high dose of 4.8 Gy X-rays for 900 s, it was found that its emission intensity under X-rays remained almost unchanged, indicating that it has high radiation resistance.

[0066] In summary, the cuprous iodide complex [CuL1(CH3CN)3] prepared in Example 1 is effective. + [Cu₂I₃L₁L₂] -The (L1=TMTP,L2=P^N) crystal emits a deep blue light spectrum in both ultraviolet and X-ray conditions, ranging from 390nm to 700nm, with the optimal emission peak ranging from 440 to 460nm. Its lifetime under room temperature ultraviolet light is 2.3μs, its luminescence quantum efficiency is 92.4%, and its photon yield under X-rays is 23974±1198 photons / MeV.

[0067] The product [CuL1(CH3CN)3] prepared in Example 1 + [Cu₂I₃L₁L₂] - (L1 = TMTP, L2 = P^N) crystal, its structure is as follows Figure 1 As shown, it consists of negative charge units [Cu2I3L1L2]. - (L1 = TMTP, L2 = P^N) and positive charge unit [CuL1(CH3CN)3] + Composed of (L1 = TMTP), and in both positive and negative charge units, there are coordinate bonds formed by copper atoms and neutral organic ligands. The positive and negative charge units are bonded by ionic bonds, belonging to the monoclinic crystal system. The smallest asymmetric unit of the single crystal structure is also as... Figure 1 As shown. This invention synthesizes a novel cuprous iodide complex by introducing two neutral organic ligands, tris(o-methylphenyl)phosphine TMTP and diphenyl-2-pyridinium phosphine P^N. This novel AIO-type cuprous iodide complex [CuL1(CH3CN)3] + [Cu₂I₃L₁L₂] - (L1 = TMTP, L2 = P^N) possesses both ionic and coordinate bonds. In typical AIO-type cuprous iodide complexes, the negatively charged portion is an inorganic cluster core, and the positively charged portion is an organic cation ligand with free P, N, or S binding sites. However, in the cuprous iodide complex of this invention, in addition to the inorganic cluster core, the negatively charged portion also contains two neutral organic ligands that form coordinate bonds with Cu(I); the positively charged portion, in addition to the organic ligands, also contains neutral organic ligands that form coordinate bonds with Cu(I), which differs from previously reported AIO (all-in-one) type cuprous halide complexes.

[0068] Example 5

[0069] Example 5 provides a method for preparing a cuprous iodide complex scintillator microcrystal according to the present invention, namely a micron-sized sheet-like [CuL1(CH3CN)3]. + [Cu₂I₃L₁L₂] -The specific synthesis process of (L1 = TMTP, L2 = P^N) microcrystals includes: at room temperature, 100 mg of polyvinylpyrrolidone (PVP) (K88-96) was completely dissolved in 20 ml of acetonitrile to prepare a 5 mg / ml PVP acetonitrile solution by stirring for 30 min. Simultaneously, tris(o-methylphenyl)phosphine TMTP (0.2 mmol, 60.8 mg) and diphenyl-2-pyridinium phosphine (0.1 mmol, 26.4 mg) were weighed and added to the prepared PVP acetonitrile solution. After thorough stirring and complete dissolution, a ligand PVP acetonitrile solution was prepared. CuI (0.3 mmol, 57.0 mg) was weighed and added to the prepared ligand PVP acetonitrile solution. After 12–16 h of thorough stirring and reaction, the mixture was centrifuged at 12000 rpm, washed three times with acetonitrile, and then the obtained microcrystals were sealed and stored in acetonitrile solution.

[0070] Example 6

[0071] Example 6 also provides a method for preparing a cuprous iodide complex scintillator microcrystal as described in this invention, namely a micron-sized sheet-like [CuL1(CH3CN)3]. + [Cu₂I₃L₁L₂] - The specific synthesis process of (L1=TMTP,L2=P^N) microcrystals differs from that in Example 5 in that 250 mg of polyvinylpyrrolidone PVP (K88-96) is completely dissolved in 20 ml of acetonitrile to prepare a 12.5 mg / ml PVP acetonitrile solution.

[0072] Example 7

[0073] Example 7 provides a method for preparing a cuprous iodide complex scintillator microcrystal according to the present invention, namely a micron-sized sheet-like [CuL1(CH3CN)3]. + [Cu₂I₃L₁L₂] - The specific synthesis process of (L1=TMTP,L2=P^N) microcrystals differs from that in Example 5 in that 400 mg of polyvinylpyrrolidone PVP (K88-96) is completely dissolved in 20 ml of acetonitrile to prepare a 20 mg / ml PVP acetonitrile solution.

[0074] In Examples 5, 6, and 7, while maintaining a constant ratio of CuI to tris(o-methylphenyl)phosphine TMTP and diphenyl-2-pyridinium phosphine P^N of 3:2:1, [CuL1(CH3CN)3] was obtained by using different concentrations of polyvinylpyrrolidone PVP (K88-96). + [Cu₂I₃L₁L₂] - (L1 = TMTP, L2 = P^N) microcrystals.

[0075] Since the ratio of CuI to tris(o-methylphenyl)phosphine TMTP and diphenyl-2-pyridinium phosphine P^N remained unchanged at 3:2:1 in Examples 5, 6, and 7, the obtained [CuL1(CH3CN)3] was... + [Cu₂I₃L₁L₂] - (L1=TMTP,L2=P^N) The microcrystalline structure remains unchanged. Changing the amount of the polymer polyvinylpyrrolidone (PVP) (K88-96) will only change the thickness and size of the microcrystals, which can be used to control the morphology of the microcrystals.

[0076] Figure 8 The product [CuL1(CH3CN)3] prepared in Example 6 + [Cu₂I₃L₁L₂] - Powder XRD, SEM and high-resolution TEM images of (L1=TMTP,L2=P^N) microcrystals. Figure 8 In this example, (a) represents the product [CuL1(CH3CN)3] prepared in Example 6. + [Cu₂I₃L₁L₂] - The XRD pattern of the tested powder (L1 = TMTP, L2 = P^N) microcrystals showed consistent peak positions at all angles with the simulated XRD pattern, and no extraneous peaks, indicating that the synthesized [CuL1(CH3CN)3]... + [Cu₂I₃L₁L₂] - (L1=TMTP,L2=P^N) The microcrystalline structure is consistent with the test results and has high purity with no other impurities. Figure 8 (b) and Figure 8 (c) in the text refers to the product [CuL1(CH3CN)3] prepared in Example 6. + [Cu₂I₃L₁L₂] - SEM and high-resolution TEM images of the (L1=TMTP, L2=P^N) microcrystals clearly show their specific morphology. Figure 8 (b) and Figure 8 As can be observed in (c) of Example 6, the product [CuL1(CH3CN)3] is... + [Cu₂I₃L₁L₂] - (L1 = TMTP, L2 = P^N) The crystallites have a plate-like morphology, and the morphology is not fixed; they are amorphous plates with a crystallite size of 1–4 μm. [CuL1(CH3CN)3] + [Cu₂I₃L₁L₂] -(L1=TMTP,L2=P^N) Cuprous iodide complex microcrystals are micron-sized plate-like cuprous iodide scintillator crystals formed by the electrostatic attraction and coordination interaction between tris(o-methylphenyl)phosphine TMTP and diphenyl-2-pyridinium phosphine P^N and cuprous iodide under polyvinylpyrrolidone (PVP). The powder X-ray diffraction results of the microcrystals are in good agreement with the simulated structure of the single crystal.

[0077] Example 8

[0078] Example 8 provides a specific process for preparing a scintillator film from cuprous iodide complex microcrystals. The specific preparation process includes: adding 0.6g of polyvinyl alcohol (PVA) to 10ml of water, and dissolving it completely by stirring thoroughly in a sand bath at 90°C to prepare a 60mg / ml PVA aqueous solution, which is colorless and transparent. Taking 40mg of the cuprous iodide complex microcrystals described in Example 2, adding 100μL of acetonitrile solution, and after thorough ultrasonic dispersion, adding 1.5ml of the prepared PVA aqueous solution, and stirring thoroughly for 6 hours to ensure complete dispersion, a scintillator ink with a certain viscosity is prepared. Then, the scintillator ink is coated onto a glass substrate using a microelectronic printer to obtain a scintillator coating, and after evaporation and drying at room temperature for 12 hours, [CuL1(CH3CN)3] is obtained. + [Cu₂I₃L₁L₂] - (L1 = TMTP, L2 = P^N) Microcrystalline scintillator thin film. Finally, the thin film was separated from the glass substrate using a utility knife.

[0079] Example 9

[0080] Example 9 also provides a specific process for preparing a scintillator film using cuprous iodide complex microcrystals. The difference from Example 8 is that 1.2g of polyvinyl alcohol (PVA) is added to 10ml of water to prepare a 120mg / ml PVA aqueous solution. Example 9 and Example 8 are examples of obtaining cuprous iodide complex microcrystal scintillator films by using different concentrations of polyvinyl alcohol (PVA) while ensuring that the content of the luminescent functional component of the scintillator ink remains unchanged.

[0081] Example 10

[0082] Example 10 also provides a specific process for preparing a scintillator film from cuprous iodide complex microcrystals. The difference from Example 8 is that 1.8g of polyvinyl alcohol (PVA) is added to 10ml of water to prepare a PVA aqueous solution of 180mg / ml. Examples 10 and 8 are both examples of obtaining cuprous iodide complex microcrystal scintillator films by using different concentrations of polyvinyl alcohol (PVA) while ensuring that the content of the luminescent functional component of the scintillator ink remains unchanged.

[0083] Examples 8 to 10 use cuprous iodide complex microcrystals to prepare scintillator films. The uniform size and lamellar morphology of the cuprous iodide complex microcrystals ensure that the microcrystal scintillators are tightly stacked, ultimately forming a particle-free, uniform, and semi-transparent scintillator film.

[0084] Example 11

[0085] X-ray Imaging: An X-ray imaging platform was constructed, utilizing a Mini-X2 as the X-ray tube system. The system consisted of a Mini-X2 X-ray tube (Amptek Inc.) as the excitation source, a charge-coupled device (CCD) camera (Nikon D850), a multi-fiber spectrometer, and the camera itself. The target material for the Mini-X2 X-ray tube was Au, P. max =4W, V max =50kV, I max =80μA, X-ray source distance 3cm from scintillator film. Specifically, during the test, the X-ray source emission current was 70μA, the voltage was 50kV, and the X-ray source distance was 3cm from the scintillator film.

[0086] The [CuL1(CH3CN)3] prepared in Example 9 + [Cu₂I₃L₁L₂] - (L1 = TMTP, L2 = P^N) Using a scintillator film as a substrate, an object is placed on top of the film. X-rays irradiating the surface of the film are absorbed by the microcrystalline scintillator film after passing through the interior of chip 1 and chip 2, and then emitted as deep blue visible light. After being reflected by a prism, the light is captured by a camera to obtain an image of the internal structure information of chip 1 and chip 2. Figure 10 The images to the right of (a) and (b) in the figure are the internal structure images of chip 1 and chip 2, respectively.

[0087] During resolution testing, the wire pair cards were also placed on the thin film surface, and the resolution was obtained through an X-ray imaging system. In operation, chip 1 and chip 2 were replaced with wire pair cards, and the standard resolution wire pair card image was as follows: Figure 9 As shown. By Figure 9 It can be seen that its imaging resolution is as high as 14 lp mm. -1 .

[0088] The results of Example 10 confirm that the scintillator film prepared by the method of the present invention can be used for biological and industrial X-ray imaging, and can realize imaging of the internal structural information of chip objects.

[0089] As described above, although the invention has been shown and described with reference to specific preferred embodiments, it should not be construed as limiting the invention itself. Various changes in form and detail may be made without departing from the spirit and scope of the invention.

Claims

1. A cuprous iodide complex scintillator, characterized in that, The chemical formula of the cuprous iodide complex scintillator is [CuL1(CH3CN)3]. + [Cu₂I₃L₁L₂] - Among them, the organic ligand component L1 is tris(o-methylphenyl)phosphine, and L2 is diphenyl-2-pyridinium phosphine.

2. A method for preparing a single crystal of a cuprous iodide complex scintillator, characterized in that, The cuprous iodide complex scintillator is the cuprous iodide complex scintillator as described in claim 1; The cuprous iodide complex scintillator single crystal was obtained by crystallizing cuprous iodide, tris(o-methylphenyl)phosphine, and diphenyl-2-pyridinium phosphine in acetonitrile solution via solution diffusion and solvent evaporation.

3. The method for preparing cuprous iodide complex scintillator single crystals according to claim 2, characterized in that, Includes the following steps: Step 1: Dissolve cuprous iodide in acetonitrile at room temperature to prepare a cuprous iodide-acetonitrile solution; Step 2: Dissolve tris(o-methylphenyl)phosphine and diphenyl-2-pyridinium phosphine in acetonitrile to prepare a mixed ligand solution; Step 3: Place a layer of acetonitrile solution on top of the completely dissolved cuprous iodide acetonitrile solution, and then slowly add the mixed ligand solution to the cuprous iodide acetonitrile solution to prepare a mixed solution; the molar ratio of cuprous iodide to tris(o-methylphenyl)phosphine and diphenyl-2-pyridinephosphine ligands is 3:2:1; Step 4: Seal the opening with aluminum foil and poke small holes in the aluminum foil with a needle. Use diffusion and volatilization methods to crystallize the resulting crystal, which is a cuprous iodide complex scintillator single crystal.

4. The method for preparing cuprous iodide complex scintillator single crystals according to claim 3, characterized in that, In the cuprous iodide acetonitrile solution of step one, the concentration of cuprous iodide is 0.05~0.1 mmol / mL; in the mixed ligand solution of step two, the concentration of tris(o-methylphenyl)phosphine is 0.0125~0.028 mmol / mL, and the concentration of diphenyl-2-pyridinium phosphine is 0.00625~0.014 mmol / mL.

5. A method for preparing cuprous iodide complex scintillator microcrystals, characterized in that, The cuprous iodide complex scintillator is the cuprous iodide complex scintillator as described in claim 1; The cuprous iodide complex microcrystals were obtained by growing cuprous iodide, tris(o-methylphenyl)phosphine, and diphenyl-2-pyridinephosphine ligands under the confinement of a polyvinylpyrrolidone surfactant.

6. The method for preparing cuprous iodide complex scintillator microcrystals according to claim 5, characterized in that, Includes the following steps: At room temperature, polyvinylpyrrolidone was dissolved in acetonitrile to prepare a PVP acetonitrile solution, and tris(o-methylphenyl)phosphine and diphenyl-2-pyridinium phosphine were dissolved in the PVP acetonitrile solution. Cuprous iodide was then added, and after 12-16 h of stirring at room temperature until the reaction was complete, the mixture was centrifuged, washed, and finally the cuprous iodide complex scintillator microcrystals were obtained; the molar ratio of cuprous iodide to tris(o-methylphenyl)phosphine and diphenyl-2-pyridinephosphine ligands was 3:2:

1.

7. The method for preparing cuprous iodide complex scintillator microcrystals according to claim 6, characterized in that, The concentration of polyvinylpyrrolidone in the PVP acetonitrile solution is 5~20 mg / ml; the centrifugation speed is 12000 rpm; and the washing solution is acetonitrile.

8. A method for preparing a cuprous iodide complex scintillator thin film, characterized in that, The scintillator film is obtained by a scraping method from the cuprous iodide complex scintillator microcrystals of claim 5.

9. The method for preparing the scintillator thin film according to claim 8, characterized in that, Includes the following steps: S1. Add polyvinyl alcohol to water to prepare a PVA aqueous solution with a concentration of 60~180 mg / mL; S2. Add cuprous iodide complex scintillator microcrystals to acetonitrile solution to prepare a solution; S3. Add the solution from S2 to the PVA aqueous solution, wherein the mass ratio of the cuprous iodide complex scintillator microcrystals to polyvinyl alcohol is 1:2.25~6.75, to prepare scintillator ink; S4. Apply the scintillator ink to the substrate material using a scraping method to obtain a scintillator coating. After drying at room temperature, scrape it off to obtain a scintillator film.

Images