X-ray delayed imaging-oriented afterglow scintillator material

Abstract

The invention discloses an afterglow scintillator material for X-ray delayed imaging, which is prepared by a high-temperature solid phase method: NaCa3Y1-x (PO4) 3F: xTb < 3 +, 0lt; x is less than or equal to 9%. The afterglow scintillator material can realize high-resolution X-ray afterglow imaging and stable low-dose detection limit, and can perform flat-plate-free X-ray imaging on an electronic object.

Description

Technical Field

[0001] This application relates to the field of inorganic functional material synthesis technology, and in particular to an afterglow scintillator material for X-ray time-lapse imaging. Background Technology

[0002] Flat panel X-ray detectors with active readout mechanisms have wide applications in medical diagnostics, security inspections, and industrial inspections. Existing X-ray detectors primarily rely on the direct conversion of X-ray energy into electrical charge, or the indirect conversion using scintillation materials. Current X-ray detection mainly depends on the integration of a flat panel detector with a thin-film transistor (TFT), resulting in a TFT-integrated flat panel detector. The TFT consists of a pixelated array of photodiodes deposited on a glass substrate.

[0003] While TFT integrated flat panel detectors offer high sensitivity for X-ray detection and internal imaging reconstruction, existing TFT integrated flat panel detectors place higher demands on high-resolution X-ray imaging. Furthermore, flat panel detectors are expensive and unsuitable for X-ray imaging of curved or irregularly shaped objects. To meet the requirements for imaging curved surfaces, flat panel-less X-ray detectors have been proposed. These detectors achieve curved surface imaging by using a flexible, stretchable "soft film" instead of the glass panel in the "glass panel + thin-film transistor (TFT) array".

[0004] The flat-panel X-ray detector uses a scintillation material film that can absorb X-ray energy for imaging detection. During detection, the detector is first irradiated with X-rays, and then the X-rays are turned off. The energy is retained in the non-conductive film in the form of "trapped electrons". The stored photons are released at once by laser scanning, and then a CMOS image is taken to obtain a high-resolution X-ray image of the interior of the object under test.

[0005] To meet the requirements of the usage environment, it is necessary to develop film materials that meet the requirements of flexible TFT substrates. However, despite great efforts, due to the strict requirements of flexible TFT substrates for thin-layer scintillators, existing technologies are unable to obtain flexible TFT substrates that meet the usage requirements, which hinders the development of flexible X-ray detectors.

[0006] Afterglow scintillator materials can store excitation energy and slowly release the captured energy in the form of light emission, making it possible to develop flat-panel-less X-ray detectors. Existing inorganic oxide phosphors, such as SrAl₂O₄:Eu... 2+ / Dy 3+ (Can produce a long green afterglow under X-ray excitation) and NaLuF4:Tb 3+@NaYF4 (can suppress the quenching afterglow time of the material surface for more than 30 days under 50 kV X-ray excitation, but due to the excessively long afterglow time, it is not suitable for biological detection but for use in equipment and instruments), but existing afterglow scintillator materials represented by NaLuF4:Tb³⁺@NaYF4 core-shell nanocrystals still have the problem of low absolute X-ray sensitivity.

[0007] In addition, the existing methods for preparing inorganic afterglow scintillator materials are complex, mainly relying on crystal growth. However, the crystal growth results are affected by many factors, have poor controllability, and require harsh external environmental conditions to generate effective electron-trapped states in the matrix lattice.

[0008] The information disclosed in the background section is intended only to enhance the understanding of the overall background of the invention and should not be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art. Summary of the Invention

[0009] This application addresses the aforementioned technical problems by providing an afterglow scintillator material for X-ray time-delay imaging. This afterglow scintillator material enables high-resolution X-ray afterglow imaging and stable low-dose detection limits, allowing for flat-panel-less X-ray imaging of electronic objects.

[0010] This application provides an afterglow scintillator material for X-ray time-lapse imaging, which is prepared by a high-temperature solid-state method: NaCa3Y 1-x (PO4)3F: x Tb 3+ ,0< x ≤9%.

[0011] Preferably, x Specifically, it is any one of 0.5%, 1%, 3%, 5%, 7%, and 9%; the emission spectrum of the afterglow scintillator material shows multiple narrow-band emission peaks in the wavelength range of 400 nm to 700 nm, and the highest peak of scintillation intensity appears at 550 nm.

[0012] Preferably, the light yield of the afterglow scintillator material is 2339~21211 photons / MeV.

[0013] Preferably, the afterglow lifetime of the afterglow scintillator material can be maintained for more than 30 minutes; The scintillation emission intensity of the afterglow scintillator material increases with increasing X-ray power, which ranges from 10 to 60 keV.

[0014] Preferably, it is NaCa3Y 1-x (PO4)3F: xTb 3+ , x= 7%.

[0015] Preferably, NaCa3Y 1-x (PO4)3F: x Tb 3+ , x= The 7% radiation dose limit is 1.11 nGy / s, and the imaging resolution is 23.2 lp / mm; the imaging effect is clear. After turning off the X-ray source, NaCa3Y 1-x (PO4)3F: x Tb 3+ , x= The afterglow flicker intensity reached its peak at 7%; NaCa3Y 1-x (PO4)3F: x Tb 3+ , x= 7% of the light output value of 21211 photons / MeV.

[0016] Preferably, the high-temperature solid-state method includes the following steps: weighing each raw material according to the stoichiometric ratio, grinding, heating to 300~400℃ and holding for 2~4 hours, taking it out and continuing to grind, heating again to 1000~1200℃ and holding for 10~13 hours, to obtain the afterglow scintillator material.

[0017] Preferably, the heating rate for both heating and reheating is 3-6°C / min.

[0018] Preferably, the raw materials include at least: NaF, CaCO3, CaF2, NH4H2PO4, Y2O3, and Tb4O7.

[0019] Preferably, the molar ratio of each substance in the raw material is NaF:CaCO3:CaF2:Y(NO3)3:NH4H2PO4:TbTb4O7 = 1:2.5:0.5:1- x 3: x， 0< x ≤9%.

[0020] The beneficial effects that this application can produce include: 1) The afterglow scintillator material for X-ray time-delay imaging provided in this application is prepared using fluorapatite (Ca5(PO4)3F) matrix structure, which belongs to hexagonal apatite type crystal, to obtain NaCa3Y. 1-x (PO4)3F: x Tb 3+The material, NaCa3Y, possesses advantages such as simple preparation process, rapid synthesis, and low cost. It is obtained by chemically substituting calcium, phosphorus, and fluorine structural sites. 1-x (PO4)3F: x Tb 3+ The material possesses good thermal, optical, and chemical stability, and utilizes the anion F of this material. - During the process of displacement from the lattice to interstitial sites under high-energy X-ray excitation, vacancies and interstitial pairs are generated, enabling the storage of excitation energy. This allows the material to exhibit afterglow luminescence intensity after X-rays are turned off, thus achieving time-delay imaging. Simultaneously, this material is doped with Tb... 3+ It achieves unique luminescent properties.

[0021] 2) The afterglow scintillator material for X-ray time-delay imaging provided in this application, the method yielding a series of NaCa3Y 1-x (PO4)3F: x Tb 3+ (0≤ x ≤9%) afterglow scintillator materials can all be effectively excited by X-rays and have strong scintillation intensity, with multiple narrow-band emission peaks appearing in the wavelength range of 400 nm to 700 nm; NaCa3Y(PO4)3F:7%Tb 3+ The afterglow lifetime of the scintillator material can be maintained for more than 30 minutes, which meets the afterglow lifetime requirements for biological detection and is suitable for use in biological detection. Its scintillation light yield intensity is higher than that of commercial scintillator Bi4Ge3O. 12 2.12 times. And NaCa3Y(PO4)3F:7%Tb 3+ The scintillator material exhibits a stable, linearly increasing scintillator intensity with increasing X-ray (10–60 keV) irradiation power. Its X-ray imaging resolution reaches 23.2 lp / mm, significantly higher than existing afterglow scintillator materials, enabling clear imaging of electronic objects, devices, plant internal contours, and circuitry. This material, with its efficient X-ray absorption, long afterglow lifetime, and long-term energy capture, provides a feasible material for realizing flat-panel-less X-ray detectors.

[0022] 3) The afterglow scintillator material for X-ray time-delay imaging provided in this application has a simple preparation method with a short reaction time, meets the requirements of energy saving and environmental protection, and is suitable for use in large-scale industrial production. Attached Figure Description

[0023] Figure 1 The NaCa3Y obtained in Examples 1-7 of this invention 1-x (PO4)3F:x Tb 3+ (0≤ x XRD patterns of ≤9%) and Ca 3.5 Y 1.5 (SiO4) 1.5 (PO4) 1.5 Comparison diagram of standard diffraction cards for F phosphor; Figure 2 The X-ray absorption diagram of NaCa3Y(PO4)3F obtained in Example 1 of this invention; Figure 3 The NaCa3Y obtained in Examples 1-7 of this invention 1-x (PO4)3F: x Tb 3+ (0≤ x XEOL and XEPL plots for ≤9%); a is the XEOL plot; b is the XEPL plot; Figure 4 Example 6 of the present invention: NaCa3Y 9.93 (PO4)3F:7%Tb 3+ Afterglow life diagram; Figure 5 Example 6 of the present invention: NaCa3Y 9.93 (PO4)3F:7%Tb 3+ Time-resolved spectra in the image; Figure 6 NaCa3Y as described in Example 6 of this invention 9.93 (PO4)3F:7%Tb 3+ XEPL plots at different X-ray powers; Figure 7 Example 6 of the present invention: NaCa3Y 9.93 (PO4)3F:7%Tb 3+ The radiation dose limit detection results are shown in the figure. Figure 8 Example 6 of the present invention: NaCa3Y 9.93 (PO4)3F:7%Tb 3+ The imaging resolution map; Figure 9 Example 6 of the present invention: NaCa3Y 9.93 (PO4)3F:7%Tb 3+ The images show the internal imaging results of the object; a is the internal imaging of the chip under test; b is a magnified image of a local part of the chip under test; c is a perspective image of the USB flash drive; and d is a perspective image of the peanut. Detailed Implementation

[0024] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The components of the embodiments of the present invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations.

[0025] Therefore, the following detailed description of the embodiments of the invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the invention without inventive effort are within the scope of protection of the invention.

[0026] Technical means not detailed in this application and not used to solve the technical problems of this application are all set according to common general knowledge in the field, and multiple common general knowledge setting methods can be implemented.

[0027] The afterglow scintillator material for X-ray time-lapse imaging provided in this application has the general chemical formula: NaCa3Y 1-x (PO4)3F: x Tb 3+ (0< x ≤9%). All samples were prepared using a high-temperature solid-state method.

[0028] Specifically, the Na element comes from NaF, the Ca element from CaCO3 and CaF2, the P element from NH4H2PO4, the Y element from Y2O3, and the Tb element from Tb4O7. The molar ratio of each reactant is NaF:CaCO3:CaF2:Y(NO3)3:NH4H2PO4:TbTb4O7 = 1:2.5:0.5:1- x 3: x， 0< x ≤9%.

[0029] x Specifically, it can be any one of 0.5%, 1%, 3%, 5%, 7%, or 9%.

[0030] Its preparation method includes the following steps: (1) Weigh NaF, CaCO3, CaF2, Y(NO3)3, NH4H2PO4, and TbTb4O7 accurately according to the stoichiometric ratio; (2) Accurately weighed NaF (AR), CaCO3 (AR), CaF2 (AR), Y(NO3)3, NH4H2PO4 and Tb4O7 are ground in an agate mortar for 10 minutes and then placed in a crucible. The reaction temperature is raised to 350℃ in a box furnace at a heating rate of 5° / min and kept at that temperature for 3 hours before being taken out.

[0031] The present invention will now be described in further detail with reference to the accompanying drawings and embodiments, but this does not limit the present invention in any way. Any modifications or improvements made based on the teachings of the present invention shall fall within the protection scope of the present invention.

[0032] Unless otherwise specified, all materials and instruments used in the following embodiments were obtained through commercial channels; and all detection methods used are existing methods unless otherwise specified.

[0033] The chemical formula of the scintillator material of this invention is NaCa3Y. 1-x (PO4)3F: x Tb 3+ (0< x ≤9%). All samples were synthesized using a high-temperature solid-state method.

[0034] Example 1: Preparation of NaCa3Y(PO4)3F matrix material (1) Weigh 0.1512g NaF (99.9%), 0.6005g CaCO3 (99.9%), 0.2342g CaF2 (99.99%), 0.3387g Y2O3 (99.99%), and 1.03523g NH4H2PO4 (99.9%) according to the stoichiometric ratio.

[0035] (2) Accurately weighed NaF (AR), CaCO3 (AR), CaF2 (AR), Y(NO3)3, NH4H2PO4 and Tb4O7 are ground in an agate mortar for 10 minutes and then placed in a crucible. The reaction temperature is raised to 350℃ in a box furnace at a heating rate of 5° / min and kept at that temperature for 3 hours before being taken out.

[0036] (3) After grinding the sample for another 15 minutes, put it back into the box furnace and raise the reaction temperature to 1100℃ at a heating rate of 5° / min. After holding the temperature for 12 hours, the sample material to be tested is obtained and used for subsequent characterization tests.

[0037] Example 2: Preparation of NaCa3Y 9.995 (PO4)3F: 0.5%Tb 3+ fluorescent powder The preparation process is the same as in Example 1, except that the specific amounts of raw materials used are 0.1512g NaF (99.9%), 0.6005g CaCO3 (99.9%), 0.2342g CaF2 (99.9%), 0.3385g Y2O3 (99.9%), 1.03523g NH4H2PO4 (99.9%), and 0.0056g Tb4O7 (99.9%).

[0038] Example 3: Preparation of NaCa3Y 9.99 (PO4)3F:1%Tb 3+ fluorescent powder The preparation process is the same as in Example 1, except that the specific amounts of raw materials used are 0.1512g NaF (99.9%), 0.6005g CaCO3 (99.9%), 0.2342g CaF2 (99.9%), 0.3353g Y2O3 (99.9%), 1.03523g NH4H2PO4 (99.9%), and 0.0112g Tb4O7 (99.9%).

[0039] Example 4: Preparation of NaCa3Y 9.97 (PO4)3F:3%Tb 3+ fluorescent powder The preparation process is the same as in Example 1, except that the amounts of each raw material are different. The specific amounts of the raw materials are 0.1512g NaF (99.9%), 0.6005g CaCO3 (99.9%), 0.2342g CaF2 (99.9%), 0.3286g Y2O3 (99.9%), 1.03523g NH4H2PO4 (99.9%), and 0.0337g Tb4O7 (99.9%).

[0040] Example 5: Preparation of NaCa3Y 9.95 (PO4)3F:5%Tb 3+ fluorescent powder The preparation process is the same as in Example 1, except that the specific amounts of raw materials used are 0.1512g NaF (99.9%), 0.6005g CaCO3 (99.9%), 0.2342g CaF2 (99.9%), 0.3218g Y2O3 (99.9%), 1.03523g NH4H2PO4 (99.9%), and 0.0561g Tb4O7 (99.9%).

[0041] Example 6 Preparation of NaCa3Y 9.93 (PO4)3F:7%Tb 3+ fluorescent powder The preparation process is the same as in Example 1, except that the specific amounts of raw materials used are 0.1512g NaF (99.9%), 0.6005g CaCO3 (99.9%), 0.2342g CaF2 (99.9%), 0.3150g Y2O3 (99.9%), 1.03523g NH4H2PO4 (99.9%), and 0.0785g Tb4O7 (99.9%).

[0042] Example 7 Preparation of NaCa3Y 9.91 (PO4)3F:9%Tb 3+ fluorescent powder The preparation process is the same as in Example 1, except that the amounts of each raw material are different. The specific amounts of the raw materials are 0.1512g NaF (99.9%), 0.6005g CaCO3 (99.9%), 0.2342g CaF2 (99.9%), 0.3048g Y2O3 (99.9%), 1.03523g NH4H2PO4 (99.9%), and 0.1122g Tb4O7 (99.9%).

[0043] The products obtained in Examples 1-7 were tested separately. Each test method was performed according to commonly used existing methods, which will not be detailed here. The results are as follows: Figures 1-4 As shown: Figure 1 NaCa3Y in Examples 1-7 of this invention 1-x (PO4)3F: x Tb 3+ (0≤ x XRD patterns of samples with a structure ≤9%). The XRD patterns of the samples obtained in Examples 1-7 of this invention are consistent with those of Ca samples with the same structure in the database. 3.5 Y 1.5 (SiO4) 1.5 (PO4) 1.5 A comparison with the standard diffraction cards for F phosphor shows that the diffraction peak positions of each sample are similar to those of Ca. 3.5 Y 1.5 (SiO4) 1.5 (PO4) 1.5 The standard diffraction peak positions of the F phosphor correspond one-to-one, indicating that the samples synthesized in each embodiment are pure-phase NaCa3Y(PO4)3F crystals, belonging to the hexagonal crystal system.

[0044] Figure 2 This is the X-ray absorption spectrum obtained from X-ray absorption fine structure spectroscopy (XAFS) of NaCa3Y(PO4)3F obtained in Example 1. Figure 2 From this, we can know that NaCa3Y(PO4)3F(Z) max= 41, Kα = 21.08 keV) compared to commercial scintillator Bi4Ge3O 12 (Z) max = 20, Kα = 4.16 keV) has a larger X-ray absorption coefficient. At room temperature, a larger X-ray absorption coefficient is beneficial for obtaining stronger afterglow scintillation luminescence.

[0045] Figure 3 a~b represent NaCa3Y in Examples 1, 2, 3, 4, 5, 6, and 7 of this invention. 1-x (PO4)3F: x Tb 3+ (0≤ x XEOL (instantaneous emission spectrum under continuous X-ray irradiation) and XEPL (afterglow scintillation spectrum after the X-ray source is turned off) plots for ≤9%). Figure 3 From a~b, we know that NaCa3Y 1-x (PO4)3F: x Tb 3+ (0≤ x The emission spectra of ≤9%) all exhibit multiple narrow-band emission peaks in the wavelength range of 400 nm to 700 nm. The highest peak of scintillation emission intensity appears at 550 nm, attributed to Tb. 3+ of 5 D4→ 7 The emission peaks at 490 nm, 588 nm, and 624 nm, associated with the F5 transition, are attributed to Tb, respectively. 3+ of 5 D4→ 7 F6, 5 D4→ 7 F4 5 D4→ 7 F3 is Tb 3+ Typical emission peak. With Tb 3+ As the doping concentration increases, the scintillation intensity gradually increases when Tb 3+ The luminescence intensity reaches its peak at a doping concentration of 7 mol%, and begins to decrease when the doping concentration exceeds 7 mol%, indicating that Tb 3+ The optimal ion doping concentration is 7 mol%. The afterglow scintillation spectrum (XEPL) obtained five minutes after the X-ray source is turned off is as follows: Figure 3 As shown in b, the afterglow scintillation intensity varies with Tb 3+ As the doping concentration increases, when Tb 3+ The afterglow scintillation intensity reached its peak at a doping concentration of 7 mol%, and began to decrease when the doping concentration exceeded 7 mol%. Based on the above results, Example 6 NaCa3Y was analyzed. 9.93 (PO4)3F:7%Tb 3+Further research and testing of the material properties are needed.

[0046] Based on the conversion of the integral intensity value, the light yield values ​​of samples 1-7 in Examples are NaCa3Y. 9.995 (PO4)3F:0.5%Tb, 2339 photons / MeV; NaCa3Y 9.995 (PO4)3F:1%Tb, 3439 photons / MeV; NaCa3Y 9.995 (PO4)3F:3%Tb, 4659 photons / MeV; NaCa3Y 9.995 (PO4)3F:5%Tb, 11797 photons / MeV; NaCa3Y 9.995 (PO4)3F:7%Tb, 21211 photons / MeV; NaCa3Y 9.995 (PO4)3F: 9% Tb, 13166 photons / MeV; Bi4Ge3O is a commercially available scintillator material. 12 The light yield is only 10,000 photons / MeV; NaCa3Y 9.995 (PO4)3F:7%Tb has a light yield value of commercially available scintillator Bi4Ge3O 12 2.12 times that is 21211 photosns / MeV.

[0047] Figure 4 Example 6 NaCa3Y 9.93 (PO4)3F:7%Tb 3+ A diagram of the afterglow's lifespan. (From...) Figure 4 As can be seen from the data, the scintillation decay curve tends to stabilize at 40 minutes, indicating that NaCa3Y 9.93 (PO4)3F:7%Tb 3+ The afterglow life of the material can last for more than 30 minutes, and can still be detected by instruments even after up to 2 hours.

[0048] Figure 5 Example 6 NaCa3Y 9.93 (PO4)3F:7%Tb 3+ The time-resolved spectra are shown in the figure, which depict XEPL spectra measured at 5 minutes, 15 minutes, 25 minutes, 40 minutes, and 2 hours after X-rays were turned off. Figure 5The resolved spectral lines obtained at 5, 15, 25, and 40 minutes after X-rays were turned off are shown from top to bottom. By comparison, it can be seen that as the X-ray time increases, the quenching phenomenon of the afterglow scintillation spectrum is still visible to the naked eye at 40 minutes. Two hours after X-rays were turned off, the emission spectrum of the material can be obtained through instrument detection. This afterglow time meets the afterglow lifetime requirements for biological detection and is suitable for use in biological detection.

[0049] Figure 6 NaCa3Y as described in Example 6 of this invention 9.93 (PO4)3F:7%Tb 3+ XEPL plots at different X-ray powers. (Source: [Original Source Name]) Figure 6 As can be seen from the data, the scintillation emission intensity increases linearly with the increase of X-ray source power, indicating that the scintillation emission intensity of the material can be controlled by the X-ray power. The X-ray power range is 10~60 KeV, which is beneficial for application in commercial equipment. Furthermore, the scintillation emission intensity has good stability at each power.

[0050] Figure 7 The NaCa3Y obtained in Example 6 of this invention 9.93 (PO4)3F:7%Tb 3+ The radiation dose limit detection results of the material are shown in Figure 7. It can be seen that after linear fitting, NaCa3Y was obtained. 9.93 (PO4)3F:7%Tb 3+ The radiation dose limit for the material is 1.11 nGy / s.

[0051] Figure 8 Example 6 of the present invention: NaCa3Y 9.93 (PO4)3F:7%Tb 3+ The imaging resolution map, such as Figure 8 As shown, based on a modulation transfer function of 0.2, the imaging resolution is 23.2 lp / mm, indicating that the NaCa3Y... 9.93 (PO4)3F:7%Tb 3+ Thin films prepared from scintillator materials exhibit high imaging resolution. Achieving high imaging resolution has been a persistent challenge for X-ray afterglow imaging. This invention addresses this issue by doping NaCa3Y(PO4)3F with Tb. 3+ After ionization, NaCa3Y 9.93 (PO4)3F:7%Tb 3+ Scintillator materials offer high afterglow imaging resolution, surpassing existing afterglow materials, thus providing a viable material option for realizing flat-panel X-ray detectors.

[0052] Example 6 of the present invention: NaCa3Y 9.93(PO4)3F:7%Tb 3+ The scintillator film required for the flat-panel X-ray detector was fabricated using existing methods and laid on the bottom of the object to be imaged. After irradiating the object surface with an X-ray generator for 30 seconds and then turning off the X-ray generator for 5 minutes, images were taken using a camera to obtain the object images. The results are as follows: Figure 9 As shown in a~d. (By...) Figure 9 From a~d, we can see that in actual testing, the thin film prepared by this scintillator material can produce clear afterglow scintillation imaging of the inside of an object. Furthermore, the circuits and structures inside electronic devices such as chips, circuit boards, and USB flash drives can be clearly observed using this material, which provides the possibility for clear imaging of the inside of objects without a flat panel X-ray detector.

[0053] Example 8 The difference from Example 1 is that the heating in step 2) is: the reaction temperature is raised to 300°C in a box furnace at a heating rate of 3° / min, and then taken out after holding at that temperature for 2 hours; In step 3), the heating process involves raising the reaction temperature to 1000℃ at a heating rate of 3° / min, holding the temperature for 10 hours, and then removing the sample to obtain the final sample.

[0054] Example 9 The difference from Example 1 is that the heating in step 2) is: the reaction temperature is raised to 400°C in a box furnace at a heating rate of 6° / min, and then taken out after holding at that temperature for 4 hours; In step 3), the heating process involves raising the reaction temperature to 1200℃ at a heating rate of 6° / min, holding the temperature for 13 hours, and then removing the sample to obtain the final sample.

[0055] Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A scintillator material for X-ray time-lapse imaging, characterized in that, NaCa3Y was prepared by a high-temperature solid-state method. 1-x (PO4)3F: x Tb 3+ ,0< x ≤9%.

2. The afterglow scintillator material for X-ray time-lapse imaging according to claim 1, characterized in that, x Specifically, it can be any one of 0.5%, 1%, 3%, 5%, 7%, or 9%. The emission spectrum of the afterglow scintillator material exhibits multiple narrow-band emission peaks in the wavelength range of 400 nm to 700 nm, with the highest scintillation intensity peak occurring at 550 nm.

3. The afterglow scintillator material for X-ray time-lapse imaging according to claim 1, characterized in that, The light yield of the afterglow scintillator material is 2339~21211 photons / MeV.

4. The afterglow scintillator material for X-ray time-lapse imaging according to claim 1, characterized in that, The afterglow lifetime of the afterglow scintillator material can be maintained for more than 30 minutes; The scintillation emission intensity of the afterglow scintillator material increases with increasing X-ray power, which ranges from 10 to 60 keV.

5. The afterglow scintillator material for X-ray time-lapse imaging according to claim 1, characterized in that, NaCa3Y 1-x (PO4)3F: x Tb 3+ , x= 7%.

6. The afterglow scintillator material for X-ray time-lapse imaging according to claim 1, characterized in that, NaCa3Y 1-x (PO4)3F: x Tb 3+ , x= The 7% radiation dose limit is 1.11 nGy / s, and the imaging resolution is 23.2 lp / mm; the imaging effect is clear. After turning off the X-ray source, NaCa3Y 1-x (PO4)3F: x Tb 3+ , x= The afterglow flicker intensity reached its peak at 7%; NaCa3Y 1-x (PO4)3F: x Tb 3+ , x= 7% of the light output value of 21211 photons / MeV.

7. The afterglow scintillator material for X-ray time-lapse imaging according to claim 1, characterized in that, The high-temperature solid-state method includes the following steps: weigh each raw material according to the stoichiometric ratio, grind them, heat them to 300~400℃ and keep them at that temperature for 2~4 hours, take them out and continue grinding, heat them again to 1000~1200℃ and keep them at that temperature for 10~13 hours to obtain the afterglow scintillator material.

8. The afterglow scintillator material for X-ray time-lapse imaging according to claim 7, characterized in that, The heating rate for "heating" and "reheating" is 3~6° / min.

9. The afterglow scintillator material for X-ray time-lapse imaging according to claim 7, characterized in that, The raw materials include at least: NaF, CaCO3, CaF2, NH4H2PO4, Y2O3, and Tb4O7.

10. The afterglow scintillator material for X-ray time-lapse imaging according to claim 9, characterized in that, The molar ratio of each substance in the raw material is NaF:CaCO3:CaF2:Y(NO3)3:NH4H2PO4:TbTb4O7 = 1:2.5:0.5:1- x 3: x， 0< x ≤9%.

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