Zero-dimensional lead-free antimony halide perovskite for high-resolution x-ray imaging and preparation method and application thereof

Abstract

The application discloses a zero-dimensional lead-free halogenated antimony perovskite for high-resolution X-ray imaging and a preparation method and application thereof, and belongs to the technical field of perovskite materials. The chemical formula of the zero-dimensional lead-free halogenated antimony perovskite for high-resolution X-ray imaging is (AcTP) 2SbCl 5 ; wherein, AcTP is a chemical composition formula C 21 H 20 OP, which has a unique cation structure, and [SbCl 5 ] 2‑ The pyramids are separated by bulky organic cations AcTP + to form a molecular-level zero-dimensional structure, realizing a strong quantum confinement effect. The material exhibits excellent luminescent performance, with a photoluminescence quantum yield (PLQY) of 95.1% at room temperature, and exhibits a negative thermal quenching (NTQ) behavior in a temperature range of 77-300K, overcoming the problem of decreased luminescent efficiency at high temperatures of most low-dimensional lead-free perovskites.

Description

Technical Field

[0001] This application relates to a zero-dimensional lead-free antimony halide perovskite for high-resolution X-ray imaging, its preparation method, and its application, belonging to the field of perovskite material technology. Background Technology

[0002] Low-dimensional lead-free perovskites (LDLFPs) have attracted increasing research interest in recent years due to their fascinating optoelectronic properties and significant environmental benefits. However, most LDLFPs exhibit thermal quenching upon heating, failing to maintain luminescence efficiency at high temperatures and resulting in poor performance under environmental conditions. For example, while reported materials such as (PPN)SbCl and (Gua)SbCl exhibit high luminescence yields under X-ray excitation, their luminescence intensity at room temperature decreases significantly compared to lower temperatures. This not only reduces luminescence efficiency but also leads to energy waste.

[0003] Commercial X-ray scintillators are mainly composed of inorganic crystals, such as BiGeO (BGO), CsI:Tl, and LuAlO:Ce (LuAG:Ce). Although they possess high luminescence yields and excellent stability, they typically require harsh crystallization processes at high temperatures, resulting in significant energy consumption. Organic scintillators offer a wide range of structures and mild growth conditions, but suffer from poor X-ray absorption and low radiation conversion efficiency. Therefore, there is an urgent need to develop novel scintillator materials with mild synthesis conditions, environmentally friendly chemical compositions, excellent stability, and high-performance radiative luminescence.

[0004] Lead halide perovskites, as a class of semiconductor materials with excellent photoelectric properties, have made significant progress in photovoltaic technology and optoelectronics. However, their toxicity and stability issues hinder their commercial application. Low-dimensional lead-free perovskites hold promise for improving stability and reducing toxicity while maintaining excellent photoelectric properties; however, thermal quenching remains a key factor limiting their performance improvement. Therefore, developing low-dimensional lead-free perovskite materials with thermally stable luminescence properties and high-quality X-ray imaging capabilities has significant scientific and application value. Summary of the Invention

[0005] To address the thermal quenching problem in existing low-dimensional lead-free perovskite materials technologies, improve their luminescence efficiency and stability at high temperatures, and enhance X-ray imaging performance, this application proposes a technical solution for a high-performance scintillator material suitable for practical applications.

[0006] The technical solution adopted in this application is as follows:

[0007] According to a first aspect of this application, a zero-dimensional lead-free antimony halide perovskite for high-resolution X-ray imaging is provided, characterized in that the chemical formula of the zero-dimensional lead-free antimony halide perovskite for high-resolution X-ray imaging is (AcTP)2SbCl5.

[0008] AcTP has the chemical formula C 21 H 20 OP.

[0009] Optionally, the chemical formula (C) of the zero-dimensional lead-free antimony halide perovskite used for high-resolution X-ray imaging is... 21 H 20 OP)2SbCl5.

[0010] Optionally, the crystal structure of the zero-dimensional lead-free antimony halide perovskite used for high-resolution X-ray imaging belongs to the orthorhombic crystal system with space group Pbca.

[0011] Optionally, the lattice parameters of the zero-dimensional lead-free antimony halide perovskite used for high-resolution X-ray imaging are as follows: α = β = γ = 90°.

[0012] Optionally, the lattice parameters of the zero-dimensional lead-free antimony halide perovskite used for high-resolution X-ray imaging are as follows: α = β = γ = 90° (at a temperature of 100K).

[0013] Optionally, the crystal structure of the zero-dimensional lead-free antimony halide perovskite for high-resolution X-ray imaging includes: an Sb 3+ Cations and five Cl - Anion coordination forms distorted [SbCl5]. 2- Pyramid, large-volume organic cation AcTP + These pyramids were separated to form a molecular-level zero-dimensional structure.

[0014] In the technical solution of this application, specific large-volume organic cations AcTP are selected. + This achieves the processing of inorganic [SbCl5] 2- The effective separation of the pyramids forms a zero-dimensional structure, achieving a strong structural quantum confinement effect, thus enhancing the quantum confinement effect and improving luminescence performance. Simultaneously, the shallow trap levels and appropriate electron-phonon coupling in the crystal structure enable the material to exhibit a negative thermal quenching effect, overcoming the thermal quenching problem. This application is based on the mechanism of the negative thermal quenching effect, primarily attributed to a phonon-assisted energy compensation process related to shallow trap levels (STLs). This mechanism was verified through temperature-dependent single-crystal X-ray diffraction, electron paramagnetic resonance (EPR) experiments, and density functional theory (DFT) calculations. The zero-dimensional lead-free antimony halide perovskite material prepared in this application for high-resolution X-ray imaging exhibits excellent luminescence performance, with a photoluminescence quantum yield (PLQY) as high as 95.1% at room temperature, and displays negative thermal quenching (NTQ) behavior in the temperature range of 77-300 K, overcoming the problem of decreased luminescence efficiency at high temperatures in most low-dimensional lead-free perovskites.

[0015] Optionally, the zero-dimensional lead-free antimony halide perovskite used for high-resolution X-ray imaging exhibits a photoluminescence quantum yield greater than 95% under room temperature conditions and excitation at a wavelength of 354 nm.

[0016] Optionally, the zero-dimensional lead-free antimony halide perovskite for high-resolution X-ray imaging exhibits negative thermal quenching behavior in the temperature range of 77-300K when excited by UV-vis wavelengths (ultraviolet-visible light range).

[0017] According to a second aspect of this application, a method for preparing the above-mentioned zero-dimensional lead-free antimony halide perovskite for high-resolution X-ray imaging is provided, comprising the following preparation steps:

[0018] The reaction was carried out in a non-polar antisolvent atmosphere by using an antisolvent diffusion method, in which a mixture containing AcTPCl, SbCl3 and a polar solvent was placed.

[0019] Optionally, the polar solvent is ethanol.

[0020] Optionally, the nonpolar antisolvent is diethyl ether.

[0021] Optionally, the amounts of AcTPCl and SbCl3 used in this application are calculated based on the corresponding amounts of (AcTP)2SbCl5.

[0022] Optionally, the molar ratio of AcTPCl to SbCl3 is 2:1.

[0023] Optionally, after the contact reaction, the colorless and transparent crystals with a regular appearance that have been grown are washed three times with diethyl ether to obtain blocky crystals.

[0024] Optionally, the zero-dimensional lead-free antimony halide perovskite crystals used for high-resolution X-ray imaging are regular, transparent, and elongated, emitting an orange-yellow glow under ultraviolet light.

[0025] This application employs an antisolvent diffusion method to synthesize (AcTP)SbCl single crystals at room temperature. The specific steps are as follows: AcTPCl and SbCl are dissolved in a polar solvent at a certain molar ratio, and then slowly added dropwise to a nonpolar antisolvent. The mixture is allowed to stand at room temperature to crystallize, thereby obtaining high-quality (AcTP)SbCl single crystals.

[0026] According to a third aspect of this application, a zero-dimensional lead-free antimony halide perovskite for high-resolution X-ray imaging as described above, and the application of the zero-dimensional lead-free antimony halide perovskite for high-resolution X-ray imaging prepared according to the above preparation method as an X-ray scintillator in the preparation of high-resolution X-ray imaging equipment and the preparation of high-transmittance scintillator screens are provided.

[0027] The scintillator screen has high light transmittance and excellent X-ray imaging performance.

[0028] Optionally, the method for preparing a high-transmittance scintillator screen includes: preparing a high-transmittance scintillator glass screen from a single crystal of zero-dimensional lead-free antimony halide perovskite obtained for high-resolution X-ray imaging by a melt-quenching method.

[0029] The beneficial effects of this application include:

[0030] The zero-dimensional lead-free antimony halide perovskite (AcTP)SbCl provided in this application for high-resolution X-ray imaging exhibits superior luminescence performance compared to existing technologies. It boasts a PLQY (light-to-light emission efficiency) of up to 95.1% at room temperature and displays negative thermal quenching behavior within a temperature range of 77-300 K, demonstrating stable luminescence efficiency at high temperatures. As an X-ray scintillator, its luminescence yield (LY) reaches 51116 ph MeV⁻¹, significantly higher than that of commercial inorganic scintillator BGO (approximately 10000 ph MeV⁻¹), with a detection limit as low as 105.79 nGyair s⁻¹, below the requirement for X-ray medical diagnostics (5.5 μGyair s⁻¹). The prepared scintillator screen exhibits high transmittance and a spatial resolution of up to 20 lp mm⁻¹, enabling clear imaging of objects such as chip circuits and metal springs, making it suitable for high-resolution X-ray imaging. These beneficial effects are fully supported by experimental data, such as PLQY testing, temperature-dependent PL spectroscopy, X-ray luminescence yield, and detection limit testing. Attached Figure Description

[0031] Figure 1 This is a schematic diagram of the structure of acetone-triphenylphosphine chloride;

[0032] Figure 2 The images are of (AcTP)2SbCl5 crystals under sunlight (top) and ultraviolet light at a wavelength of 365nm (bottom), respectively, taken by a metallographic microscope.

[0033] Figure 3 The crystal structure units of (AcTP)₂SbCl₅ are: (a) the asymmetric unit of (AcTP)₂SbCl₅; (b) the organic cation: acetone-triphenylphosphine; (c) [SbCl₅]. 2- Pyramid-shaped pentahedron;

[0034] Figure 4 The crystal structure is (AcTP)2SbCl5;

[0035] Figure 5 [SbCl5] in (AcTP)2SbCl5 2- Unit diagram;

[0036] Figure 6Experimental and simulated powder X-ray spectra of (AcTP)2SbCl5 single crystals;

[0037] Figure 7 The images of (AcTP)2SbCl5 under sunlight and ultraviolet light were taken immediately after synthesis and after being placed in an environment with an air humidity of 60% for sixty days.

[0038] Figure 8 XPS spectrum of (AcTP)2SbCl5;

[0039] Figure 9 The XPS spectrum of (AcTP)₂SbCl₅ is shown for peak separation, where (a) is the 1s peak of C and (b) is the 2p peak of P. 1 / 2 and 2p 3 / 2 Peak (c) is the 3d peak of Sb. 3 / 2 The 1s peaks of 3d5 / 2 and O, and (d) is the 2p peak of Cl. 1 / 2 and 2p 3 / 2 peak;

[0040] Figure 10 Scanning electron microscope image and energy dispersive spectroscopy (EDS) mapping image of (AcTP)₂SbCl₅.

[0041] Figure 11 The room temperature variable excitation fluorescence spectrum of (AcTP)2SbCl5;

[0042] Figure 12 The room temperature excitation and emission spectra of (AcTP)2SbCl5;

[0043] Figure 13 The fluorescence quantum yield of (AcTP)2SbCl5;

[0044] Figure 14 The room-temperature time-resolved fluorescence decay curve of (AcTP)2SbCl5;

[0045] Figure 15 Temperature-varying photographs of (AcTP)2SbCl5 taken at different excitation wavelengths;

[0046] Figure 16 The temperature-varying fluorescence spectra of (AcTP)2SbCl5 under different excitation conditions are shown in (a) at 317 nm excitation and (b) at 354 nm excitation.

[0047] Figure 17 (a) Relationship between photon energy and X-ray absorption coefficient of (AcTP)2SbCl5 and commercial scintillators; (b) Relationship between material thickness and X-ray attenuation efficiency of (AcTP)2SbCl5 and commercial scintillators.

[0048] Figure 18 (a) Fluorescence spectra of (AcTP)2SbCl5 crystal and BGO crystal under X-ray excitation; (b) Fluorescence spectra of (AcTP)2SbCl5 glassy state and BGO crystal under X-ray excitation.

[0049] Figure 19 (a) The fluorescence intensity of the material under X-ray irradiation with different radiation doses; (b) A graph showing the linear relationship between radiation dose and the fluorescence intensity of the material.

[0050] Figure 20 At a dose rate of 13.74 mGys -1 Under X-ray irradiation: (a) Changes in fluorescence emission intensity of the material within 1 hour; (b) Changes in fluorescence emission intensity of the material after 40 switching cycles; (c) Comparison of fluorescence emission intensity of the material after 1, 7 and 14 days in air.

[0051] Figure 21 This is a schematic diagram of the fabrication process of a glassy thin film.

[0052] Figure 22 (a) The variable excitation emission spectrum of (AcTP)2SbCl5 in the glassy state; (b) The UV-Vis transmittance scan.

[0053] Figure 23 Fourier transform infrared spectrum of (AcTP)2SbCl5;

[0054] Figure 24 To use (AcTP)2SbCl5 vitreous film for line-to-card imaging;

[0055] Figure 25 (a) Imaging a lead sheet using an (AcTP)2SbCl5 glassy film; (b) The relationship between the modulation transfer function and spatial resolution calculated from lead sheet imaging.

[0056] Figure 26 For resolution comparison;

[0057] Figure 27 This is a schematic diagram showing the imaging effect of the (AcTP)2SbCl5 glassy film on different objects. Detailed Implementation

[0058] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0059] Antimony trichloride (SbCl3), acetone-triphenylphosphine chloride (structural formula as follows) Figure 1Shown, Acetonyltriphenylphosphonium Chloride, C 21 H 20 OPCl, ethanol (EtOH), and diethyl ether (Ether). All related chemicals and solvents were of analytical grade and used directly in the synthesis process; they were purchased commercially and not further purified.

[0060] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.

[0061] Unless otherwise specified, all test methods are standard and all instrument settings are those recommended by the manufacturer.

[0062] In this application, "room temperature" means 300K.

[0063] Example 1: Synthesis of (AcTP)2SbCl5 crystals

[0064] 0.5 mmol (114.05 mg) of antimony trichloride and 1 mmol (319.3 mg) of acetone-triphenylphosphine chloride were completely dissolved in 5 mL of ethanol in a 20 mL sample vial using ultrasonic dissolution at room temperature. The open sample vial was placed in a wide-mouth bottle containing diethyl ether and sealed. After two days, colorless, transparent crystals with a regular appearance grew inside the sample vial. The crystals were carefully removed from the vial with tweezers and rinsed three times with diethyl ether to obtain blocky crystals. Figure 2 As shown, the crystals are regular, transparent, and elongated, emitting an orange-yellow glow under ultraviolet light.

[0065] Test Example 1: Structure and Characterization of (AcTP)2SbCl5

[0066] (1) Determination and analysis of single crystal structure

[0067] The structure of (AcTP)₂SbCl₅ was determined using single-crystal X-ray diffraction (SCXRD). SCXRD data were acquired using a Synergy-S-plane probe single-crystal diffractometer (Rigaku, Japan) and analyzed using Cu K₂. α ( The X-ray source was used, and data collection was performed using the ω-2θ scanning method. Single-crystal data were collected under 100K conditions with non-in-situ measurements. All raw diffraction data were restored using the CrystalLiaPro program, and empirical absorption correction and crystal plane correction were performed on the absorption coefficients. For structural analysis and refinement, the crystal structure was solved using the Intrinsicphasing algorithm of the ShelXT program. The positions of hydrogen atoms were obtained theoretically by combining the riding model with the raw data, and then the least squares (LS) method of the ShelXL program was used for anisotropic structure refinement to obtain the final data. The final crystallographic information file (CIF) was verified by the PLATON program and the International Union of Crystallography (IUCr) website checkCIF without any A or B type alarms. The crystallographic data and refinement parameters of (AcTP)2SbCl5 are shown in Table 1.

[0068] like Figure 3 , Figure 4 The single-crystal diffraction data shown in Table 1 indicate that (AcTP)₂SbCl₅ crystallizes in the orthorhombic Pbca space group, and one asymmetric unit consists of two AcTP cells. + A cation and a pyramidal [SbCl5] structure with Sb at its center and five Cl atoms coordinated to it. 2- Composition with anions. For example... Figure 5 As shown, [SbCl5] 2- The distances between each Cl atom and the central Sb are not entirely the same. Specifically, the bond length of the Sb-Cl5 bond formed between Cl5 and Sb at the apex of the pyramid varies. Significantly shorter than the bond lengths of the four Cl atoms at the four corners of the pyramid with Sb (Sb-Cl1 is...). Sb-Cl2 is Sb-Cl3 is Sb-Cl4 is There is no coordination between the ions, resulting in a zero-dimensional structure. For example... Figures 2 to 4 It can be seen that the adjacent [SbCl5] 2- Because they are separated by large acetone-triphenylphosphine cations and independently distributed within the crystal structure, this structure allows the luminescent centers [SbCl5] to... 2- Electron transfer is concentrated in a small area and cannot be transferred over long distances, which usually leads to a strong quantum confinement effect.

[0069] Table 1. Crystallographic data and refinement parameters of (AcTP)2SbCl5

[0070]

[0071]

[0072] (2) Powder X-ray diffraction test and material stability

[0073] The freshly synthesized (AcTP)₂SbCl₅ crystals were carefully ground and then subjected to powder X-ray diffraction at room temperature. The remaining crystals were then exposed to air. Figure 6 The image shows a comparison between the experimental X-ray diffraction pattern of (AcTP)₂SbCl₅ crystal and the pattern obtained through simulation using crystal data. It can be seen that the experimental pattern and the simulated pattern obtained from the crystal data obtained by single-crystal X-ray diffraction (simulation program: VESTA) overlap very well, indicating that the prepared crystal is the desired pure phase.

[0074] After being placed in air for 60 days, the diffraction pattern obtained after retesting still maintained a clear and distinguishable peak shape and the same peak position as when the crystal was first synthesized, indicating that (AcTP)2SbCl5 has good air stability. Figure 7 The images show the crystals immediately after synthesis and after being exposed to sunlight and ultraviolet light for 60 days in the air, demonstrating the crystals' excellent stability.

[0075] (3) X-ray photoelectron spectroscopy

[0076] X-ray photoelectron spectroscopy (XPS) can further characterize the phase purity of a sample, such as... Figure 8 and Figure 9 As shown, the photoelectron peaks corresponding to all elements in the crystal agree with the theoretical values, indicating good phase purity of the crystal. High-resolution XPS spectrum. Figure 8 , Figure 9 Multiple peaks for various elements, including Sb, Cl, and P, are displayed. These peaks correspond to the 3d phases of Sb, respectively. 3 / 2 (530.5 eV) and 3d5 / 2 (539.8 eV); 1s of O (532.0 eV); 1s of C (284.8 eV); 2p of Cl 1 / 2 (198.8 eV); Cl 2p 3 / 2 (197.5 eV); 2p of P 1 / 2 (133.4 eV) and 2p 3 / 2 (132.5eV).

[0077] (4) Scanning electron microscopy analysis

[0078] Scanning electron microscopy (SEM) images and elemental mapping using energy dispersive spectrometer (EDS) can reveal the surface morphology of tiny crystals at high resolution and further characterize the actual elemental distribution on the crystals. The crystals were placed on a copper substrate and secured with conductive adhesive. Because the conductive adhesive contains oxygen, the oxygen (O) element in the crystals could not be detected. Figure 10 As shown, the crystal surface is smooth, and Sb, Cl and P elements are uniformly distributed in the crystal without local aggregation, indicating good phase purity of the crystal.

[0079] Test Example 2: Photoluminescence properties of (AcTP)2SbCl5

[0080] (1) Fluorescence spectrum and fluorescence decay curve at room temperature

[0081] like Figure 11 and Figure 12 The fluorescence emission spectrum of (AcTP)₂SbCl₅ under varying excitation was measured. During the test, (AcTP)₂SbCl₅ exhibited a large, broad low-energy (LE) emission peak at 607 nm and a weak, narrow high-energy (HE) emission peak at 463 nm, corresponding to excitation wavelengths of 317 nm and 354 nm, respectively. It is noteworthy that excitation light at 317 nm can simultaneously induce both HE and LE emission peaks in the crystal. Under excitation at 354 nm, the measured quantum yield of the crystal was 95.1%. Figure 13 Under excitation at a wavelength of 317 nm, the fluorescence lifetimes of the HE and LE peaks were 2.03 ns and 4.221 μs, respectively. Figure 14 ).

[0082] (2) Temperature-dependent fluorescence spectroscopy

[0083] like Figure 15 Temperature-dependent photographs were taken of the crystal under different excitation wavelengths, ranging from 77 to 420 K. It can be seen that under 317 nm excitation, the crystal's emission gradually changed from light purple-pink to orange and finally disappeared. Under 354 nm excitation, the crystal's emission gradually changed from orange-red to pale yellow and finally disappeared.

[0084] like Figure 17The temperature-dependent fluorescence spectra of the crystal from 77 to 420 K were tested under different excitation wavelengths. Under 317 nm excitation, the two emission peaks of the crystal exhibited different changes during temperature variation. As the temperature increased, the HE peak underwent normal thermal quenching, but the LE peak showed a significant reverse thermal quenching. When using 354 nm excitation, the remaining LE peak still underwent a very similar reverse thermal quenching.

[0085] Test Example 3: X-ray excitation and luminescence properties and imaging applications of (AcTP)₂SbCl₅

[0086] (1) X-ray excitation and luminescence properties

[0087] The absorption capacity of a crystal for X-rays and the attenuation coefficient of X-rays in the crystal can be obtained through theoretical calculations (e.g., Figure 17 As shown in the figure, its X-ray absorption performance far surpasses that of the organic scintillator anthracene and is very close to that of commercial inorganic scintillators, thanks to the presence of the metal element.

[0088] The fluorescence spectrum of the crystal under X-ray excitation is as follows Figure 18 As shown in (a), it is compared with the commercial scintillator BGO in terms of light yield (LY) (assuming its light yield is 10000ph MeV). -1 By comparison, the light yield of (AcTP)2SbCl5 is approximately 51116 ph MeV. -1 The light yield is significantly higher than that of BGO. As shown in the table, compared with some previously reported scintillators, the superior light yield characteristics of (AcTP)₂SbCl₅ are evident. Besides light yield, the detection limit is also a key performance indicator for evaluating scintillators. A low detection limit not only reduces radiation damage but also improves detection sensitivity. For example... Figure 19 With a signal-to-noise ratio of 3 as the threshold, the detection limit of the crystal is 105.79 nGy. air s -1 This is far below the X-ray requirement for medical diagnosis (5.5 μGy). air s -1 This further highlights its potential for X-ray detection.

[0089] The stability of (AcTP)₂SbCl₅ was tested. For example... Figure 20 The dosage rate used was 13.74 mGy s. -1The stability of (AcTP)₂SbCl₅ under X-ray irradiation was tested for one hour continuously, followed by 40 cycles of switching stability testing and stability testing under humid conditions. The results show that (AcTP)₂SbCl₅ exhibits excellent stability. Furthermore, it maintains good stability even under humid conditions, a traditional weakness of perovskites; after 14 days of exposure to 60% humidity, its radioluminescence intensity remained at 96.9%.

[0090] (2) X-ray imaging

[0091] To explore the practical applications of the materials. Based on previous literature reports, triphenylphosphine-based derivative cations (Ph3P...) - R + Zero-dimensional hybrid perovskites formed by compounds such as (MTP)₂SbCl₅ (Methyltriphenylphosphonium, MTP), (ETP)₂SbCl₅ (Ethyltriphenylphosphonium, ETP), and (HTP)₂SbCl₅ (Heptyltriphenylphosphonium, HTP) typically have low phase transition points. When heated from a low temperature to above the phase transition point, the crystal or powder melts into a liquid state. If a suitable cooling rate is used to lower it to room temperature, a glassy sample with high light transmittance can be obtained. Therefore, thermogravimetric analysis (TG) and differential scanning calorimetry (DSC) were used to characterize the melting point and thermal stability of (AcTP)₂SbCl₅.

[0092] Method for fabricating the scintillation film: After grinding the crystal, place it on aluminum foil, roughly adjusting it into a square shape. Place the aluminum foil on a hot plate and heat it to 180°C. After the crystal is completely melted, adjust the placement of the aluminum foil to spread the molten (AcTP)₂SbCl₅ evenly. Then, quickly remove the aluminum foil from the hot plate and allow the (AcTP)₂SbCl₅ to cool rapidly in air. After the film has completely cooled and hardened, carefully peel off the aluminum foil and remove the film (e.g., ...). Figure 21 (As shown).

[0093] The variation excitation fluorescence spectrum of the scintillation film is as follows Figure 22 As shown in (a). Figure 22 (b) The resulting scintillation film exhibits good transmittance. Fourier transform infrared spectroscopy. Figure 23 The results show that the crystalline, glassy, ​​and AcTPCl salt states are essentially the same, indicating that the organic components remain stable at high temperatures. The light yield (LY) of the scintillation film was measured to be approximately 12,979 ph MeV. -1 ( Figure 18 (b) Imaging tests were performed using a scintillator. First, online X-ray imaging of the card was performed, achieving a maximum resolution of 20 lpmm. -1 ( Figure 24 This is already among the top tier of similar materials. Figure 26 ).like Figure 25 As shown, the modulation transfer function (MTF) calculated using the slanted-edge method also demonstrates a resolution as high as 17.595 lp mm. -1 .

[0094] This ultra-high spatial resolution surpasses that of most commercially available inorganic single-crystal scintillators, lead-based perovskite scintillators, and other zero-dimensional lead-free perovskites. X-ray imaging experiments were conducted on the chip and a plastic capsule containing springs. The camera clearly captured the internal wiring of the chip and the outline of the metal springs within the capsule (e.g., ...). Figure 27 (As shown). Therefore, the excellent X-ray imaging performance and ease of manufacture make these scintillating films very suitable for large-scale production and have broad prospects for commercial applications.

[0095] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and all fall within the scope of the technical solution.

Claims

1. A zero-dimensional lead-free antimony halide perovskite for high-resolution X-ray imaging, characterized in that, The chemical formula of the zero-dimensional lead-free antimony halide perovskite used for high-resolution X-ray imaging is (AcTP)2SbCl5. AcTP has the chemical formula C 21 H 20 OP.

2. The zero-dimensional lead-free antimony halide perovskite for high-resolution X-ray imaging according to claim 1, characterized in that, The zero-dimensional lead-free antimony halide perovskite crystal structure used for high-resolution X-ray imaging belongs to the orthorhombic crystal system with space group Pbca.

3. The zero-dimensional lead-free antimony halide perovskite for high-resolution X-ray imaging according to claim 1, characterized in that, The lattice parameters of the zero-dimensional lead-free antimony halide perovskite used for high-resolution X-ray imaging are as follows: α = β = γ = 90°.

4. The zero-dimensional lead-free antimony halide perovskite for high-resolution X-ray imaging according to claim 1, characterized in that, The crystal structure of the zero-dimensional lead-free antimony halide perovskite used for high-resolution X-ray imaging includes: an Sb 3+ Cations and five Cl - Anion coordination forms distorted [SbCl5]. 2- Pyramid, large-volume organic cation AcTP + These pyramids were separated to form a molecular-level zero-dimensional structure.

5. The zero-dimensional lead-free antimony halide perovskite for high-resolution X-ray imaging according to claim 1, characterized in that, The zero-dimensional lead-free antimony halide perovskite used for high-resolution X-ray imaging exhibits a photoluminescence quantum yield greater than 95% under room temperature conditions and excitation at a wavelength of 354 nm.

6. The zero-dimensional lead-free antimony halide perovskite for high-resolution X-ray imaging according to claim 1, characterized in that, The zero-dimensional lead-free antimony halide perovskite used for high-resolution X-ray imaging exhibits negative thermal quenching behavior in the temperature range of 77-300K when excited by UV-vis wavelengths.

7. The method for preparing zero-dimensional lead-free antimony halide perovskite for high-resolution X-ray imaging according to any one of claims 1 to 6, characterized in that, The preparation steps include the following: The zero-dimensional lead-free antimony halide perovskite for high-resolution X-ray imaging was obtained by reacting a mixture containing AcTPCl, SbCl3, and a polar solvent in a non-polar antisolvent atmosphere using an antisolvent diffusion method.

8. The preparation method according to claim 7, characterized in that, The polar solvent is ethanol; The nonpolar antisolvent is diethyl ether.

9. The zero-dimensional lead-free antimony halide perovskite for high-resolution X-ray imaging as described in any one of claims 1 to 6, and the zero-dimensional lead-free antimony halide perovskite for high-resolution X-ray imaging prepared by the preparation method according to claim 7 or 8, are used as X-ray scintillators in the preparation of high-resolution X-ray imaging equipment and high-transmittance scintillator screens.

10. The application according to claim 9, characterized in that, The method for preparing a high-transmittance scintillator screen includes: preparing a high-transmittance scintillator glass screen from a single crystal of zero-dimensional lead-free antimony halide perovskite used for high-resolution X-ray imaging by a melt quenching method.

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