A bionic stereoscopic artificial compound eye scintillator detection device for spatiotemporal perception and time delay reading in three-dimensional space
Patent Information
- Application Number
- CN202611159063.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-07-31
- Publication Date
- 2026-10-27
AI Technical Summary
[0006]针对现有技术中纳米晶直接掺入光敏树脂时易团聚、沉降、界面结合差、光学散射强和光纤耦合效率低的问题，本发明提出一种用于三维空间中时空感知与延时读取的仿生立体人工复眼闪烁体探测装置，采用稀土卤氟化物纳米晶作为X射线响应发光组分，并通过表面有机配体处理或表面可聚合改性，使纳米晶能够稳定分散于光敏树脂基体中；随后通过光固化成型，制备均相复合闪烁微透镜；再通过原位光固化方式实现复合闪烁微透镜与光纤端面的光耦合连接，形成独立的X射线响应探测单元；最后将多个探测单元排布于半球形支撑体表面，形成仿生立体人工复眼闪烁体探测装置
（1）本发明采用仿生立体复眼闪烁体探测装置通过多个探测单元的空间光强分布实现X射线入射方向感知，适用于核安全监测、工业无损检测、空间辐射探测和复杂辐射场监测；
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Figure CN122983995A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a biomimetic three-dimensional artificial compound eye scintillator detection device for spatiotemporal perception and delayed reading in three-dimensional space, belonging to the fields of radiation detection and biomimetic optical sensing. Background Technology
[0002] With the development of fields such as nuclear safety monitoring, medical radiology, industrial non-destructive testing, space radiation detection, and complex environmental radiation field monitoring, higher requirements have been placed on the spatial positioning, orientation identification, dose distribution acquisition, and radiation event recording of X-ray radiation sources. Traditional X-ray detectors mostly adopt planar or single-point detection structures, which can usually only obtain local dose information or two-dimensional projection information, making it difficult to simultaneously achieve a large field of view, multi-channel parallel response, and three-dimensional spatial orientation perception.
[0003] Bionic compound eye structures possess characteristics such as a large field of view, multiple channels, and parallel sensing, making them suitable for constructing space-distributed radiation detection arrays. However, most existing bionic compound eye detection structures focus on geometric arrangement and optical structure design, while their core detection unit materials still suffer from problems such as insufficient X-ray absorption efficiency, unstable emission output, low fiber coupling efficiency, and poor response consistency between channels.
[0004] Rare-earth-doped nanocrystalline materials possess high chemical stability and tunable luminescence properties, making them suitable for X-ray responsive luminescence detection. Among them, Lu-based rare-earth halofluoride nanocrystals, due to their high atomic number Lu content, exhibit good X-ray absorption capabilities; Tb... 3+ Ions can produce green characteristic luminescence and can serve as centers for X-ray radiative luminescence response. Furthermore, by adjusting the F / Br or F / I halogen composition, the local structure, defect states, and trap levels of the material can be further modulated, thus facilitating the realization of a dual-mode response of radiative luminescence (RL) and photoluminescence (OSL).
[0005] However, the following problems still exist when nanocrystals are directly added to photosensitive resin to prepare composite microlenses: First, the surface of nanocrystals is often coated with organic ligands such as oleic acid and oleylamine, which have insufficient compatibility with acrylate photosensitive resins and are prone to aggregation and sedimentation; Second, uneven dispersion of nanocrystals will lead to decreased light transmittance, enhanced scattering, and unstable light output of the composite resin; Third, if there are bubbles or interface defects between the microlens and the fiber end face, it will reduce the optical signal coupling efficiency; Fourth, the existing technology lacks a nanocrystal composite scintillating microlens suitable for multi-channel biomimetic compound eye array integration and its fiber coupling preparation method. Summary of the Invention
[0006] To address the problems of easy aggregation, sedimentation, poor interfacial bonding, strong optical scattering, and low fiber coupling efficiency when nanocrystals are directly incorporated into photosensitive resins in existing technologies, this invention proposes a biomimetic three-dimensional artificial compound eye scintillator detection device for spatiotemporal sensing and delayed reading in three-dimensional space. Rare-earth halofluoride nanocrystals are used as the X-ray responsive luminescent component, and surface organic ligand treatment or surface polymerizability modification enables the nanocrystals to be stably dispersed in the photosensitive resin matrix. Subsequently, a homogeneous composite scintillator microlens is prepared by photocuring. Then, in-situ photocuring is used to achieve optical coupling between the composite scintillator microlens and the fiber end face, forming an independent X-ray responsive detection unit. Finally, multiple detection units are arranged on the surface of a hemispherical support to form the biomimetic three-dimensional artificial compound eye scintillator detection device.
[0007] A biomimetic stereoscopic artificial compound eye scintillator detection device for spatiotemporal perception and delayed reading in three-dimensional space. The biomimetic stereoscopic artificial compound eye includes several X-ray response detection units 3, a hemispherical support 2, and a hollow cylindrical support substrate 1. The X-ray response detection units 3 are arranged in a fixed array and inserted sequentially into the outer surface of the hemispherical support 2 to form a curved compound eye detection structure. Each X-ray response detection unit 3 includes a photocurable rare-earth halofluoride nanocrystalline composite scintillator microlens 4 and a cladding fiber conduction component 5. The cladding fiber conduction component 5 and the photocurable rare-earth halofluoride nanocrystalline composite scintillator microlens are connected in a conductive structure. Lens 4 is coupled to form a detection unit. Cladding fiber transmission component 5 converges along the inner side of hemispherical support 2 and passes downward through hollow cylindrical support substrate 1. Cladding fiber transmission component 5 is externally connected to image data receiver. The photocurable rare earth halide fluoride nanocrystal composite scintillation microlens 4 includes a photosensitive resin matrix and rare earth halide fluoride nanocrystals uniformly dispersed in the photosensitive resin matrix. The photocurable rare earth halide fluoride nanocrystal composite scintillation microlens 4 generates a radioluminescence RL response under X-ray irradiation and a photoexcited emission OSL response under near-infrared light excitation, thereby realizing real-time X-ray response and delayed reading of radiation information.
[0008] Preferably, the rare earth halide fluoride nanocrystals are NaLuF4:Tb 3+ NaLu(F / Br)4:Tb 3+ NaLu(F / I)4:Tb 3+ One or more of these, Lu matrix is beneficial for improving X-ray absorption capacity, Tb 3+ Ions provide a green luminescence response, and the F / Br or F / I composition modulation is beneficial to improve the defect states and trap energy levels of nanocrystals, thereby realizing a dual-mode response of radiative luminescence (RL) and photo-induced luminescence (OSL).
[0009] Preferably, the photosensitive resin is one or more of polyurethane acrylate, epoxy acrylate, polyester acrylate, polyether acrylate, amino acrylate, or acrylate; the rare earth halide fluoride nanocrystal composite scintillation microlens contains 1-15 wt% rare earth halide fluoride nanocrystals. By adjusting the nanocrystal doping amount, resin composition, and photocuring conditions, a photocurable rare earth halide fluoride nanocrystal composite scintillation microlens with good luminescence intensity, light transmittance, and mechanical stability can be obtained. The shape of the photocurable rare earth halide fluoride nanocrystal composite scintillation microlens can be made into a hemispherical, spherical, micro-convex lens shape, or a curved structure matching the fiber end face to improve the collection of X-ray response luminescence signals and fiber coupling efficiency.
[0010] Preferably, the maximum lateral dimension of the photocurable rare earth halide fluoride nanocrystal composite scintillation microlens is 0.5~3mm, the height is 0.2~2mm, and the radius of curvature is 0.3~3mm.
[0011] Preferably, the fabrication method of the X-ray response detection unit includes the following specific steps: S1. Preparation of rare earth halofluoride nanocrystals: LuCl3 solution, TbCl3 solution, oleic acid and 1-octadecene are mixed evenly. Under an inert atmosphere, mixture A is placed at 120~180℃ for 20~60 min for dehydration reaction to obtain mixture A. After cooling to room temperature, NaOH methanol solution and fluorinated halofluoride methanol solution are added to obtain mixture B. The mixture is kept at 40~70℃ for 20~60 min, heated to 70~100℃ and kept at this temperature to remove methanol, and then heated to 260~320℃ for 10~120 min. After cooling to room temperature, the solid and liquid are separated. The solid is washed successively with cyclohexane and anhydrous ethanol to obtain rare earth halofluoride nanocrystals; the fluorinated halofluoride methanol solution is NH4F methanol solution, NH4F / NH4Br methanol mixture or NH4F / NH4I methanol mixture. S2. Surface treatment of rare earth halide fluoride nanocrystals: Rare earth halide fluoride nanocrystals are uniformly dispersed in a non-polar solvent to obtain a rare earth halide fluoride nanocrystal dispersion. Organic ligands are added to the rare earth halide fluoride nanocrystal dispersion, and the reaction is carried out at a temperature of 40~120℃ for 0.5~12h to form an organic coating layer on the surface of the rare earth halide fluoride nanocrystals. Unreacted organic ligands are removed by centrifugation with ethanol to obtain modified rare earth halide fluoride nanocrystals. S3. Modified rare earth halide fluoride nanocrystals are uniformly dispersed in isoborneol acrylate, and the non-polar solvent is removed under reduced pressure to obtain a pre-dispersion slurry of modified rare earth halide fluoride nanocrystals. Photosensitive resin and photoinitiator are added to the pre-dispersion slurry of modified rare earth halide fluoride nanocrystals and mixed evenly. After vacuum degassing treatment, a composite photosensitive resin slurry of modified rare earth halide fluoride nanocrystals is obtained. S4. Preparation of X-ray Response Detection Unit: Modified rare earth halide fluoride nanocrystalline composite photosensitive resin slurry is injected into the material tank of a 3D printer to create a hollow hemispherical mold. The modified rare earth halide fluoride nanocrystalline composite photosensitive resin slurry is then injected into the hollow hemispherical mold. The fiber end face of the cladding fiber transmission component is inserted into the modified rare earth halide fluoride nanocrystalline composite photosensitive resin slurry. The slurry is then cured by ultraviolet light with a wavelength of 365~405nm, which couples the photocured rare earth halide fluoride nanocrystalline composite scintillation microlens of the cladding fiber transmission component with electrical signals, thus obtaining the X-ray response detection unit.
[0012] More preferably, in step S1, the concentration of LuCl3 solution is 0.05~2.0 mol / L; the concentration of TbCl3 solution is 0.05~2.0 mol / L; the concentration of NaOH methanol solution is 0.1~5.0 mol / L; the concentration of NH4F methanol solution is 0.05~2.0 mol / L; the concentration of NH4F in the NH4F / NH4Br methanol mixed solution is 0.05~2.0 mol / L; the molar ratio of NH4F to NH4Br is 1:0.001~0.5; the concentration of NH4F in the NH4F / NH4I methanol mixed solution is 0.05~2.0 mol / L; the molar ratio of NH4F to NH4I is 1:0.001~0.5; the volume ratio of oleic acid to 1-octadecene is 1:0.5~5; and the concentration of LuCl3 in mixed solution A is 0.005~0.15 mol / L.
[0013] More preferably, in step S2, the nonpolar solvent is cyclohexane, n-hexane, toluene, or chloroform, the concentration of the rare earth halofluoride nanocrystal dispersion is 0.1~100g / L, the organic ligand contains acrylate, methacrylate, vinyl, phosphate, or silane groups, and the amount of organic ligand added is 0.1~30wt% of the rare earth halofluoride nanocrystal.
[0014] More preferably, in step S3, the concentration of modified rare earth halofluoride nanocrystals in the pre-dispersed slurry is 1-15 wt%, the photoinitiator is one or more of 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylphenylacetone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, or bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and the amount of photoinitiator added is 0.1-5 wt% of the mass of the photosensitive resin; the viscosity of the modified rare earth halofluoride nanocrystal composite photosensitive resin slurry is 500-5000 mPa·s.
[0015] Preferably, the radius of the hemispherical support 2 is 5~50mm, and the distance between the centers of adjacent X-ray response detection units 3 is 1~2mm.
[0016] Preferably, the incident polar angle θ of the X-ray irradiation is 0~90°, the azimuth angle φ is 0~360°, and the wavelength of the near-infrared light is 800~1100nm.
[0017] The number of X-ray response detection units is 7 to 300, preferably 112. When the number of X-ray response detection units is 112, it is divided into 7 rings from the top to the bottom of the hemisphere, with the number of detection units in each ring being 1, 6, 11, 16, 21, 26, and 31 respectively. The biomimetic stereoscopic artificial compound eye scintillator detection device is used to acquire the spatial light intensity distribution generated by X-ray irradiation in real time in radiative emission (RL) mode, and to store and read radiation history information in optically excited emission (OSL) mode. By acquiring the emission images of each cladding fiber output end and extracting the corresponding ROI light intensity value, the X-ray incident response center is determined by the region of maximum light intensity or the light intensity weighting center, thereby obtaining the X-ray incident polar angle θ and azimuth angle φ, where θ is 0 to 90° and φ is 0 to 360°.
[0018] The beneficial effects of this invention are: (1) The present invention uses a biomimetic three-dimensional compound eye scintillator detection device to realize the X-ray incident direction sensing through the spatial light intensity distribution of multiple detection units, which is suitable for nuclear safety monitoring, industrial non-destructive testing, space radiation detection and complex radiation field monitoring; (2) This invention uses rare earth halofluoride nanocrystals as X-ray responsive luminescent components, wherein the Lu matrix is beneficial for improving X-ray absorption capacity, and Tb 3+ Ions provide green luminescence centers, and F / Br or F / I halogen modulation is beneficial for improving material trapping and luminescence response; (3) The present invention improves the compatibility between nanocrystals and photosensitive resin by treating the surface of nanocrystals with organic ligands or by polymerizing them, thereby reducing the risk of nanocrystal agglomeration and sedimentation and improving the uniformity and stability of the composite microlens. (4) The present invention uses in-situ photocuring to connect the photocured rare earth halofluoride nanocrystal composite scintillation microlens to the fiber end face, which can reduce interface bubbles and mechanical shedding, improve optical signal coupling efficiency and detection unit stability; the hemispherical or spherical crown-shaped composite scintillation microlens are prepared by photocuring one-time molding method, which solves the problem of how to further prepare the luminescent nanocrystals into fiber-coupled microlens structures. (5) The photocurable rare earth halofluoride nanocrystal composite scintillation microlens of the present invention simultaneously supports real-time response of X-ray radiation emission (RL) and delayed readout of near-infrared light-excited emission (OSL), and can be used for real-time radiation sensing and storage and retrieval of radiation history information. Attached Figure Description
[0019] Figure 1 A schematic diagram of the overall structure of the biomimetic three-dimensional artificial compound eye scintillator detection device; Figure 2 A schematic diagram showing the coupling between the photocurable rare earth halide fluoride nanocrystal composite scintillation microlens and the cladding fiber transmission component of the X-ray response detection unit. Figure 3 This is a schematic diagram showing the relationship between the X-ray incident distance and the fiber array response. Figure 4 This is a schematic diagram showing the relationship between the X-ray incident direction and the fiber array response. Figure 5 The images shown are the orientation photos calculated by simulation and the actual experimental photos of the photocurable rare earth halide fluoride nanocrystal composite scintillation microlens in Example 1. Figure 6 The images shown are the orientation photos calculated from the simulation of the photocurable rare earth halide fluoride nanocrystal composite scintillation microlens in Example 2, and the actual experimental photos. Figure 7 The images shown are simulation calculations of the orientation of the photocurable rare earth halide fluoride nanocrystal composite scintillation microlens in Example 3, and actual experimental photographs. Detailed Implementation
[0020] The present invention will be further described in detail below with reference to specific embodiments, but the scope of protection of the present invention is not limited to the content described.
[0021] This invention relates to a biomimetic stereoscopic artificial compound eye scintillator detection device for spatiotemporal perception and delayed reading in three-dimensional space (see embodiment). Figure 1 The biomimetic three-dimensional artificial compound eye scintillator detection device includes several X-ray response detection units 3, a hemispherical support 2, and a hollow cylindrical support substrate 1. The X-ray response detection units 3 are arranged in a fixed array and sequentially inserted into the outer surface of the hemispherical support 2 to form a curved compound eye detection structure. Each X-ray response detection unit 3 includes a photocurable rare-earth halofluoride nanocrystal composite scintillator microlens 4 and a cladding fiber conduction component 5. The cladding fiber conduction component 5 (commercially available cladding fiber) and the photocurable rare-earth halofluoride nanocrystal composite scintillator... Microlenses 4 are coupled together to form a detection unit. Cladding fiber transmission components 5 converge along the inner side of the hemispherical support 2 and pass downward through the hollow cylindrical support substrate 1. The cladding fiber transmission components 5 are externally connected to an image data receiver. The photocurable rare earth halide fluoride nanocrystal composite scintillation microlens 4 includes a photosensitive resin matrix and rare earth halide fluoride nanocrystals uniformly dispersed in the photosensitive resin matrix. The photocurable rare earth halide fluoride nanocrystal composite scintillation microlens 4 generates a radioluminescence RL response under X-ray irradiation and a photoexcited luminescence OSL response under near-infrared light excitation.
[0022] A schematic diagram of the coupling between the photopolymerized rare-earth halide fluoride nanocrystal composite scintillation microlens and the cladding fiber transmission component of the X-ray response detection unit is shown below. Figure 2This structure effectively improves the coupling efficiency of incident light signals at different angles and enhances the system's ability to detect weak radiation signals. By adjusting the radius of curvature, refractive index, and numerical aperture of the fiber, the optical signal transmission efficiency and spatial response characteristics can be further optimized. The X-ray responsive luminescent component supports both radiative emission (RL) and optically stimulated emission (OSL) modes. In RL mode, the probe material generates an instantaneous luminescence response during X-ray irradiation. The light signal is collected by the microlens radiation absorption component and transmitted to the data receiver through the cladding fiber transmission component, enabling real-time acquisition of radiation intensity, incident direction, and dynamic change information. In OSL mode, electrons generated by irradiation are trapped in the trap energy level of the microlens radiation absorption component and released under the stimulation of 800-1100 nm light, achieving delayed reading and spatiotemporal storage of radiation events.
[0023] like Figure 3 As shown, when the distance between the X-ray source and the biomimetic stereoscopic artificial compound eye scintillator detection device changes, the response intensity distribution of different cladding fiber transmission components will change accordingly; as the distance to the X-ray source increases, the overall received light intensity gradually weakens, and at the same time, the response distribution characteristics of the detection units in different regions of the array also change; by analyzing the light intensity matrix output by the fiber array, the identification and prediction of X-ray source distance information can be realized; for example... Figure 4 As shown, when X-rays are incident in different directions, the detection units located in different spatial positions will generate different response signals, thus forming an array activation mode with directional characteristics. By analyzing the output signals of different cladding fiber transmission components, the incident polar angle θ and azimuth angle φ of the X-ray source can be obtained, realizing direction perception in three-dimensional space.
[0024] The biomimetic three-dimensional artificial compound eye scintillator detection device has an incident polar angle θ of 0~90° and an azimuth angle φ of 0~360° for X-ray irradiation; the wavelength of the near-infrared light is 800~1100nm.
[0025] Example 1: This example describes a biomimetic stereoscopic artificial compound eye scintillator detection device for spatiotemporal perception and delayed storage retrieval in three-dimensional space. It comprises 112 X-ray response detection units 3, with a center-to-center spacing of 0.3 mm between adjacent X-ray response detection units 3. The photocurable rare-earth halofluoride nanocrystal composite scintillator microlens includes a photosensitive resin (polyurethane acrylate) and rare-earth halofluoride nanocrystals (NaLuF4:Tb) uniformly dispersed in the photosensitive resin matrix. 3+ The rare earth halide fluoride nanocrystal composite scintillation microlens contains 1.0 wt% rare earth halide fluoride nanocrystals; the rare earth halide fluoride nanocrystals contain Tb 3+ The doping molar concentration is 15 mol%, and the particle size of the rare earth halide nanocrystals is 42 nm. The specific steps for fabricating the X-ray response detection unit are as follows: S1. Preparation of rare earth halofluoride nanocrystals: LuCl3 and TbCl3 were dissolved in deionized water to prepare 0.5 mol / L LuCl3 and 0.5 mol / L TbCl3 solutions, respectively; NaOH and NH4F were dissolved in methanol to prepare 1 mol / L NaOH methanol solution and 0.5 mol / L NH4F methanol solution, respectively; LuCl3 solution, TbCl3 solution, oleic acid, and 1-octadecene were mixed evenly (the volume ratio of oleic acid to 1-octadecene was 2:1). 3. Under argon atmosphere protection, the mixture was placed at 150℃ for 30 min to dehydrate and obtain mixture A (the concentration of LuCl3 in mixture A was 0.039 mol / L). After cooling to room temperature, NaOH methanol solution and NH4F methanol solution were added to obtain mixture B. The mixture was kept at 50℃ for 30 min, then heated to 80℃ and kept at 80℃ for 30 min to remove methanol. The mixture was then heated to 295℃ and reacted for 30 min. After cooling to room temperature, the solid and liquid were separated. The solid was washed with cyclohexane and anhydrous ethanol to obtain rare earth halide fluoride nanocrystals. S2. Surface treatment of rare earth halide fluoride nanocrystals: Rare earth halide fluoride nanocrystals are uniformly dispersed in a non-polar solvent (cyclohexane) to obtain a rare earth halide fluoride nanocrystal dispersion with a concentration of 10 g / L. Organic ligands (methacrylate phosphate ligands) are added to the rare earth halide fluoride nanocrystal dispersion, and the reaction is carried out at 80°C under a nitrogen atmosphere for 4 h to form an organic coating layer on the surface of the rare earth halide fluoride nanocrystals, introducing methacrylate functional groups that can participate in the photocuring reaction. Unreacted methacrylate phosphate ligands are removed by centrifugation with ethanol to obtain modified rare earth halide fluoride nanocrystals; the amount of methacrylate phosphate ligands added is 1 wt% of the rare earth halide fluoride nanocrystals. S3. Modified rare earth halide fluoride nanocrystals are uniformly dispersed in isoborneol acrylate, and cyclohexane is removed under reduced pressure to obtain a pre-dispersed slurry of modified rare earth halide fluoride nanocrystals (the concentration of modified rare earth halide fluoride nanocrystals is 20wt%). Photosensitive resin (polyurethane acrylate) and photoinitiator (1-hydroxycyclohexylphenyl ketone) are added to the pre-dispersed slurry of modified rare earth halide fluoride nanocrystals and mixed evenly. After vacuum degassing treatment for 20 min, a modified rare earth halide fluoride nanocrystal composite photosensitive resin slurry is obtained. The amount of photoinitiator added is 1wt% of the photosensitive resin, and the viscosity of the modified rare earth halide fluoride nanocrystal composite photosensitive resin slurry is 1500 mPa·s. S4. Preparation of X-ray Response Detection Unit: Modified rare earth halofluoride nanocrystalline composite photosensitive resin slurry was injected into the 3D printer slurry tank to 3D print a hollow hemispherical mold. The modified rare earth halofluoride nanocrystalline composite photosensitive resin slurry was then injected into the hollow hemispherical mold. The fiber end face of the cladding fiber transmission component was inserted into the semi-cured microlens (insertion depth of 0.5 mm). The fiber was then cured by ultraviolet light with a wavelength of 365 nm for 60 min, so that the internal transmission fiber of the cladding fiber transmission component was electrically coupled and connected to the photocured rare earth halofluoride nanocrystalline composite scintillation microlens to obtain the X-ray response detection unit. X-ray response detection units are fixedly inserted in an array on the outer surface of the hemispherical support 2 to form a curved compound eye detection structure; the cladding fiber transmission component of each X-ray response detection unit 3 converges along the inner side of the hemispherical support 2 and passes downward through the hollow cylindrical support base 1, and the cladding fiber transmission component is connected to an image data receiver. The orientation photographs calculated using the photocurable rare-earth halofluoride nanocrystalline composite scintillation microlens in this embodiment, along with the actual experimental photographs, are shown below. Figure 5 ,from Figure 5 It can be seen that when X-rays are incident from a set orientation, the simulated luminescence intensity distribution and the actual experimentally captured image of the fiber optic output end exhibit similar spatial distribution characteristics, both showing local enhancement regions corresponding to the incident direction. Regions with higher light intensity correspond to detection units closer to the X-ray incident direction within the hemispherical compound eye, indicating that this biomimetic three-dimensional artificial compound eye scintillator detection device can convert the X-ray incident orientation into a two-dimensional light intensity distribution at the fiber optic output end. By extracting the ROI light intensity values from each fiber output end and calculating based on the region of maximum light intensity or the weighted center of light intensity, the X-ray incident direction can be reconstructed.
[0026] Example 2: This example describes a biomimetic stereoscopic artificial compound eye scintillator detection device for spatiotemporal perception and delayed storage retrieval in three-dimensional space. It comprises 148 X-ray response detection units 3, with a center-to-center spacing of 0.1 mm between adjacent X-ray response detection units 3. The photocurable rare-earth halofluoride nanocrystal composite scintillator microlens includes a photosensitive resin matrix (epoxy acrylate) and rare-earth halofluoride nanocrystals (NaLu(F / Br)4:Tb) uniformly dispersed in the photosensitive resin matrix. 3+ The rare earth halide fluoride nanocrystal composite scintillation microlens contains 1.5 wt% rare earth halide fluoride nanocrystals; the rare earth halide fluoride nanocrystals contain Tb 3+ The doping molar concentration is 10 mol%, and the particle size of the rare earth halide nanocrystals is 45 nm. The specific steps for fabricating the X-ray response detection unit are as follows: S1. Preparation of rare earth halofluoride nanocrystals: LuCl3 and TbCl3 were dissolved in deionized water to prepare LuCl3 solutions and TbCl3 solutions with a concentration of 0.8 mol / L, respectively; NaOH was dissolved in methanol to prepare NaOH methanol solutions with a concentration of 1.5 mol / L; NH4F and NH4Br were dissolved in methanol to prepare NH4F / NH4Br methanol solutions (the concentration of NH4F in the NH4F / NH4Br methanol mixture was 0.8 mol / L, and the molar ratio of NH4F to NH4Br was 1:1); LuCl3 solution, TbCl3 solution, Oleic acid and 1-octadecene were mixed evenly (the volume ratio of oleic acid to 1-octadecene was 1:2). Under an inert atmosphere (argon), the mixture was subjected to a dehydration reaction at 160℃ for 40 min to obtain mixture A (the concentration of LuCl3 in mixture A was 0.050 mol / L). After cooling to room temperature, NaOH methanol solution and NH4F / NH4Br methanol mixture were added to obtain mixture B. The mixture was then subjected to a reaction at 60℃ for 40 min. The temperature was then raised to 90℃ and held to remove methanol. The temperature was then raised to 300℃ and reacted for 45 min. After cooling to room temperature, the solid and liquid were separated. The solid was washed successively with cyclohexane and anhydrous ethanol to obtain rare earth halide fluoride nanocrystals. S2. Surface treatment of rare earth halide fluoride nanocrystals: Rare earth halide fluoride nanocrystals are uniformly dispersed in a non-polar solvent (n-hexane) to obtain a rare earth halide fluoride nanocrystal dispersion with a concentration of 20 g / L. An organic ligand (3-methacryloxypropyltrimethoxysilane) is added to the rare earth halide fluoride nanocrystal dispersion, and the mixture is reacted at 70℃ for 6 h to form an organic coating layer on the surface of the rare earth halide fluoride nanocrystals. Unreacted 3-methacryloxypropyltrimethoxysilane is removed by centrifugation with ethanol to obtain modified rare earth halide fluoride nanocrystals; the amount of 3-methacryloxypropyltrimethoxysilane added is 5 wt% of the rare earth halide fluoride nanocrystals. S3. Modified rare earth halide fluoride nanocrystals are uniformly dispersed in isoborneol acrylate, and n-hexane is removed under reduced pressure to obtain a pre-dispersed slurry of modified rare earth halide fluoride nanocrystals (the concentration of modified rare earth halide fluoride nanocrystals is 30wt%). Photosensitive resin (epoxy acrylate) and photoinitiator (2,4,6-trimethylbenzoyl diphenylphosphine oxide) are added to the pre-dispersed slurry of modified rare earth halide fluoride nanocrystals and mixed evenly. After vacuum degassing treatment, a modified rare earth halide fluoride nanocrystal composite photosensitive resin slurry is obtained. The amount of photoinitiator added is 2wt% of the photosensitive resin, and the viscosity of the modified rare earth halide fluoride nanocrystal composite photosensitive resin slurry is 2200 mPa·s. S4. Preparation of X-ray Response Detection Unit: Modified rare earth halide fluoride nanocrystalline composite photosensitive resin slurry is injected into the 3D printer slurry tank to 3D print a hollow hemispherical mold. The modified rare earth halide fluoride nanocrystalline composite photosensitive resin slurry is then injected into the hollow hemispherical mold. The fiber end face of the cladding fiber transmission component is inserted into the modified rare earth halide fluoride nanocrystalline composite photosensitive resin slurry. The slurry is cured by ultraviolet light with a wavelength of 405nm, so that the internal transmission fiber of the cladding fiber transmission component is electrically coupled and connected to the photocured rare earth halide fluoride nanocrystalline composite scintillation microlens to obtain the X-ray response detection unit. The orientation photographs calculated using the photocurable rare-earth halofluoride nanocrystalline composite scintillation microlens in this embodiment, along with the actual experimental photographs, are shown below. Figure 6 ,from Figure 6 It can be seen that using NaLu(F / Br)4 3+ After nanocrystal formation, the compound eye detection unit can form a clear luminescence response distribution under X-ray irradiation; the location of the high-intensity region in the simulation diagram is basically consistent with the high-brightness region at the fiber output end in the experimental diagram, indicating that Br - The introduced rare-earth halofluoride nanocrystals still maintain stable spatial response characteristics. Compared with Example 1, the nanocrystal content and resin system changed in this example, resulting in a more concentrated luminescence intensity distribution, which is beneficial for improving the light intensity difference and the accuracy of incident direction identification.
[0027] Example 3: This example describes a biomimetic stereoscopic artificial compound eye scintillator detection device for spatiotemporal perception and delayed storage retrieval in three-dimensional space. It comprises 81 X-ray response detection units 3, with a center-to-center spacing of 0.5 mm between adjacent X-ray response detection units 3. The photocurable rare earth halide fluoride nanocrystal composite scintillator microlens includes a photosensitive resin matrix (polyether acrylate) and rare earth halide fluoride nanocrystals (NaLu(F / Br)4:Tb) uniformly dispersed in the photosensitive resin matrix. 3+ The rare earth halide fluoride nanocrystal composite scintillation microlens contains 10 wt% rare earth halide fluoride nanocrystals; the rare earth halide fluoride nanocrystals contain Tb 3+ The doping molar concentration is 20 mol%, and the particle size of the rare earth halide nanocrystals is 48 nm. The specific steps for fabricating the X-ray response detection unit are as follows: S1. Preparation of rare earth halofluoride nanocrystals: LuCl3 and TbCl3 were dissolved in deionized water to prepare LuCl3 solutions and TbCl3 solutions with a concentration of 1.0 mol / L, respectively; NaOH was dissolved in methanol to prepare NaOH methanol solutions with a concentration of 2.0 mol / L; NH4F and NH4I were dissolved in methanol to prepare NH4F / NH4I methanol solutions (the concentration of NH4F in the NH4F / NH4I methanol mixture was 1.0 mol / L, and the molar ratio of NH4F to NH4I was 1:1); LuCl3 solution, TbCl3 solution, oil... Oleic acid and 1-octadecene were mixed evenly (the volume ratio of oleic acid to 1-octadecene was 2:1). Under an inert atmosphere (argon), the mixture was subjected to a dehydration reaction at 140℃ for 50 min to obtain mixture A (the concentration of LuCl3 in mixture A was 0.08 mol / L). After cooling to room temperature, NaOH methanol solution and NH4F / NH4I methanol mixture were added to obtain mixture B. The mixture was then subjected to a reaction at 45℃ for 50 min. The temperature was then raised to 85℃ and held to remove methanol. The temperature was then raised to 310℃ and reacted for 60 min. After cooling to room temperature, the solid and liquid were separated. The solid was washed successively with cyclohexane and anhydrous ethanol to obtain rare earth halide fluoride nanocrystals. S2. Surface treatment of rare earth halide fluoride nanocrystals: Rare earth halide fluoride nanocrystals are uniformly dispersed in a non-polar solvent (toluene) to obtain a rare earth halide fluoride nanocrystal dispersion with a concentration of 30 g / L. An organic ligand (methacrylic acid) is added to the rare earth halide fluoride nanocrystal dispersion, and the mixture is reacted at 90℃ for 8 h to form an organic coating layer on the surface of the rare earth halide fluoride nanocrystals. Unreacted methacrylic acid is removed by centrifugation with ethanol to obtain modified rare earth halide fluoride nanocrystals; the amount of methacrylic acid added is 10 wt% of the rare earth halide fluoride nanocrystals. S3. Modified rare earth halide fluoride nanocrystals are uniformly dispersed in isoborneol acrylate, and toluene is removed under reduced pressure to obtain a pre-dispersion slurry of modified rare earth halide fluoride nanocrystals (the concentration of modified rare earth halide fluoride nanocrystals is 40wt%). Photosensitive resin (polyether acrylate) and photoinitiator (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide) are added to the pre-dispersion slurry of modified rare earth halide fluoride nanocrystals and mixed evenly. After vacuum degassing treatment, a modified rare earth halide fluoride nanocrystal composite photosensitive resin slurry is obtained. The amount of photoinitiator added is 3.0wt% of the photosensitive resin, and the viscosity of the modified rare earth halide fluoride nanocrystal composite photosensitive resin slurry is 3000mPa·s. S4. Preparation of X-ray Response Detection Unit: Modified rare earth halide fluoride nanocrystalline composite photosensitive resin slurry is injected into the material tank of a 3D printer to create a hollow hemispherical mold. The modified rare earth halide fluoride nanocrystalline composite photosensitive resin slurry is then injected into the hollow hemispherical mold. The fiber end face of the cladding fiber transmission component is inserted into the modified rare earth halide fluoride nanocrystalline composite photosensitive resin slurry. The slurry is then cured by ultraviolet light with a wavelength of 385nm. This process couples the internal transmission fiber of the cladding fiber transmission component with the photocured rare earth halide fluoride nanocrystalline composite scintillation microlens, thus obtaining the X-ray response detection unit. The orientation photographs calculated using the photocurable rare-earth halofluoride nanocrystalline composite scintillation microlens in this embodiment, along with the actual experimental photographs, are shown below. Figure 7 ,from Figure 7 It can be seen that using NaLu(F / I)4 3+ After nanocrystal formation, the luminescence images obtained from actual experiments and the orientation response maps obtained from simulation calculations showed a good correspondence, with the bright areas shifting positionally as the X-ray incident direction changed; I - The introduction of features enhances the trap-related response and delayed readout capability of the material, enabling the detection unit to exhibit effective responses in both radiative emission (RL) mode and photoluminescence (OSL) mode. This demonstrates that the biomimetic stereoscopic artificial compound eye obtained in this embodiment can be used not only for real-time X-ray orientation sensing but also for delayed reading of radiation history information.
[0028] The specific embodiments of the present invention have been described in detail above. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention.
Claims
1. A biomimetic stereoscopic artificial compound eye scintillator detection device for spatiotemporal perception and delayed reading in three-dimensional space, characterized in that: The biomimetic three-dimensional artificial compound eye includes several X-ray response detection units (3), a hemispherical support (2), and a hollow cylindrical support substrate (1). The several X-ray response detection units (3) are arranged in a fixed array and inserted into the outer surface of the hemispherical support (2) to form a curved compound eye detection structure. Each X-ray response detection unit (3) includes a photocurable rare earth halofluoride nanocrystal composite scintillation microlens (4) and a cladding fiber conduction component (5) conduction structure. The cladding fiber conduction component (5) and the photocurable rare earth halofluoride nanocrystal composite scintillation microlens (4) are connected. The coupling connection forms a detection unit. The cladding fiber transmission component (5) converges along the inner side of the hemispherical support (2) and passes downward through the hollow cylindrical support substrate (1). The cladding fiber transmission component (5) is externally connected to the image data receiver. The photocurable rare earth halide fluoride nanocrystal composite scintillation microlens (4) includes a photosensitive resin matrix and rare earth halide fluoride nanocrystals uniformly dispersed in the photosensitive resin matrix. The photocurable rare earth halide fluoride nanocrystal composite scintillation microlens (4) generates a radiation emission RL response under X-ray irradiation and an optically excited emission OSL response under near-infrared light excitation.
2. The biomimetic stereoscopic artificial compound eye scintillator detection device for spatiotemporal perception and delayed reading in three-dimensional space according to claim 1, characterized in that: The rare earth halide fluoride nanocrystals are NaLuF4:Tb 3+ NaLu(F / Br)4:Tb 3+ NaLu(F / I)4:Tb 3+ One or more of the following are used: the photosensitive resin is one or more of polyurethane acrylate, epoxy acrylate, polyester acrylate, polyether acrylate, amino acrylate or acrylate; the rare earth halide fluoride nanocrystal composite scintillation microlens contains 1 to 15 wt% rare earth halide fluoride nanocrystals.
3. The biomimetic stereoscopic artificial compound eye scintillator detection device for spatiotemporal perception and delayed reading in three-dimensional space according to claim 2, characterized in that: Tb in the rare earth halide nanocrystals 3+ The doping molar concentration is 5-30%, and the particle size of rare earth halide fluoride nanocrystals is 10-80 nm.
4. The biomimetic stereoscopic artificial compound eye scintillator detection device for spatiotemporal perception and delayed reading in three-dimensional space according to claim 1, characterized in that: The maximum lateral dimension of the photocurable rare earth halide fluoride nanocrystal composite scintillation microlens is 0.5~3mm, the height is 0.2~2mm, and the radius of curvature is 0.3~3mm.
5. The biomimetic stereoscopic artificial compound eye scintillator detection device for spatiotemporal perception and delayed reading in three-dimensional space according to claim 2, characterized in that: The specific steps for fabricating the X-ray response detection unit are as follows: S1. Preparation of rare earth halofluoride nanocrystals: LuCl3 solution, TbCl3 solution, oleic acid and 1-octadecene are mixed evenly. Under an inert atmosphere, mixture A is placed at 120~180℃ for 20~60 min for dehydration reaction to obtain mixture A. After cooling to room temperature, NaOH methanol solution and fluorinated halofluoride methanol solution are added to obtain mixture B. The mixture is kept at 40~70℃ for 20~60 min, heated to 70~100℃ and kept at this temperature to remove methanol, and then heated to 260~320℃ for 10~120 min. After cooling to room temperature, the solid and liquid are separated. The solid is washed successively with cyclohexane and anhydrous ethanol to obtain rare earth halofluoride nanocrystals; the fluorinated halofluoride methanol solution is NH4F methanol solution, NH4F / NH4Br methanol mixture or NH4F / NH4I methanol mixture. S2. Surface treatment of rare earth halide fluoride nanocrystals: Rare earth halide fluoride nanocrystals are uniformly dispersed in a non-polar solvent to obtain a rare earth halide fluoride nanocrystal dispersion. Organic ligands are added to the rare earth halide fluoride nanocrystal dispersion, and the reaction is carried out at a temperature of 40~120℃ for 0.5~12h to form an organic coating layer on the surface of the rare earth halide fluoride nanocrystals. Unreacted organic ligands are removed by centrifugation with ethanol to obtain modified rare earth halide fluoride nanocrystals. S3. Modified rare earth halide fluoride nanocrystals are uniformly dispersed in isoborneol acrylate, and the non-polar solvent is removed under reduced pressure to obtain a pre-dispersion slurry of modified rare earth halide fluoride nanocrystals. Photosensitive resin and photoinitiator are added to the pre-dispersion slurry of modified rare earth halide fluoride nanocrystals and mixed evenly. After vacuum degassing treatment, a composite photosensitive resin slurry of modified rare earth halide fluoride nanocrystals is obtained. S4. Preparation of X-ray Response Detection Unit: Modified rare earth halide fluoride nanocrystalline composite photosensitive resin slurry is injected into the material tank of a 3D printer to create a hollow hemispherical mold. The modified rare earth halide fluoride nanocrystalline composite photosensitive resin slurry is then injected into the hollow hemispherical mold. The fiber end face of the cladding fiber transmission component is inserted into the modified rare earth halide fluoride nanocrystalline composite photosensitive resin slurry. The slurry is then cured by ultraviolet light with a wavelength of 365~405nm, thereby coupling the electrical signal between the cladding fiber transmission component and the photocured rare earth halide fluoride nanocrystalline composite scintillation microlens to obtain the X-ray response detection unit.
6. The biomimetic stereoscopic artificial compound eye scintillator detection device for spatiotemporal perception and delayed reading in three-dimensional space according to claim 5, characterized in that: In step S1, the concentrations of the LuCl3 solution, TbCl3 solution, NaOH methanol solution, and NH4F methanol solution are 0.05–2.0 mol / L, respectively. The concentrations of the NH4F / NH4Br methanol solution and NH4F methanol solution are 0.05–2.0 mol / L, respectively. In the NH4F / NH4Br methanol mixed solution, the concentration of NH4F is 0.05–2.0 mol / L, and the molar ratio of NH4F to NH4Br is 1:0.001–0.
5. In the NH4F / NH4I methanol mixed solution, the concentration of NH4F is 0.05–2.0 mol / L, and the molar ratio of NH4F to NH4I is 1:0.001–0.
5. The volume ratio of oleic acid to 1-octadecene is 1:0.5–5. The concentration of LuCl3 in mixed solution A is 0.005–0.15 mol / L.
7. The biomimetic stereoscopic artificial compound eye scintillator detection device for spatiotemporal perception and delayed reading in three-dimensional space according to claim 5, characterized in that: In step S2, the nonpolar solvent is cyclohexane, n-hexane, toluene, or chloroform, the concentration of the rare earth halide fluoride nanocrystal dispersion is 0.1~100 g / L, the organic ligand contains acrylate, methacrylate, vinyl, phosphate, or silane groups, and the amount of organic ligand added is 0.1~30 wt% of the rare earth halide fluoride nanocrystal.
8. The biomimetic stereoscopic artificial compound eye scintillator detection device for spatiotemporal perception and delayed reading in three-dimensional space according to claim 5, characterized in that: In step S3, the concentration of modified rare earth halofluoride nanocrystals in the pre-dispersed slurry is 1-15 wt%, and the photoinitiator is one or more of 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylphenylacetone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, or bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide. The amount of photoinitiator added is 0.1-5 wt% of the mass of the photosensitive resin. The viscosity of the modified rare earth halofluoride nanocrystal composite photosensitive resin slurry is 500-5000 mPa·s.
9. The biomimetic stereoscopic artificial compound eye scintillator detection device for spatiotemporal perception and delayed reading in three-dimensional space according to claim 1, characterized in that: The radius of the hemispherical support (2) is 5~50mm, and the distance between the centers of adjacent X-ray response detection units (3) is 1~2mm.
10. The biomimetic stereoscopic artificial compound eye scintillator detection device for spatiotemporal perception and delayed reading in three-dimensional space according to claim 1, characterized in that: The incident polar angle θ of X-ray irradiation is 0~90°, and the azimuth angle φ is 0~360°; the wavelength of near-infrared light is 800~1100nm.