Double-glm-value circular polarization light-emitting metal halide material and preparation method and application of double-glm-value circular polarization light-emitting metal halide material

Abstract

The invention discloses a double-glm-value circular polarization luminescent metal halide material and a preparation method and application thereof, and relates to the technical field of radiation detection imaging and encryption, the chemical formula of the metal halide material is (C44H38P2) MnxZn1-xBr4, and x is more than 0 and less than 1. According to the invention, bimetal center doping is utilized for the first time, synthesis of the achiral double-glm circular polarization luminescent material is realized through a simple self-assembly synthesis method, and X-ray imaging and multi-mode encryption application are realized by utilizing the efficient luminous efficiency, X-ray response and double-glm CPL properties of the luminescent material.

Description

Technical Field

[0001] The present invention relates to the field of radiation detection materials and encryption technology, and in particular to a double g lum Circularly polarized luminescent metal halide material and its preparation method and application. Background Art

[0002] X-ray detection has been the focus of intensive research in materials science due to its widespread applications in medical imaging, security inspection, and advanced display technology. Metal halide materials have emerged as promising candidates in these fields, primarily due to their unique properties that distinguish them from traditional materials.

[0003] In the context of X-ray detection, scintillators play a crucial role in converting high-energy X-ray photons into visible light, which can then be detected and analyzed. High-performance scintillators need to have high light yield and good radiation resistance. Metal halides show great potential in meeting these requirements, with some materials achieving light yields comparable to or even higher than commercially available scintillators.

[0004] Circularly polarized luminescence (CPL) of metal halides is another fascinating property that has attracted great interest in recent years. CPL-active materials can emit circularly polarized light, which has important applications in 3D displays, optical data storage, and chiral sensing. However, realizing CPL in achiral crystalline materials remains a challenge. Most reported CPL materials are either organic molecules with relatively low luminescence efficiency or complex organic systems. Lanthanide compounds have high luminescence asymmetry factors but generally have low emission efficiency. In the pursuit of materials with multifunctional properties, doping strategies have been widely explored. Doping metal halides with different metal ions can change their electronic structure and optical properties, resulting in synergistic effects that are beneficial to improving luminescence efficiency and CPL performance.

[0005] Chemical strategies for generating CPLs mainly include: Chiral organic molecular systems require the use of chiral organic ligands (such as R- / S-MBA) combined with metal halides to induce CPL through molecular chirality. The disadvantage is that the luminescence asymmetry factor (g lum The low (value) value makes it difficult to meet practical application requirements. It relies on the synthesis and purification of chiral ligands, which is complex and costly. The organic components are susceptible to moisture and thermal degradation.

[0006] Lanthanide complexes utilize lanthanide ions (such as Eu 3+ , Tb 3+ ) ff transition to achieve high g lum Its disadvantages are low emission efficiency (generally PLQY < 30%) and limited excitation wavelength. The material is also unstable and easily affected by humidity and radiation.

[0007] Chemical strategies for generating CPLs also include: introducing chiral side chains into achiral conjugated polymer backbones; using chiral solvents to induce circularly polarized light from achiral molecules; doping small chiral molecules into achiral light-emitting polymers; and using supramolecular co-assembled materials to induce CPL. However, the production of CPLs using supramolecular materials is uncertain. Complex synthesis, uncertainty about supramolecular helical structures, and the complexity of CPL transfer limit the application of this approach.

[0008] In summary, CPL luminescence requires the participation of chiral ligands, and the luminescence efficiency and luminescence asymmetry factor g lum You can't have it all. Most reported CPL materials are either chiral organic small molecules with relatively low luminescence efficiency or complex organic systems. Chiral lanthanide compounds have high luminescence asymmetry factors, but usually have low emission efficiency. The complex synthesis of supramolecular materials, the uncertainty of supramolecular helical structure and the complexity of CPL transfer have limited the application of CPL materials. Summary of the Invention

[0009] The technical problem to be solved by the present invention is to provide a double g lum The present invention is the first to use double metal center doping to realize non-chiral double g through a simple self-assembly synthesis method. lum Synthesis of circularly polarized luminescent materials and utilization of their high luminescence efficiency and X-ray response as well as double g lum CPL properties, realizing X-ray imaging and multimodal encryption applications.

[0010] In order to solve the above technical problems, the technical solution of the present invention is: One of the purposes of the present invention is to provide a double g lum Value of circularly polarized luminescent metal halide materials.

[0011] The double g of the present invention lum The circularly polarized luminescent metal halide material has a chemical formula of: (C 44 H 38 P2)Mn x Zn 1-x Br4, where 0<x<1.

[0012] In a preferred embodiment of the present invention: Where 0.5≤x<1.

[0013] In a preferred embodiment of the present invention: The metal halide material has a crystalline structure, preferably, a space group of Pbcn; and / or The metal halide material has dual emission wavelengths, preferably, under 365nm excitation, the emission wavelengths are 417nm and 518nm; and / or, The metal halide material is double g lum Value circularly polarized light, preferably, vertical direction g lum The value is 1.52×10 -2 and 2.24×10 -2 and / or, The X-ray linear response range of the metal halide material is 9-23.5 μGy / s, and / or the linearity R 2 >0.99.

[0014] The crystal structure is stable and ordered, which is a suitable platform for generating stable and efficient CPL signals. However, currently non-chiral crystal materials generally have only a single g lum Value, and the present invention (C 44 H 38 P2)Mn x Zn 1-x Br4 crystals have significant g lum The material also boasts high luminous efficiency and excellent X-ray response, with a light yield of 42,000 photons / MeV, meeting the requirements for scintillator applications in most scenarios. Combining the triple mechanisms of wavelength, CPL polarization state, and X-ray response enables multimodal encryption applications.

[0015] In a preferred embodiment of the present invention: The metal halide material is prepared by self-assembly of raw materials including 1,2-dibromomethylbenzene, triphenylphosphine, MnBr2 and ZnBr2 through intermolecular forces.

[0016] In a preferred embodiment of the present invention: The molar ratio of 1,2-dibromomethylbenzene to triphenylphosphine is 1:(1-3), preferably 1:(1.5-2.5); and / or, The molar ratio of MnBr2 to ZnBr2 is 1:(0.5-2), preferably 1:(0.8-1.2); and / or, The molar ratio of the 1,2-dibromomethylbenzene to MnBr2 is (1-3):1, preferably (1.5-2.5):1.

[0017] The second object of the present invention is to provide a double g as described in one of the objects of the present invention. lum The invention discloses a preparation method of circularly polarized luminescent metal halide material.

[0018] The double g of the present invention lumA method for preparing a circularly polarized luminescent metal halide material, the method comprising: 1,2-dibromomethylbenzene and triphenylphosphine are dissolved in a first solvent, MnBr2 and ZnBr2 are dissolved in a second solvent, the two solutions are mixed, the solvent is evaporated to precipitate crystals, and the metal halide material is obtained after washing and drying.

[0019] In a preferred embodiment of the present invention: The molar ratio of 1,2-dibromomethylbenzene to triphenylphosphine is 1:(1-3), preferably 1:(1.5-2.5); and / or, The concentration of 1,2-dibromomethylbenzene after being dissolved in the first solvent is 0.05-0.2 mol / L, preferably 0.08-0.12 mol / L; and / or, The molar ratio of MnBr2 to ZnBr2 is 1:(0.5-2), preferably 1:(0.8-1.2); and / or, The concentration of MnBr2 after being dissolved in the second solvent is 0.05-0.2 mol / L, preferably 0.08-0.12 mol / L; and / or, The volume ratio of the first solvent to the second solvent is (1-3):1, preferably (1.5-2.5):1.

[0020] In a preferred embodiment of the present invention: The first solvent is at least one of dichloromethane, ether, and n-hexane; and / or, The second solvent is at least one of anhydrous ethanol, ethylene glycol, and isopropyl alcohol.

[0021] In a preferred embodiment of the present invention: The volatilization temperature is room temperature, and / or the volatilization time is 1-5 days.

[0022] The third object of the present invention is to provide a double g as described in one of the objects of the present invention. lum Value circularly polarized luminescent metal halide material or double g prepared by the method according to the second object of the present invention lum Application of circularly polarized luminescent metal halide materials in multimodal encryption and X-ray imaging.

[0023] The present invention utilizes the helical structure of achiral metal halides to stimulate CPL luminescence, does not require complex and expensive chiral components, and utilizes simple organic ligands and metal halide centers to synthesize helical structure compounds through self-assembly. At the same time, the present invention optimizes the energy level transition path by doping the Zn / Mn metal center, taking into account both efficiency and performance, and synthesizes double g lum High-value achiral metal halides with breakthrough luminescence efficiency and high g lumThe preparation process of the present invention is simple, the yield is high, and the cost of raw materials is reduced.

[0024] The present invention also utilizes the high luminous efficiency and high X-ray response of metal halides to apply them to the field of X-ray imaging; using dual wavelength and dual g lum value and different responsiveness to X-rays, and is applied to high-intensity encryption-related fields; and the metal halide material of the present invention has good environmental tolerance.

[0025] The beneficial effects of the present invention are further reflected in: 1. Comparative advantages: Existing achiral materials (such as (KC)2MnBr4) can only achieve single-wavelength CPL, while this invention achieves dual g for the first time through a helical superstructure and a bimetallic doping strategy. lum value CPL, significantly improving the optical information encoding capability.

[0026] 2. High light yield and X-ray response performance: Light yield advantage: The X-ray excitation light yield reaches 42,000 photons / MeV, far exceeding the traditional scintillators BGO (10,000 photons / MeV) and LYSO (33,000 photons / MeV), suitable for high-resolution medical imaging; Linear response: Within the dose range of 9-23.5μGy / s, the light intensity is linearly related to the X-ray dose, ensuring imaging accuracy.

[0027] 3. Excellent stability and environmental resistance: The material exhibits no significant degradation in luminescence performance and an extended service life under conditions of high temperature (315°C), high humidity (95% RH), and radiation (100 Gy). Compared to conventional materials, the PLQY of conventional lanthanide complexes decreases significantly at the same humidity, while the stability of the material presented in this invention is significantly improved.

[0028] 4. Multifunctional integration expands application scenarios: Multimodal encryption applications: (1) Wavelength encryption: Short-pass (<450nm) and long-pass (>475nm) filters are used to separate dual-wavelength emissions, achieving layered information encryption. (2) CPL encryption: Combining a quarter-wave plate with a polarizer switches the left / right optical state, enhancing anti-counterfeiting security. (3) X-ray response encryption: Only CPM and pure Mn materials are sensitive to X-rays, allowing for the design of multiple verification mechanisms.

[0029] 5. High-resolution X-ray imaging: The spatial resolution reaches 5-8lp / mm, which can clearly identify chip microstructures, spring details, etc.; Light transmittance: The transmittance in the visible light and infrared bands is good, and it is compatible with a variety of optical detection systems.

[0030] 6. Synthesis process optimization and cost reduction: Single crystals are synthesized by the slow evaporation method (yield ≥ 85%), without the need for high temperature and high pressure or complex purification steps; without chiral ligands: CPL is excited by the spontaneous symmetry breaking of the helical superstructure, eliminating expensive chiral raw materials (such as R- / S-MBA), resulting in cost reduction.

[0031] 7. Material scalability and flexibility of bimetal doping: By adjusting the Mn / Zn ratio (0 < x < 1), the emission wavelength and CPL intensity can be customized to meet the requirements of different applications.

[0032] 8. Economic benefits and social value: Reducing equipment costs in the medical field, high light yield reduces the demand for X-ray doses, lowering the radiation risk to patients and equipment power consumption; high-precision diagnosis, high-resolution imaging helps in early tumor detection and minimally invasive surgery navigation.

[0033] 9. In the field of information security, it helps to upgrade anti-counterfeiting: The triple encryption mode (wavelength, CPL, X-ray) can be applied to high-end product labels, digital currency carriers, etc., improving anti-copying performance.

[0034] 10. Non-destructive industrial inspection: The radiation-resistant properties of the material are suitable for long-term online monitoring of nuclear power plants and aerospace components.

[0035] In summary, through the design of the helical superstructure and the synergistic effect of bimetals, the present invention achieves dual g lum -value CPL, high light yield, strong stability and multi-functional integration, significantly improving the technical performance. Its low-cost synthesis process and multi-scenario applicability provide new solutions for the fields of medical imaging, information security and industrial inspection, with significant technological breakthroughs and market application potential. Brief Description of the Drawings

[0036] Figure 1 Schematic diagram of the crystal structure of (C 44 H 38 P2)Mn <00000​​​​​​​​​​​​​​​​​​​​​​​​​0.19 Energy dispersive spectroscopy (EDS) diagram of Br4 crystal; Figure 4 (C 44 H 38 P2)Mn 0.81 Zn 0.19 Br4 crystal quantum yield results diagram; Figure 5 (C 44 H 38 P2)Mn 0.81 Zn 0.19 Circularly polarized luminescence image of Br4 crystal; Figure 6 (C 44 H 38 P2)Mn 0.81 Zn 0.19 Light yield diagram of Br4 crystal; Among them, BGO is bismuth germanium oxide scintillation crystal; LYSO is lutetium yttrium silicate scintillation crystal; CPM is (C 44 H 38 P2)Mn 0.81 Zn 0.19 Br4 crystals; Figure 7 (C 44 H 38 P2)Mn 0.81 Zn 0.19 Br4 crystal linear response to X-rays; Figure 8 (C 44 H 38 P2)Mn 0.81 Zn 0.19 Thermogravimetric analysis of Br4 crystals; Figure 9 (C 44 H 38 P2)Mn 0.81 Zn 0.19 Radiation stability and humidity stability results of Br4 crystals; Figure 10 This is the waveform of the short-pass filter (HSPH450D25); Figure 11 This is the waveform of the long-pass filter (HGLPD25GG475); Figure 12 The short-pass filter and the long-pass filter are used to filter the (C 44 H38 P2)Mn 0.81 Zn 0.19 The effect of wavelength encryption by Br4 crystal; Among them, a is the luminescence image under ultraviolet light; b is the luminescence image under a short-pass filter; c is the luminescence image under a long-pass filter; Figure 13 In order to verify the (C 44 H 38 P2)Mn 0.81 Zn 0.19 The Br4 crystal is switched between left-handed (a) and right-handed (b) light, and the brightness change of the crystal is detected; Figure 14 For the (C 44 H 38 P2)Mn 0.81 Zn 0.19 The effect of X-ray encryption of Br4 crystal; Among them, a is the image under natural light; b is the image under ultraviolet light; c is the image under X-ray light; Figure 15 Schematic diagram of the structure of CMOS camera and single crystal imaging system; Figure 16 (C 44 H 38 P2)Mn 0.81 Zn 0.19 Resolution test results of Br4 crystal; Figure 17 (C 44 H 38 P2)Mn 0.81 Zn 0.19 Br4 crystals are used for high-contrast imaging of chips, springs, and resistors; Among them, a is a picture of the chip under natural light (top) and the imaging under X-ray (bottom); b is a picture of the spring under natural light (top) and the imaging under X-ray (bottom); c is a picture of the resistor under natural light (top) and the imaging under X-ray (bottom); d is a picture of the chip metal foot under natural light (top) and the imaging under X-ray (bottom). DETAILED DESCRIPTION

[0037] The following is a further description of specific embodiments of the present invention in conjunction with the accompanying drawings. It should be noted that the description of these embodiments is intended to facilitate understanding of the present invention and does not constitute a limitation of the present invention. In addition, the technical features involved in the various embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.

[0038] Unless otherwise specified, the raw materials used in the examples of the present invention are all commercially available products.

[0039] [Example 1] Double glum value circularly polarized luminescent single crystal (C 44 H 38 P2)Mn 0.81 Zn 0.19 Br4 (denoted as CPM) synthesis: 1. Dissolve 1,2-dibromomethylbenzene (1 mmol) and triphenylphosphine (2 mmol) in 10 mL of dichloromethane.

[0040] 2. Dissolve MnBr2 (0.5 mmol) and ZnBr2 (0.5 mmol) in 5 mL of anhydrous ethanol.

[0041] 3. Mix the two solutions, slowly evaporate the solvent and let it stand at room temperature for 2-3 days to precipitate light green transparent single crystals (yield ≥ 85%).

[0042] 4. Post-processing: The crystals are washed with ethanol and then dried at room temperature. No high temperature annealing or complex purification is required.

[0043] [Example 2] Synthesis of double glum value circularly polarized luminescent single crystal: 1. Dissolve 1,2-dibromomethylbenzene (1 mmol) and triphenylphosphine (1 mmol) in 20 mL of diethyl ether.

[0044] 2. Dissolve MnBr2 (1 mmol) and ZnBr2 (0.5 mmol) in 20 mL of ethylene glycol.

[0045] 3. Mix the two solutions, slowly evaporate the solvent and let it stand at room temperature for 2-3 days to precipitate light green transparent single crystals (yield ≥ 85%).

[0046] 4. Post-processing: The crystals are washed with ethylene glycol and then dried at room temperature, without the need for high temperature annealing or complex purification.

[0047] [Example 3] Synthesis of double glum value circularly polarized luminescent single crystal: 1. Dissolve 1,2-dibromomethylbenzene (1 mmol) and triphenylphosphine (3 mmol) in 5 mL of n-hexane.

[0048] 2. Dissolve MnBr2 (0.3 mmol) and ZnBr2 (0.6 mmol) in 2 mL of isopropanol.

[0049] 3. Mix the two solutions, slowly evaporate the solvent and let it stand at room temperature for 2-3 days to precipitate light green transparent single crystals (yield ≥ 85%).

[0050] 4. Post-processing: The crystals are washed with isopropanol and then dried at room temperature. No high temperature annealing or complex purification is required.

[0051] The (C 44 H 38 P2)Mn 0.81 Zn 0.19 Br4 crystals were analyzed by crystal XRD, PLATON version of 28 / 11 / 2022, and verified by EDS. The crystal data are shown in Table 1 below: From the test results in Table 1, it can be seen that the space group of the crystal is Pbcn, and the unit cell parameters are a=11.87Å, b=18.93Å, and c=18.79Å.

[0052] Depend on Figure 2 The optical performance results show that under 365nm ultraviolet light, the crystal prepared in Example 1 has two luminescence centers: the Zn center: dominates the 417nm emission (blue light, self-trapped exciton luminescence, STE); the Mn center: dominates the 518nm emission (green light, dd transition); the CIE color coordinates are (0.18, 0.40); and the fluorescence lifetimes are 6.39 microseconds and 293.13 microseconds, respectively.

[0053] Depend on Figure 3 The energy dispersive spectrum (EDS) diagram can determine the Mn / Zn metal doping ratio of the crystal prepared in Example 1.

[0054] Depend on Figure 4 It can be seen from the quantum yield results that the photoluminescence quantum yield (PLQY) of the crystal prepared in Example 1 reaches 57.1%, which has high quantum efficiency.

[0055] The CPL luminescence of the crystal prepared in Example 1 was detected by CPL3000. The test results are as follows: Figure 5 As shown, the crystal is double g lum Value of circularly polarized light, g in the vertical direction lum The value is 1.52×10 -2 (417nm) and 2.24×10 -2 (518nm).

[0056] Depend on Figure 6 As can be seen from the light yield graph, the light yield of the crystal prepared in Example 1 reaches 42,000 photons / MeV, far exceeding the traditional scintillators LYSO (33,000 photons / MeV) and BGO (10,000 photons / MeV).

[0057] The crystal was irradiated with an X-ray machine at different doses and the luminescence intensity was measured with a spectrometer. Figure 7 The linear response result of the crystal to X-ray is shown in the figure. It can be seen from the results that the linear response range of the crystal X-ray prepared in Example 1 is 9-23.5μGy / s, and the linearity R 2 >0.99, the light intensity and X-ray dose are linearly related, ensuring imaging accuracy.

[0058] Depend on Figure 8 It can be seen from the thermogravimetric analysis diagram that the crystals prepared in Example 1 have no weight loss below 315°C and have high temperature resistance.

[0059] Radiation stability test: First test and record the luminescence intensity of the crystal, then irradiate the crystal with X-rays at doses of 30Gy, 60Gy, and 100Gy, and then test and record the luminescence intensity of the crystal. Humidity stability test: First test and record the luminescence intensity of the crystal, then place the crystal in a humidity environment of 40%, 65%, and 95% for half an hour, and then test and record the luminescence intensity of the crystal.

[0060] Depend on Figure 9 From the radiation stability and humidity stability results, it can be seen that the luminous intensity of the crystal prepared in Example 1 remains >95% after 100Gy dose irradiation; there is no performance attenuation in a 95% RH environment; and the crystal has radiation resistance and moisture resistance.

[0061] Depend on Figure 10-12 It can be seen from the wavelength encryption effect that a short-pass filter (HSPH450D25) (<450nm) can be used to display blue light, and a long-pass filter (HGLPD25GG475) (>475nm) can be used to display green light, thereby achieving the effect of wavelength encryption.

[0062] CPL Encryption: Figure 13 By combining a quarter-wave plate with a polarizer, the switching between left-handed (LCP) and right-handed (RCP) light was verified, and the switching of the crystal brightness change was detected, further verifying its CPL properties.

[0063] (C 44 H 38 P2) Preparation of MnBr4 (denoted as pure Mn): 1,2-dibromomethylbenzene (1 mmol) and triphenylphosphine (2 mmol) were dissolved in 10 mL of dichloromethane, and MnBr2 (1 mmol) was dissolved in 5 mL of anhydrous ethanol. The two solutions were mixed and the solvent was evaporated to precipitate crystals, which were washed and dried to obtain (C 44 H 38 P2)MnBr4.

[0064] (C 44 H 38P2) Preparation of ZnBr4 (denoted as pure Zn): 1,2-dibromomethylbenzene (1 mmol) and triphenylphosphine (2 mmol) were dissolved in 10 mL of dichloromethane, and ZnBr2 (1 mmol) was dissolved in 5 mL of anhydrous ethanol. The two solutions were mixed and the solvent was evaporated to precipitate crystals, which were washed and dried to obtain (C 44 H 38 P2)ZnBr4.

[0065] The prepared CPM crystal, pure Mn crystal and pure Zn crystal were ground into powder respectively, placed into a mold, added with UV curing glue, and cured under UV light for 5-10 seconds to test their X-ray encryption effect.

[0066] Depend on Figure 14 From the X-ray encryption effect, it can be seen that only CPM and pure Mn materials are sensitive to X-rays and can be used to design dynamic encryption tags.

[0067] Use Figure 15 The industrial-grade CMOS camera shown in the figure was tested for resolution with a single-crystal imaging system. The test results are shown in the figure below. Figure 16 As shown, the standard line pair card verification spatial resolution is about 5-8lp / mm.

[0068] Depend on Figure 17 From the high-contrast imaging of chips, springs and resistors, it can be seen that CPM can be actually applied to high-contrast imaging of chips, springs and resistors, etc., and can clearly identify chip microstructures, spring details, etc.

[0069] The embodiments of the present invention are described in detail above with reference to the accompanying drawings, but the present invention is not limited to the described embodiments. It is apparent to those skilled in the art that various changes, modifications, substitutions, and variations to these embodiments may be made without departing from the principles and spirit of the present invention, and these changes and modifications still fall within the scope of protection of the present invention.

Claims

1. A double G lum Circularly polarized luminescent metal halide material, characterized in that The chemical formula of the metal halide material is: (C 44 H 38 P2)Mn x Zn 1-x Br4, where 0<x<1.

2. The metal halide material according to claim 1, wherein: Where 0.5≤x<1.

3. The metal halide material according to claim 1 or 2, characterized in that: The metal halide material has a crystalline structure, preferably, a space group of Pbcn; and / or The metal halide material has dual emission wavelengths, preferably, under 365nm excitation, the emission wavelengths are 417nm and 518nm; and / or, The metal halide material is double g lum Value circularly polarized light, preferably, vertical direction g lum The value is 1.52×10 -2 and 2.24×10 -2 and / or, The X-ray linear response range of the metal halide material is 9-23.5 μGy / s, and / or the linearity R 2 >0.

99.

4. The metal halide material according to claim 1 or 2, characterized in that: The metal halide material is prepared by self-assembly of raw materials including 1,2-dibromomethylbenzene, triphenylphosphine, MnBr2 and ZnBr2 through intermolecular forces.

5. The metal halide material according to claim 4, wherein: The molar ratio of 1,2-dibromomethylbenzene to triphenylphosphine is 1:(1-3), preferably 1:(1.5-2.5); and / or, The molar ratio of MnBr2 to ZnBr2 is 1:(0.5-2), preferably 1:(0.8-1.2); and / or, The molar ratio of the 1,2-dibromomethylbenzene to MnBr2 is (1-3):1, preferably (1.5-2.5):

1.

6. A double g as claimed in any one of claims 1 to 5 lum A method for preparing a circularly polarized luminescent metal halide material, characterized in that The method comprises: 1,2-dibromomethylbenzene and triphenylphosphine are dissolved in a first solvent, MnBr2 and ZnBr2 are dissolved in a second solvent, the two solutions are mixed, the solvent is evaporated to precipitate crystals, and the metal halide material is obtained after washing and drying.

7. The method according to claim 6, characterized in that: The molar ratio of 1,2-dibromomethylbenzene to triphenylphosphine is 1:(1-3), preferably 1:(1.5-2.5); and / or, The concentration of 1,2-dibromomethylbenzene after being dissolved in the first solvent is 0.05-0.2 mol / L, preferably 0.08-0.12 mol / L; and / or, The molar ratio of MnBr2 to ZnBr2 is 1:(0.5-2), preferably 1:(0.8-1.2); and / or, The concentration of MnBr2 after being dissolved in the second solvent is 0.05-0.2 mol / L, preferably 0.08-0.12 mol / L; and / or, The volume ratio of the first solvent to the second solvent is (1-3):1, preferably (1.5-2.5):

1.

8. The method according to claim 6, wherein: The first solvent is at least one of dichloromethane, ether, and n-hexane; and / or, The second solvent is at least one of anhydrous ethanol, ethylene glycol, and isopropyl alcohol.

9. The method according to claim 6, wherein: The volatilization temperature is room temperature, and / or the volatilization time is 1-5 days.

10. A double g as claimed in any one of claims 1 to 5 lum Value circularly polarized luminescent metal halide material or double g prepared by the method according to any one of claims 6 to 9 lum Application of circularly polarized luminescent metal halide materials in multimodal encryption and X-ray imaging.

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