A thermally excited exciton type organic glass scintillator material, its preparation method and applications

Abstract

A thermo-exciton type organic glass scintillator material, its preparation method and application are disclosed. The thermo-exciton type organic glass scintillator material includes a glass matrix material and a thermo-exciton type highly efficient luminescent guest material. This thermo-exciton type organic glass scintillator material can be efficiently prepared by precise temperature control and simple melting processing means, and has the advantages of high transparency, large area and stable performance. This thermo-exciton type organic glass scintillator material has a photoluminescence quantum efficiency of more than 95% and a nanosecond-level decay lifetime. At the same time, under the excitation of X-rays, it can exhibit high-efficiency radiation luminescence performance, extremely low detection limit and high imaging resolution. These characteristics make it have extremely broad application prospects in many fields such as medical diagnosis and treatment, security inspection and industrial non-destructive testing.

Description

Technical Field

[0001] This application relates to the technical field of luminescent materials, and mainly relates to a thermally-excited organic glass scintillator material, its preparation method and application. Background Art

[0002] X-ray scintillators are a class of materials that exhibit luminescent properties under X-ray excitation, and can convert high-energy X-rays into low-energy visible light. With this unique property, X-ray scintillators can be applied to key fields such as radiation detection, security inspection, and biomedicine, and have received extensive attention. However, most of the X-ray scintillation materials widely used commercially at present are mainly inorganic materials represented by ceramic scintillators. These inorganic scintillator materials usually need to be prepared under high-temperature conditions and often have a long growth cycle, and it is difficult to achieve large-area and high-performance scintillators through an economical and easily replicable method.

[0003] Pure organic luminescent materials have attracted much attention because they do not contain metal elements and have significant advantages such as rich raw material reserves, high mechanical flexibility, excellent processing performance, easy synthesis and modification. However, there are some fundamental limitations in the practical application of organic scintillator materials, mainly manifested as low exciton utilization efficiency and low radiation stopping power inherent in low atomic numbers. Traditional organic fluorescent molecules can only utilize 25% of singlet excitons, while thermally activated delayed fluorescence and phosphorescent materials, although they can improve the scintillation light yield, their delayed fluorescence or phosphorescent processes will cause the scintillation lifetime to extend to the microsecond or even second level, which is not conducive to the imaging application of scintillators. Thermally-excited materials achieve non-delayed fluorescence by "manipulating" thermally-excited excitons, and have the advantages of high exciton utilization efficiency and fast time decay, and can effectively avoid the dilemmas of traditional organic scintillators.

[0004] In addition, currently, X-ray imaging is mainly achieved by growing large-sized organic scintillator single crystals (>1 cm 2 ), or doping scintillator microcrystals (5-60 wt%) into a polymer matrix to form a scintillator film. However, the former requires a long single crystal growth process and is difficult to control in terms of thickness and size, severely limiting its application; the latter can prepare large-area films, but significantly reduces the content of organic scintillators, resulting in a decrease in radiation luminescence intensity, and the matrix usually has limited X-ray absorption ability. Moreover, a high doping level often causes the film to be opaque, resulting in optical scattering and seriously affecting the imaging effect.

[0005] Therefore, it is of great practical significance and application value to develop a new type of thermally-excited pure organic scintillator material with efficient X-ray luminescence, short decay lifetime, large-area processing ability, amorphous transparency and stability. Summary of the Invention

[0006] In view of the technical problems existing in the prior art, the present application proposes a thermally-excited-exciton type organic glass scintillator material, its preparation method and application.

[0007] According to one aspect of the present invention, there is provided a thermally-excited-exciton type organic glass scintillator material, comprising a glass host material and a thermally-excited-exciton type highly efficient luminescent guest material; the glass host material comprises or ; the thermally-excited-exciton type highly efficient luminescent guest material comprises , , or .

[0008] The thermally-excited-exciton type luminescent guest material can make full use of high-energy triplet excitons, and convert triplet excitons into singlet excitons through reverse intersystem crossing, so as to achieve efficient radiative luminescence. By combining the thermally-excited-exciton type highly efficient luminescent guest material with a specific glass host material, making full use of the thermally-excited-exciton mechanism to achieve efficient radiative luminescence, it can significantly improve the photoluminescence quantum efficiency, while maintaining the transparency and large-area processing ability of the material, providing a high-performance organic scintillator material for fields such as X-ray imaging.

[0009] In a specific embodiment, the above-mentioned glass host material has excellent thermal stability, optoelectronic properties and film-forming properties, which can ensure the stable operation of the thermally-excited-exciton type organic glass scintillator material in a high-temperature environment, improve its service life and reliability, and can ensure that the final product forms a large-area and uniform thin film. In addition, the above-mentioned glass host material also has excellent biocompatibility, making the scintillator material also have great development potential in the field of biomedicine.

[0010] In a specific embodiment, the above-mentioned thermally-excited-exciton type luminescent guest material has high luminescence efficiency, fast luminescence decay characteristics, good thermal stability and biocompatibility, etc., and can perfectly cooperate with the above-mentioned glass host material to form a thermally-excited-exciton type organic glass scintillator material with excellent performance and broad application prospects.

[0011] Preferably, R in the glass host material includes H, F, Cl, Br, I or CH3.

[0012] In a specific embodiment, different R groups will affect the energy level structure of the molecule, and thus affect the optical properties of the glass host material; at the same time, different R groups will also affect the solubility, biocompatibility and mechanical properties of the glass host material. By reasonably selecting and designing the R group, the chemical and physical properties of the glass host material can be adjusted, and the interaction with the thermally-excited-exciton type luminescent guest material can be further optimized, so as to better match the energy transfer requirements of the luminescent guest, reduce energy loss, and further improve the luminescence efficiency and material stability.

[0013] Preferably, X in the thermally-excited-exciton type highly efficient light-emitting guest material includes N or P.

[0014] In a specific embodiment, the atomic radius of the N atom is small and the electronegativity is high, and it usually forms a strong covalent bond in the compound, having a high bond energy and stability. While the atomic radius of the P atom is large and the electronegativity is low, the bond formed in the compound is usually weak, and the compound is prone to exhibit a greater steric hindrance effect. By selecting N or P, the electronic structure and energy level distribution of the light-emitting guest can be adjusted, thereby optimizing its thermally-excited-exciton utilization efficiency and light-emitting intensity, enabling the material to emit visible light more efficiently under X-ray excitation and improving the imaging quality.

[0015] Preferably, R1 in the thermally-excited-exciton type highly efficient light-emitting guest material includes , , , or .

[0016] In a specific embodiment, different R1 groups will affect the intermolecular packing and π-π interactions, and thus affect the crystallinity and molecular order of the thermally-excited-exciton type highly efficient light-emitting guest material, which is crucial for improving the light-emitting efficiency and stability of the product. In addition, the R1 group will also affect the emission wavelength and color, thermal stability, solubility, mechanical properties and biocompatibility. By reasonably selecting and designing the R1 group, the desired properties can be brought to the glass host material to meet the requirements of different application scenarios.

[0017] Preferably, R2 in the thermally-excited-exciton type highly efficient light-emitting guest material includes H, F, Cl, Br or I.

[0018] In a specific embodiment, different halogen atoms have different atomic radii and electronegativities. By introducing different R2 groups, the electronic properties and intermolecular interactions of the thermally-excited-exciton type light-emitting guest material can be adjusted, thereby affecting its exciton formation and energy transfer processes. At the same time, different halogen atoms can achieve the adjustment of X-ray absorption. In addition, selecting different R2 groups can optimize the light-emitting efficiency and decay lifetime of the thermally-excited-exciton type highly efficient light-emitting guest material, enabling it to exhibit a faster time response and higher imaging clarity in X-ray imaging.

[0019] According to the second aspect of the present invention, a preparation method of a thermally-excited-exciton type organic glass scintillator material is provided, which specifically includes the following steps:

[0020] S1. Dope the thermally-excited-exciton type light-emitting guest material into the glass host material to obtain a mixture, and the mass ratio of the thermally-excited-exciton type light-emitting guest material to the glass host material is 0.001% - 6%;

[0021] S2, placing the mixture on a silica gel substrate to melt, the melting temperature program is: first heating to 160 ° C and keeping it for 5 min, then heating by 10 ° C every 3 min until the temperature reaches the preset melting temperature;

[0022] S3, the mixture is completely melted, stirred until no bubbles are generated, and then kept warm for 5 minutes, and then naturally cooled to room temperature to obtain a thermoexciton type organic glass scintillator film material.

[0023] This method can achieve uniform doping and high-quality film preparation by precisely controlling the doping ratio of the hot exciton luminescent guest material and the glass host material and the melting temperature program. This method is simple and easy to implement, suitable for large-area processing, and can effectively avoid the problems of slow single crystal growth and opaque films in traditional preparation methods, thereby improving the preparation efficiency and imaging performance of the material.

[0024] In a specific embodiment, the thickness of the thermoexciton organic glass scintillator film material manufactured by this method is 0.5-3 mm.

[0025] Preferably, in S1, the mass ratio of the thermoexciton type luminescent guest material to the glass host material is 0.001%, 0.01%, 0.1%, 0.5%, 2%, 4% or 6%.

[0026] In a specific embodiment, different doping ratios will affect the generation and recombination efficiency of excitons, thereby affecting the luminescence efficiency; different doping ratios will also affect the energy level structure of the material, thereby affecting the luminescence wavelength and color; at the same time, a suitable doping ratio helps to form a uniform film. By selecting a suitable ratio, the material can achieve the best performance balance in X-ray imaging while ensuring the transparency and stability of the material.

[0027] Preferably, in S2, the melting heating device is a heating block.

[0028] In a specific embodiment, the heating block can achieve precise temperature control, provide a stable and uniform heating environment, help maintain the integrity of temperature-related reactions, avoid quality problems caused by local overheating or overcooling, thereby improving the quality and uniformity of the film and ensuring the consistency and repeatability of experimental results.

[0029] Preferably, in S2, the melting temperature is 180-220°C.

[0030] In a specific embodiment, the melting temperature is determined by the melting points of the selected glass matrix material and the thermally-excited luminescence guest material. Within this temperature range, it can not only ensure the full melting of the mixture but also avoid the decomposition of materials or the degradation of properties caused by excessive temperature, ensuring the stability and repeatability of the preparation process. At the same time, it ensures that the optical and mechanical properties of the materials are not affected, which helps to achieve high-quality organic glass scintillator films.

[0031] According to the third aspect of the present invention, an application of a thermally-excited organic glass scintillator material in X-ray imaging is proposed.

[0032] This thermally-excited organic glass scintillator material has high-efficient X-ray luminescence ability, short decay lifetime, large-area processing ability, amorphous transparency, and good stability, which can significantly improve the performance of X-ray imaging equipment. Its application in X-ray imaging can achieve higher imaging resolution, lower detection limit, and better stability, which has important practical significance and broad application prospects in the fields of medical diagnosis, security detection, etc.

[0033] Compared with the prior art, the present application has the following beneficial effects:

[0034] The solution of the present application can efficiently prepare a scintillator film with high transparency, large area, and stable performance through precise temperature control and simple melting processing means. Moreover, this thermally-excited organic glass scintillator material has low cost and can be industrially produced;

[0035] The thermally-excited organic glass scintillator material of the present application has a photoluminescence quantum efficiency of more than 95% and a decay lifetime in the nanosecond range, which shows great application potential in the field of dynamic imaging and can significantly improve image clarity;

[0036] The thermally-excited organic glass scintillator material of the present application exhibits high-efficient radioluminescence performance, extremely low detection limit, and high imaging resolution under X-ray excitation. These characteristics make it have extremely broad application prospects in multiple fields such as medical diagnosis and treatment, security inspection, and industrial non-destructive testing, and are expected to bring technological innovation to related industries and improve detection efficiency and accuracy. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] The drawings are included to provide a further understanding of the embodiments and are incorporated into and constitute a part of this specification. The drawings illustrate the embodiments and, together with the description, are used to explain the principles of the present invention. Other embodiments and many of the expected advantages of the embodiments will be readily recognized as they become better understood by reference to the following detailed description. The elements of the drawings are not necessarily to scale with each other. The same reference numerals refer to corresponding similar components.

[0038] Figure 1 Shows a schematic flow chart of fabricating a thermally-excited exciton type organic glass scintillator material according to an embodiment of the present invention;

[0039] Figure 2 Shows a photoluminescence spectrum diagram according to a specific embodiment of the present invention;

[0040] Figure 3 Shows a fluorescence decay curve diagram according to a specific embodiment of the present invention;

[0041] Figure 4 Shows a diagram of the relationship between Stokes shift and solvent orientation polarization according to a specific embodiment of the present invention;

[0042] Figure 5 Shows a luminescence spectrum diagram under X-ray irradiation according to a specific embodiment of the present invention;

[0043] Figure 6 Shows a statistical chart of photoluminescence quantum efficiency according to a specific embodiment of the present invention;

[0044] Figure 7 Shows a transmission spectrum diagram according to a specific embodiment of the present invention;

[0045] Figure 8 Shows an X-ray detection limit spectrum diagram according to a specific embodiment of the present invention;

[0046] Figure 9 Shows an X-ray imaging photo and an X-ray imaging resolution diagram according to a specific embodiment of the present invention;

[0047] Figure 10 Shows a stability spectrum diagram under X-ray irradiation according to a specific embodiment of the present invention;

[0048] Figure 11 Shows a luminescence spectrum diagram under X-ray irradiation according to another specific embodiment of the present invention;

[0049] Figure 12 Shows a luminescence spectrum diagram under X-ray irradiation according to still another specific embodiment of the present invention. Detailed implementation manners

[0050] The present application will be further described in detail below with reference to the accompanying drawings and embodiments. It can be understood that the specific embodiments described herein are only used to explain the related invention and are not intended to limit the invention. Additionally, it should be noted that for the convenience of description, only the parts related to the relevant invention are shown in the drawings.

[0051] It should be noted that, without conflict, the embodiments in the present application and the features in the embodiments may be combined with each other. The present application will be described in detail below with reference to the accompanying drawings and in conjunction with the embodiments.

[0052] Figure 1 The figure shows a schematic diagram of the manufacturing process of a thermally excited exciton type organic glass scintillator material. Refer to Figure 1 , and the specific manufacturing process is as follows:

[0053] S1. Dope the thermally excited exciton type luminescent guest material into the glass host material to obtain a mixture. The mass ratio of the thermally excited exciton type luminescent guest material to the glass host material is 0.001% - 6%.

[0054] S2. Place the mixture on a silicone substrate and melt it. Select an 8 ml × 16-hole heating block to accurately control the temperature on a heating table. The melting temperature rising program is as follows: First, heat up to 160 °C and keep it warm for 5 minutes, then raise the temperature by 10 °C every 3 minutes until the temperature reaches the preset melting temperature.

[0055] S3. After the mixture is completely melted and stirred until no bubbles are generated, keep it warm for 5 minutes, and then naturally cool it to room temperature to obtain a thermally excited exciton type organic glass scintillator thin film material. Example 1

[0056] A thermally excited exciton type organic glass scintillator material, including a glass host material ( m CP) and a thermally excited exciton type luminescent guest material (N - BA), and the molecular structures are respectively:

[0057] and .

[0058] m The NMR characterization results of CP are as follows: 1 H NMR (DMSO - d6) δ (ppm) 7.56 (d, J J = 8.8Hz, 4H), 7.34 - 7.23 (m, 2H), 7.11 - 7.03 (m, 1H), 6.75 (d, J J = 8.8Hz, 4H).

[0059] The preparation route of N - BA is as follows:

[0060] (1)

[0061] (2)

[0062] In formula (1), the nuclear magnetic characterization results of 9, 10-bis(4-bromophenyl)anthracene are as follows: 1 H NMR (600 MHz, DMSO-d6): δ(ppm) 7.87 (4H, d, J J = 7.2 Hz); 7.59 - 7.57 (4H, m); 7.47 (4H, m); 7.44 (4H, d, J J = 7.32 Hz).

[0063] The specific preparation process of 4, 4'-(anthracene-9,10-diyl) bis(N-butyl-N-phenyl) dianiline in formula (2) is as follows: In an inert gas atmosphere, 9, 10-bis(4-bromophenyl)anthracene (0.55 mmol), 2-(di-tert-butylphosphino)biphenyl (CAS: 224311-51-7, 0.05 mmol), tris(dibenzylideneacetone)dipalladium (CAS: 51364-51-3 0.02 mmol) and sodium tert-butoxide (CAS: 865-48-5, 2.20 mmol) are mixed in a flask, and then N-butylaniline (CAS: 1126-78-9, 1.65×10 − 3 mol) and toluene are added under a nitrogen stream. The reaction mixture is stirred under nitrogen and refluxed at 85 - 120 °C for 12 h. After the reaction is completed, it is extracted with saturated brine, dried over anhydrous magnesium sulfate, and the solvent is removed by rotary evaporation. The crude product is purified by column chromatography (petroleum ether:dichloromethane = 4:1), recrystallized, and then dried under vacuum to obtain a green solid product N-BA (87.9%). The nuclear magnetic characterization results are as follows: 1 HNMR (400MHz, CDCl3): δ 7.86–7.82 (m, 4H), 7.39–7.31 (m, 12H), 7.23 (d, J J = 7.8Hz, 4H), 7.15 (d, J J = 8.4 Hz, 4H), 7.05 (t, J J = 7.4 Hz, 2H), 3.86–3.81 (m, 4H),1.82–1.77 (m, 4H), 1.47–1.43 (m, 4H), 1.00 (t, J J = 7.4 Hz, 6H).

[0064] Based onm The fabrication process of the thermally excited organic glass scintillator film of CP and N-BA (N-BA@ m CP) is as follows:

[0065] S11. Take 0.1 g of m CP and mix it with 0.001 mg of N-BA to obtain a mixture;

[0066] S12. Place the mixture on a 3×3 cm circular silicone substrate, select an 8 ml×16-hole heating block to accurately control the temperature on a heating platform. The melting and heating program is as follows: first heat up to 160 °C and hold for 5 min, then heat up 10 °C every 3 min and hold for 2 min, and finally heat up to 190 °C;

[0067] S13. Wait for the mixture to completely melt, stir until there are no bubbles, then hold for 5 min, and then naturally cool to room temperature to obtain the thermally excited organic glass scintillator film.

[0068] Repeat the above steps. Take 0.1 g of m CP and mix it with 0.01 mg, 0.1 mg, 0.5 mg, 2 mg, 4 mg, and 6 mg of N-BA respectively, melt and cool to obtain another 6 groups of thermally excited organic glass scintillator film samples.

[0069] Figure 2 are the photoluminescence spectra of the N-BA crystalline sample, the N-BA glassy sample, and the 2 wt% N-BA@ m CP sample under X-ray irradiation. It can be seen from Figure 2 that the characteristic emission peaks of the three samples are all located near 500 nm, showing green luminescence.

[0070] Figure 3 are the fluorescence decay curves of the N-BA crystalline sample, the N-BA glassy sample, and the 2 wt% N-BA@ m CP sample. It can be seen from Figure 3 that all samples show very fast nanosecond-level decay lifetimes, which means that there will be no residual images when this material is applied to the field of X-ray imaging.

[0071] Figure 4 is the relationship diagram of the Stokes shift and solvent orientation polarization of N-BA. As shown in Figure 4As shown, by combining the emission spectra and absorption spectra changes of N-BA molecules in different polar solvents and using the Lippert-Mataga model based on Stokes shift and solvent orientation polarizability, it can be found that the fitting line of the Stokes shift of N-BA with the solvent polarity (f) shows two different slopes, indicating the existence of two different excited states: the local excited state (LE) in low-polarity solvents and the charge transfer state (CT) in high-polarity solvents.

[0072] In summary, Figure 2-4 it is proved that the N-BA molecule has the emission characteristics of the HLCT state, making it an organic hot exciton molecule.

[0073] Figure 5 For 7 groups of hot exciton-type organic glass scintillator samples and the m radioluminescence spectra of the CP samples without doped luminescent guest materials, as Figure 5 shown, under X-ray excitation, all 7 groups of hot exciton-type organic glass scintillator samples show an obvious characteristic emission peak near 500 nm, and with the increase of the doping concentration of the luminescent guest material, the intensity of the characteristic emission peak increases significantly. While the m CP samples without doped luminescent guest materials hardly emit light near 500 nm, indicating that the luminescence of the hot exciton-type organic glass scintillator mainly comes from the hot exciton-type luminescent guest material.

[0074] Figure 6 For the statistical chart of the photoluminescence quantum efficiency of 7 groups of hot exciton-type organic glass scintillator samples, as Figure 6 shown, all 7 groups of hot exciton-type organic glass scintillator samples show high photoluminescence quantum efficiency. Among them, the photoluminescence quantum efficiency of the scintillators with doping mass ratios of 0.001% and 0.01% is relatively low compared with other samples. When the doping mass ratio rises to 0.1%, the photoluminescence quantum efficiency has an obvious increase, reaching 97.7%.

[0075] In a specific embodiment, a scintillation screen (diameter 2.5 mm, thickness 1 mm) based on 2 wt% N-BA@ m CP was prepared on a flexible silica gel substrate by the method of temperature-controlled melting with a heating block. Figure 7 For the transmission spectrum of the 2 wt% N-BA@ m CP scintillation screen and the glass host material m CP, as Figure 7 shown, this hot exciton-type organic glass scintillation screen has good transparency and a transmittance greater than 80% in the visible light region. Figure 8 For the X-ray detection limit spectrum of the 2 wt% N-BA@ m CP scintillation screen, from Figure 8It can be seen that the thermally excited exciton type PMMA scintillator screen has a detection limit as low as 37 nGy s -1 , which is much lower than the detection limit of 5.5 μGy s for medical standard X-rays -1 . This indicates that this material can respond very sensitively to radiation dose, which helps to improve image quality and reduce the radiation dose received by patients.

[0076] Figure 9 X-ray imaging photos and X-ray imaging resolution diagrams of the 2 wt% N-BA@ m CP scintillator screen are shown. As can be seen from Figure 9 a and Figure 9 b, the internal structure of the small electronic chip and the hollow metal label can both be clearly presented. Referring to Figure 9 c and Figure 9 d, the spatial resolution of this thermally excited exciton type PMMA scintillator screen was characterized by line pair card imaging and modulation transfer function (MTF) calculation. The results show that when MTF = 0.3, the spatial resolution of this scintillator screen is 12.5 lp / mm, showing clear imaging potential.

[0077] Figure 10 The stability spectrum diagram of the 2 wt% N-BA@ m CP scintillator screen under X-ray irradiation is shown. As shown in Figure 10 , the radiation luminescence intensity of this scintillator screen hardly decreases under long-term repeated switching, showing good radiation stability. Example 2

[0078] A thermally excited exciton type PMMA scintillator material, comprising a glass matrix material ( m CP-1Br) and a thermally excited exciton type luminescent dopant material (N-BA). m The molecular structure of CP-1Br is: .

[0079] m The NMR characterization results of CP-1Br (9, 9'-(5-bromo-1, 3-phenylene) bis(9H-carbazole)) are as follows:

[0080] 1 1H NMR (400 MHz, CDCl3): δ: 8.20–8.13 (m, 4H), 7.89 (d, J J = 1.9 Hz, 2H), 7.82 (t, J= 1.9 Hz, 1H), 7.57 (dt, J = 8.2, 0.8 Hz, 4H), 7.52–7.45 (m, 4H), 7.38–7.32 (m, 4H).

[0081] 13 C NMR (101 MHz, CDCl3): δ: 140.44, 140.26, 128.62, 126.34, 124.09, 123.90, 123.77, 120.74, 120.54, 109.57.

[0082] m The specific preparation method of CP-1Br is as follows:

[0083]

[0084] Based on m The fabrication process of the thermoexciton-based organic glass scintillator film of CP-1Br and N-BA (2 wt% N-BA@ m CP-1Br) is as follows:

[0085] S21. Take 0.1 g of m CP-1Br and mix it with 2 mg of N-BA to obtain a mixture;

[0086] S22. Place the mixture on a 3×3 cm circular silicone substrate, select an 8 ml×16-hole heating block to precisely control the temperature on a heating platform. The melting and heating program is as follows: first heat to 160 °C and hold for 5 min, then heat 10 °C every 3 min and hold for 2 min, and finally heat to 200 °C;

[0087] S23. Wait for the mixture to completely melt, stir until there are no bubbles, then hold for 5 min, and then naturally cool to room temperature to obtain the thermoexciton-based organic glass scintillator film.

[0088] Figure 11 For the radioluminescence spectra of the thermoexciton-based organic glass scintillator film of 2 wt% N-BA@ m CP-1Br and 2 wt% N-BA@ m CP, as can be seen from Figure 11 Among them, for the glass scintillator with m CP-1Br as the host, an obvious characteristic emission peak also appears near 500 nm, and its radioluminescence intensity is significantly stronger than that of 2 wt% N-BA@ m CP. This is because the glass host material mThe heavy bromine atoms in CP-1Br have stronger absorption of X-rays, resulting in more efficient radioluminescence properties. It can also be seen from this that the choice of the glass host material has an important impact on the scintillation performance of the final glass scintillator. Example 3

[0089] A thermally excited organic glass scintillator material, including a glass host material ( m CP-2Br) and a thermally excited luminescent guest material (N-BA), m The molecular structure of CP-2Br is:

[0090] .

[0091] m The preparation route of CP-2Br is as follows:

[0092] (3)

[0093] (4)

[0094] In formula (3), the NMR characterization results of 3-bromocarbazole are as follows: 1 H NMR (400MHz,CDCl3): δ: 8.30–8.27 (m, 2H), 8.15–8.10 (m, 2H), 7.92–7.86 (m, 1H), 7.77 (t, J = 1.9 Hz, 1H), 7.71 (dd, J = 7.9, 2.0 Hz, 2H), 7.57–7.46 (m, 6H), 7.44–7.32 (m,4H).

[0095] In formula (4), the NMR characterization results of 1, 3-bis(3-bromo-9H-carbazol-9-yl)benzene are as follows:

[0096] 1 H NMR (400MHz, CDCl3): δ: 8.30-8.27 (m, 2H), 8.15–8.10 (m, 2H),7.92–7.86 (m, 1H), 7.77 (t, J = 1.9 Hz, 1H), 7.71 (dd, J = 7.9, 2.0 Hz, 2H),7.57–7.46 (m, 6H), 7.44–7.32 (m, 4H).

[0097] 13 13C NMR (101 MHz, CDCl3): δ: 140.90, 139.24, 139.04, 131.52, 128.88, 126.97, 126.08, 125.39, 125.16, 123.28, 122.55, 120.84, 120.71, 113.19, 111.12, 109.85。

[0098] Based on m The production process of the thermo-exciton type polymethyl methacrylate scintillator film (2 wt% N-BA@ m CP-2Br) is as follows:

[0099] S31. Take 0.1 g of m CP-2Br and mix it with 2 mg of N-BA to obtain a mixture;

[0100] S32. Place the mixture on a 3×3 cm circular silicone substrate, select an 8 ml×16-hole heating block to accurately control the temperature on a heating table. The melting and heating program is as follows: First, heat to 160 °C and hold for 5 min, then increase the temperature by 10 °C every 3 min and hold for 2 min, and finally heat to 220 °C;

[0101] S33. Wait for the mixture to completely melt, stir until there are no bubbles, then hold for 5 min, and then naturally cool to room temperature to obtain the thermo-exciton type polymethyl methacrylate scintillator film.

[0102] Figure 12 For the radiation emission spectra of the thermo-exciton type polymethyl methacrylate scintillator film 2 wt% N-BA@ m CP-2Br and 2 wt% N-BA@ m CP, as can be seen from Figure 12 it that the thermo-exciton type polymethyl methacrylate scintillator film 2 wt% N-BA@ m CP-2Br also shows an obvious characteristic emission peak near 500 nm, and shows bright green luminescence, and its radiation emission intensity is significantly stronger than that of 2 wt% N-BA@ m CP.

[0103] The specific implementation manners of the present application are described above, but the protection scope of the present application is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present application can easily think of changes or substitutions, which should all be covered within the protection scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.

[0104] In the description of the present application, it should be understood that the term 'comprising' does not exclude the presence of elements or steps not recited in the claims. The articles 'a' or 'an' preceding an element do not exclude the presence of a plurality of such elements. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage. Any reference signs in the claims should not be construed as limiting the scope.

Claims

1. A thermally excited exciton type organic glass scintillator material, characterized in that, It includes a glass host material and a highly efficient thermoexciton luminescent guest material; The glass main body material is ; The thermally activated delayed fluorescence (TADF) high-efficiency luminescent host material is ; wherein R is H or Br; X is N; The R1 is ; R2 is H.

2. A method for preparing the thermally excited exciton type organic glass scintillator material as described in claim 1, characterized in that, Specifically, it includes the following steps: S1. Dope the thermoexciton luminescent guest material into the glass host material to obtain a mixture, and the mass ratio of the thermoexciton luminescent guest material to the glass host material is 0.001% - 6%; S2. Place the mixture on a silicone substrate and melt it. The melting temperature - rising program is: first raise the temperature to 160 °C and keep it warm for 5 min, then raise the temperature by 10 °C every 3 min until the temperature reaches the preset melting temperature; S3. After the mixture is completely melted, stir it until no bubbles are generated, then keep it warm for 5 min, and then naturally cool it to room temperature to obtain a thermoexciton - type organic glass scintillator film material.

3. The preparation method of the thermally excited exciton type organic glass scintillator material according to claim 2, wherein, In S1, the mass ratio of the thermoexciton luminescent guest material to the glass host material is 0.001%, 0.01%, 0.1%, 0.5%, 2%, 4% or 6%.

4. The preparation method of the thermally excited exciton type organic glass scintillator material according to claim 2, characterized in that, In S2, the melting heating device is a heating block.

5. The preparation method of the thermally excited exciton type organic glass scintillator material according to claim 2, characterized in that, In S2, the melting temperature is 180 - 220 °C.

6. An application of the thermoexciton - type organic glass scintillator material as described in claim 1 in X - ray imaging, and the application is for non - disease treatment and diagnosis purposes.

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