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CN-122010986-A - Preparation method of near infrared luminous halide monocrystal scintillator

CN122010986ACN 122010986 ACN122010986 ACN 122010986ACN-122010986-A

Abstract

The invention discloses a preparation method of a near infrared luminous halide monocrystal scintillator, and belongs to the technical field of scintillators. The basic unit of the near infrared luminescent copper-based metal halide (4-ATHP) 2CuI3 consists of a protonated ATHP + (4-aminotetrahydropyran) cation and a [ CuI3] 2-anionic cluster. Appears as a yellow transparent mass in daylight, with a volume of about 1 cubic centimeter. Under ultraviolet excitation, the crystal shows multicolor photoluminescence, and based on the unique excitation, the crystal relies on multicolor emission to be successfully used for anti-counterfeiting and information encryption. Near infrared luminescent copper-based metal halide (4-ATHP) 2CuI3 has a high light yield of 55,923ev/MeV and a low detection limit of 81.99 nGyair of 81.99 nGyair in X-ray detection. The prepared flexible scintillator film based on (4-ATHP) 2CuI3 with large area (15×20cm2) realizes high spatial resolution of 20 lp/mm. By integrating the thin film into a CMOS imager, the great potential of these materials in high performance X-ray imaging applications.

Inventors

  • XIAO JIAWEN
  • Men Luxuan
  • Guan Haoyang
  • YAN ZHENGGUANG

Assignees

  • 北京工业大学

Dates

Publication Date
20260512
Application Date
20260202

Claims (10)

  1. 1. A near infrared light-emitting halide single crystal scintillator is characterized in that the chemical formula of the near infrared light-emitting halide single crystal scintillator is (4-ATHP) 2 CuI 3 ; wherein 4-ATHP is 4-aminotetrahydropyran, each copper atom is coordinated by four iodine atoms to form a tetrahedral geometry. 4-ATHP ligands remain in the aprotic state, directly attached to the metal center. Copper-iodine tetrahedrons are interconnected by edge sharing and extend to one-dimensional 1D chain structures by vertex sharing.
  2. 2. The near infrared emitting halide single crystal scintillator of claim 1, wherein the crystal structure has unit cell parameters of a= 11.8986 a, b= 12.3535 a, c= 12.6596 a, α= 90.264 °, β= 90.243 °, γ= 92.897 °.
  3. 3. The near infrared light emitting halide single crystal scintillator of claim 1, wherein the high energy emission band of one near infrared light emitting metal halide (4-ATHP) 2 CuI 3 exhibits the strongest PLE peak at 340 nm with an emission peak position at 535 nm when excited at that wavelength. The low energy emission band shows strong PLE peaks in both the 380 nm and 450nm bands. At 380 nm excitation, the dominant emission peak was 715nm, accompanied by a high energy emission shoulder at 535 nm. A red emission peak was generated at 715nm upon 450nm excitation.
  4. 4. The near infrared light emitting single crystal halide scintillator of claim 1, wherein the near infrared light emitting copper based metal halide (4-ATHP) 2 CuI 3 achieves >95% absorption of 13keV photons at 121 microns thickness, light yield up to 55,923 photons/MeV, and detection limit of 81.99 ngay e /s.
  5. 5. A method for producing a near infrared light-emitting halide single crystal scintillator as claimed in any one of claims 1 to 4, comprising: dissolving copper oxide with preset mass in hydroiodic acid, and stirring and dissolving to synthesize a precursor CuI; injecting a first preset volume of 4-aminotetrahydropyran into the completely dissolved precursor solution, and continuously stirring the solution at the same time, so as to obtain a mixed solution by dissolution; adding the mixed solution into a second preset volume of hypophosphorous acid to obtain a colorless solution; filtering the colorless growth solution through a PTFE filter membrane with a pore size of 0.22 microns to obtain a purified solution; And placing the purified solution in a ventilation hood for room temperature growth, and obtaining the near infrared luminescent copper-based metal halide (4-ATHP) 2 CuI 3 monocrystal after a preset time.
  6. 6. The method of claim 5, wherein the predetermined mass is 1.43 g, the first predetermined volume is 4.0 ml, the second predetermined volume is 1.0 ml, and the predetermined time is 1-3 days.
  7. 7. A method for preparing a near infrared luminescent copper-based metal halide (4-ATHP) 2 CuI 3 flexible film, comprising: (4-ATHP) 2 CuI 3 powder and ‌ N, N-dimethylformamide and thermoplastic polyurethane in a predetermined ratio; the mixture is coated on a flexible polyethylene terephthalate substrate in a spinning way; Curing at room temperature gave a flexible (4-ATHP) 2 CuI 3 @ TPU scintillation film, a near infrared luminescent copper-based metal halide (4-ATHP) 2 CuI 3 flexible film.
  8. 8. The process of claim 7, wherein the predetermined ratio is 8 g (4-ATHP) 2 CuI 3 powder, 6 ml DMF,3 g TPU.
  9. 9. The method of claim 7 or 8, wherein a near infrared luminescent copper-based metal halide (4-ATHP) 2 CuI 3 flexible film is transparent in sunlight and emits bright luminescence under 254 nm ultraviolet radiation.
  10. 10. The method of any one of claims 7 to 9, wherein the flexible film of a near infrared luminescent copper-based metal halide (4-ATHP) 2 CuI 3 has a spatial resolution of generally 20lp/mm.

Description

Preparation method of near infrared luminous halide monocrystal scintillator Technical Field The invention relates to the technical field of scintillators, in particular to a preparation method of a near infrared luminous copper-based metal halide (4-ATHP) 2CuI3 monocrystal Background X-ray detection techniques are widely used in medical diagnostic imaging, oil exploration, security screening, and aerospace exploration. The low cost, high sensitivity and excellent stability make indirect detection systems the dominant technique for X-ray imaging. As a core component of indirect detection, high performance scintillators play a key role in achieving efficient X-ray detection and imaging. Traditional commercially pure inorganic scintillators, such as CsI: tl and LaBr3: ce, have been widely used over the past few decades. However, these scintillators also have several limitations, including complex and expensive manufacturing processes, insufficient flexibility, and relatively low light yield, which prevent their further development. Copper-based halide scintillators have been of great interest in the fields of radiation detection and X-ray imaging because of their non-toxicity, high photoluminescence quantum yield (PLQY), and high optical yield. The initially developed inorganic crystals possess structural rigidity and stability, but their low solubility and solution processability prevent wider application. To overcome these challenges, organic-inorganic mixed copper halide scintillators have been engineered. The incorporation of the organic component combines the structural stability of the inorganic clusters with the tunability of the organic cation. Such as (TMAA) 2Cu4Br6 、[BAPMA]Cu2Br5, which significantly improves the optoelectronic properties, material processability and environmental stability of the material However, the structure-property relationship of the organic component to the induction of copper-iodide clusters is still insufficient in the current study. Current research is still lacking in comprehensive reports on how the specific bonding patterns between the organic component and clusters affect the performance of copper-based halide scintillators. Reports on copper-based halides to achieve high resolution X-ray imaging remain rare and few studies have demonstrated their practical integration as scintillator screens in commercial devices. Therefore, the feasibility of research on the application of copper-based halides in commercial imaging equipment is of great importance and is a key step toward practical application Disclosure of Invention The embodiment of the invention provides a preparation method of near infrared luminescent copper-based metal halide (4-ATHP) 2CuI3 monocrystal and related products, which shows unique excitation-dependent multicolor emission and is used for X-ray imaging, anti-counterfeiting and information encryption. The specific scheme is as follows: The embodiment of the invention provides a near infrared luminescent copper-based metal halide (4-ATHP) 2CuI3 monocrystal, which has the following chemical formula composition: (4-ATHP)2CuI3; In one possible implementation manner, in the above-mentioned near infrared luminescent copper-based metal halide (4-ATHP) 2CuI3 provided by the embodiment of the present invention, the 4-ATHP is 4-aminotetrahydropyran, and each copper atom is coordinated by four iodine atoms to form a tetrahedral geometry. The 4-ATHP ligand remains in an aprotic state, directly attached to the metal center. Copper-iodine tetrahedra are interconnected by edge sharing and further extended to a one-dimensional (1D) chain structure by vertex sharing. In one possible implementation manner, in the above-mentioned one near-infrared light emitting copper-based metal halide (4-ATHP) 2CuI3 provided by the embodiment of the present invention, the unit cell parameter of the crystal structure of the one near-infrared light emitting copper-based metal halide (4-ATHP) 2CuI3 is a= 11.8986 a, b= 12.3535 a, c= 12.6596 a, α= 90.264 °, β= 90.243 °, γ= 92.897 °. In one possible implementation manner, in the above-mentioned one near infrared light emitting copper-based metal halide (4-ATHP) 2CuI3, the high energy emission band of one near infrared light emitting copper-based metal halide (4-ATHP) 2CuI3 shows the strongest PLE peak at 340 nm, and the emission peak position is 535 nm when the wavelength is excited. The low energy emission band shows strong PLE peaks in both the 380 nm and 450nm bands. At 380 nm excitation, the dominant emission peak was 690 nm, accompanied by a weak high energy emission shoulder at 535 nm. 450 A red emission peak was generated at 690 nm upon nm excitation. In one possible implementation manner, in the above-mentioned one near infrared light emitting copper-based metal halide (4-ATHP) 2CuI3 provided by the embodiment of the present invention, the one near infrared light emitting copper-based metal halide (4-ATHP) 2CuI3 achieves absorption