An organic-inorganic hybrid manganese halide luminescent material, a preparation method and application thereof

Abstract

The application belongs to the technical field of new materials, and particularly relates to an organic-inorganic hybrid manganese halide luminescent material, a preparation method and application thereof. 19 H 18 P)2MnBr4, and a chemical formula weight is 929 g / mol; the (C 19 H 18 P)2MnBr4 is a crystal, and the (C 19 H 18 P)2MnBr4 crystal has a space group of R-3c, cell parameters of alpha = beta = 90 degrees, gamma = 120 degrees, and Z = 6. The organic-inorganic hybrid manganese halide prepared by the application has high luminescence and high stability.

Description

Technical Field

[0001] This invention belongs to the field of new materials technology, specifically relating to an organic-inorganic hybrid manganese halide luminescent material, its preparation method, and its application. Background Technology

[0002] Organic-inorganic hybrid metal halides have broad application prospects in fields such as solid-state lighting, flat panel displays, and scintillators due to their excellent optical properties and simple preparation methods. Among them, organic-inorganic hybrid lead halides have attracted widespread attention due to their superior optical properties, including high light absorption coefficient, high quantum yield, and tunable fluorescence emission wavelength. However, lead halides suffer from lead toxicity and instability, which seriously hinder their practical application.

[0003] In recent years, organic-inorganic hybrid manganese halides have attracted great interest from researchers due to their non-toxicity and good stability. Compared with other precious metals, manganese has the advantages of abundant resources, environmental friendliness, low cost, and a wide variety of coordination types, among which Mn... 2+ The spin-forbidden dd transition of is closely related to the crystal field strength, and its absorption and emission wavelengths can be tuned by changing the coordination environment, making it a good luminescent center ion.

[0004] Although numerous studies have reported the preparation of organic-inorganic hybrid manganese halides, the currently prepared organic-inorganic hybrid manganese halides suffer from limitations such as low luminescence efficiency and poor luminescence stability, restricting their practical applications in solid-state lighting, flat panel displays, and X-ray scintillation. Obtaining organic-inorganic hybrid manganese halide luminescent materials that possess both high luminescence efficiency and high stability is a cutting-edge research hotspot and a major challenge in this field. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides an organic-inorganic hybrid manganese halide luminescent material, its preparation method, and its applications. The organic-inorganic hybrid manganese halide exhibits both high luminescence efficiency and high stability.

[0006] In a first aspect, the present invention provides an organic-inorganic hybrid manganese halide luminescent material, wherein the chemical formula of the organic-inorganic hybrid manganese halide is (C 19 H 18 P)2MnBr4, with a chemical formula weight of 929 g / mol; the (C) 19 H 18 P)2MnBr4 is a crystal, and the (C) 19 H 18 The space group of P)2MnBr4 crystal is R-3c, and its unit cell parameters are... α=β=90°, γ=120°, Z=6.

[0007] According to the present application, the (C 19 H 18 P)2MnBr4 is a crystal with a tetrahedral structure, and the Mn 2+ is asymmetrically extended along the c-axis, and is statistically distributed.

[0008] According to the present application, the (C 19 H 18 P)2MnBr4 crystal is a pure phase.

[0009] According to the present application, the (C 19 H 18 P)2MnBr4 crystal has a structure substantially as shown in Figure 1 .

[0010] According to the present application, the (C 19 H 18 P)2MnBr4 crystal has an X-ray powder diffraction spectrum substantially as shown in Figure 2 .

[0011] According to the present application, the (C 19 H 18 P)2MnBr4 crystal has an X-ray photoelectron spectrum substantially as shown in Figure 3 .

[0012] According to the present application, the (C 19 H 18 P)2MnBr4 crystal has an infrared spectrum substantially as shown in Figure 4 .

[0013] According to the present application, the (C 19 H 18 P)2MnBr4 crystal has an emission spectrum substantially as shown in Figure 5 .

[0014] According to the present application, the (C 19 H 18 P)2MnBr4 crystal has a thermogravimetric spectrum substantially as shown in Figure 6 .

[0015] According to the present application, the (C 19 H 18 P)2MnBr4 crystal has a thermal decomposition temperature greater than 350°C, and preferably the (C 19 H 18 P)2MnBr4 crystal has a thermal decomposition temperature greater than 360°C.

[0016] According to the present application, the (C 19H 18 The thermal quenching temperature of the (C 19 H 18 The luminescence intensity of the (C

[0017] According to the present application, the (C 19 H 18 The air stability of the (C

[0018] In a second aspect, the present application provides a method for preparing the above-mentioned organic-inorganic hybrid manganese halide luminescent material, comprising using a method known in the art, such as room temperature evaporation crystallization method or coprecipitation method, for example, the coprecipitation method to prepare the (C 19 H 18 The (C

[0019] According to the present application, the (C 19 H 18 The method for preparing the (C

[0020] S1, mixing and dissolving a manganese compound, triphenyl-methyl phosphonium bromide and a solvent to obtain a precursor solution;

[0021] S2, reacting the precursor solution at a temperature of 80-140℃ for 20-120min to obtain a reaction solution.

[0022] According to an embodiment of the present application, the molar ratio of the manganese compound to triphenyl-methyl phosphonium bromide in step S1 is 1:(1-3), for example, 1:1, 1:2, 1:3.

[0023] According to the present application, the manganese compound is selected from at least one of manganese carbonate, manganese oxalate, manganese nitrate, manganese acetate, manganese acetylacetonate, manganese bromide, manganese chloride, manganese iodide.

[0024] According to the present application, the solvent is a hydrobromic acid solution.

[0025] According to the present application, step S1 comprises the following steps: mixing the manganese compound, triphenyl-methyl phosphonium bromide and the solvent, and heating to 80-140℃ until the solution is clear and transparent.

[0026] According to the present application, step S1 is carried out under ambient conditions.

[0027] According to the present application, step S2 is carried out under ambient conditions.

[0028] According to the present application, the ambient temperature refers to the condition of normal temperature and pressure, and humidity of 15-35%.

[0029] According to the present application, the step S2 is followed by the step of cooling the reaction solution to obtain the solid product.

[0030] According to the present application, the cooling comprises cooling the reaction solution to room temperature.

[0031] According to the present application, the step S2 is followed by the step of separating the solid product from the reaction solution after cooling, and washing the solid product.

[0032] According to the present application, the separating the solid product from the reaction solution comprises using common methods in the art, such as filtration and centrifugation.

[0033] According to the present application, the washing the solid product comprises rinsing the surface of the solid product with a washing solvent to remove the hydrogen bromide solution and the unreacted precursor remaining on the surface of the solid product.

[0034] According to the present application, the washing solvent is an organic solvent, preferably the washing solvent can be ethanol or isopropanol, for example, ethanol.

[0035] According to the present application, the washing can be filtration washing or centrifugation washing.

[0036] According to the present application, the washing is followed by the step of drying the washed product to obtain the (C 19 H 18 P)2MnBr4 crystal.

[0037] According to the present application, the drying is performed at a temperature of 30-80°C, preferably the drying is performed at a temperature of 50-80°C, for example, 50°C, 60°C, 70°C, 80°C.

[0038] In a third aspect, the present application further provides a use of the above-mentioned organic-inorganic hybrid manganese halide or the organic-inorganic hybrid manganese halide prepared by the above-mentioned method as a luminescent material, preferably as a photoluminescent device, for example, for light emitting diodes and / or X-ray scintillators.

[0039] In a fourth aspect, the present application further provides a luminescent material comprising the above-mentioned organic-inorganic hybrid manganese halide, preferably the luminescent material further comprises a fluorescent powder.

[0040] Advantages

[0041] 1. The reaction raw materials for preparing the organic-inorganic hybrid manganese halide luminescent material according to the present application can be directly purchased from a reagent company without further purification, so that the preparation cost can be effectively reduced, and meanwhile, the preparation steps are simple, the reaction temperature is relatively low, and the reaction time is relatively short, so that the present application is convenient for large-scale preparation and industrialization, and realizes the synthesis of the organic-inorganic hybrid manganese halide luminescent material with high luminescence and high stability.

[0042] 2. The organic-inorganic hybrid manganese halide material according to the present application has good luminescence performance, a high quantum yield of 99.5%, and excellent stability, and the thermal weight loss is only 5% at a temperature of 367 DEG C, the phase change does not occur under normal temperature conditions for 6 months, meanwhile, the luminescence intensity can be maintained at 84% at 150 DEG C, and the luminescence intensity can be maintained at more than 97% after constant temperature at 150 DEG C for 3h; and the main element Mn contained therein has low toxicity, and has high practicability. BRIEF DESCRIPTION OF DRAWINGS

[0043] Figure 1 It is a crystal structure framework diagram of the product obtained in Example 1;

[0044] Figure 2 It is an X-ray powder diffraction spectrum diagram of the product obtained in Example 1;

[0045] Figure 3 It is a related X-ray photoelectron spectrum (XPS) of the product obtained in Example 1;

[0046] Figure 4 It is an infrared spectrum (FTIR) of the product obtained in Example 1;

[0047] Figure 5 It is an excitation emission spectrum of the product obtained in Example 1; solid line: emission spectrum (excitation wavelength is 363 nm); dotted line: excitation spectrum (emission wavelength is 516 nm).

[0048] Figure 6 It is a thermogravimetric spectrum of the product obtained in Example 1;

[0049] Figure 7 It is a variable temperature spectrum of the product obtained in Example 1;

[0050] Figure 8 It is the light irradiation stability of the product obtained in Example 1 at different temperatures;

[0051] Figure 9 It is an X-ray powder diffraction spectrum diagram of the product obtained in Example 1 after being placed in air for 6 months;

[0052] Figure 10 It is the luminescence intensity change of the product obtained in Example 1 after being placed in air for 6 months;

[0053] Figure 11 The electroluminescence spectrum, specific parameters, and physical image of the product obtained in Example 1 after mixing with a gallium nitride chip and a commercial red phosphor under blue light excitation are shown.

[0054] Figure 12 The image shows the X-ray excitation spectrum of the product obtained in Example 1 and a comparison with that of the commercial scintillator bismuth germanate.

[0055] Figure 13 This is an X-ray scintillation image of the organic-inorganic hybrid manganese halide. Detailed Implementation

[0056] The following detailed description, in conjunction with specific embodiments, further illustrates the organic-inorganic hybrid manganese halide luminescent material of the present invention, its preparation method, and its applications. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0057] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0058] The raw material manganese compound used in the following examples was selected from manganese acetate, purchased from Aladdin, with a purity of 99.99%; and triphenylmethylphosphonium bromide, purchased from Aladdin, with a purity of 98%.

[0059] The organic-inorganic hybrid manganese halide luminescent materials prepared in the following examples were characterized using the following instruments and equipment:

[0060] The instrument used for X-ray powder diffraction was a MiniFlex2 manufactured by Rigaku, and the copper target radiation wavelength was λ = 0.154187 nm.

[0061] The instrument used for X-ray energy dispersive spectroscopy analysis was model JSM-6700F, manufactured by JEOL.

[0062] The instrument used for emission spectroscopy characterization was an FLS980 manufactured by Edinburgh, with a xenon lamp as the excitation source, an excitation wavelength of 363 nm, and a monitoring wavelength of 516 nm.

[0063] Example 1:

[0064] S101. Weigh 10 mmol of triphenylmethylphosphonium bromide (C) at room temperature. 19 H 18PBr) powder and 5 mmol of manganese acetate powder were added into a 100 mL two-necked flask, 5 mL of hydrobromic acid was added, and the mixture was uniformly mixed at room temperature. The precursor was completely dissolved in the flask by heating to 120°C while stirring until the mixed solution was clear and transparent, obtaining a precursor solution.

[0065] S102、the precursor solution prepared in step S101 was reacted at 120°C for 20 min, and then naturally cooled to room temperature, obtaining a reaction solution. The reaction solution was washed with ethanol to obtain stable (C 19 H 18 P)2MnBr4 block crystals.

[0066] The obtained (C 19 H 18 P)2MnBr4 block crystals were characterized by X-ray single crystal diffraction, as shown in Figure 1 It can be seen that the (C 19 H 18 P)2MnBr4 crystal belongs to the R-3c space group, and the unit cell parameters are as follows: α = β = 90°, γ = 120°, Z = 6.

[0067] The XRD powder diffraction pattern of the (C 19 H 18 P)2MnBr4 crystal is shown in Figure 2 The diffraction peak position and relative intensity of the obtained sample are consistent with the theoretical XRD diffraction pattern, indicating that the (C 19 H 18 P)2MnBr4 crystal has a tetrahedral structure, and the (C 19 H 18 P)2MnBr4 block crystal prepared in this embodiment is a pure phase.

[0068] XPS characterization of Figure 3 It can be confirmed that the (C 19 H 18 P)2MnBr4 contains C, H, P, Br and Mn elements.

[0069] FTIR characterization of Figure 4 It can be confirmed that the organic components in the (C 19 H 18 P)2MnBr4 have the same peak value as the benzene ring and C-H bond in the precursor C 19 H 18 PBr.

[0070] As shown in Figure 5 Under 363 nm excitation, the (C 19 H18 The P)2MnBr4 crystal has an emission peak at 516 nm, and the measured (C) 19 H 18 The photoluminescent quantum yield of P)2MnBr4 bulk crystal is 99.5%.

[0071] For (C) 19 H 18 Thermogravimetric analysis (TGA) was performed on P)₂MnBr₄ crystals under nitrogen atmosphere, with a heating rate of 10 °C / min. The measurement temperature range was 30–500 °C. (See [reference needed]). Figure 6 As shown, (C) 19 H 18 P)2MnBr4 crystals retain 95% of their initial mass at 367℃, but above 367℃, (C) 19 H 18 The rapid loss of mass in the P)2MnBr4 crystal indicates that (C) 19 H 18 P)2MnBr4 crystals have high thermal stability (367℃).

[0072] Under environmental conditions (temperature 25℃, humidity 30%), the effect on (C) 19 H 18 The thermal quenching resistance of P)2MnBr4 crystals was tested at temperatures ranging from 30℃ to 200℃, with a stabilization time of 4 minutes at each temperature point (per℃). The data obtained are as follows: Figure 7 As shown, the sample can maintain 84% of its luminescence intensity at 150°C, indicating that the (C) prepared in this embodiment... 19 H 18 P)2MnBr4 crystals have high resistance to thermal quenching.

[0073] (C) 19 H 18 P)2MnBr4 crystals were kept at 30℃, 90℃, and 150℃ for 3 hours each under ambient conditions (temperature 25℃, humidity 30%), and their luminescence intensity was measured every ten minutes. The results are as follows: Figure 8 As shown, (C) 19 H 18 P)2MnBr4 crystals maintained over 97% luminescence intensity after being held at three different temperatures for three hours, indicating that (C) 19 H 18 P)2MnBr4 crystals exhibit excellent resistance to light exposure.

[0074] See Figure 9 It can be seen that (C) 19 H 18 The P)2MnBr4 crystal did not undergo a phase transition after being placed under environmental conditions for six months, indicating that (C)19 H 18 P)2MnBr4 crystals have good stability in air.

[0075] Referring to Figure 10 shown, the (C 19 H 18 P)2MnBr4 crystals after being placed for six months under ambient conditions, the results show that the (C 19 H 18 P)2MnBr4 crystals after being placed for six months, the luminescent intensity can still maintain 87% of the initial intensity, indicating that the (C 19 H 18 P)2MnBr4 crystals have good light stability.

[0076] The (C 19 H 18 P)2MnBr4 crystals prepared in this embodiment are mixed with commercial KSF red fluorescent powder, and then coated in the middle of a gallium nitride chip and solidified, the driving voltage of the gallium nitride chip is 1V, the driving current is 0-300mA, and the gallium nitride chip is fixed in an LED device, referring to Figure 11 shown, the (C 19 H 18 P)2MnBr4 crystals mixed with a gallium nitride chip and commercial red fluorescent powder (KSF) under blue light chip excitation, the actual picture of the packaged white light LED device is shown in Figure 11 the drawing Figure 11 in the upper left corner, wherein the CIE coordinates fall in the white light region, and have good luminous efficiency and color rendering index, indicating that the prepared sample has good application prospect in the field of white light emitting diodes.

[0077] Referring to Figure 12 shown, the (C 19 H 18 P)2MnBr4 crystals and commercial bismuth germanate scintillator (BGO) under X-ray excitation, from the figure, it can be seen that the (C 19 H 18 P)2MnBr4 crystals under X-ray excitation, the luminescent intensity is much higher than that of BGO, it can be inferred that the (C 19 H 18 P)2MnBr4 crystals under X-ray excitation, have excellent optical properties, and the luminescent performance is much higher than that of commercial bismuth germanate scintillator.

[0078] Figure 13The upper part is the actual image of the sample, and the lower part is the scintillation imaging effect diagram of the sample under X-ray excitation. 19 H 18 P)2MnBr4crystal has excellent imaging performance. 19 H 18 P)2MnBr4crystal has excellent imaging performance.

[0079] X-ray scintillation imaging is based on the penetration of X-rays, fluorescence effect and photosensitive effect. On the other hand, there are differences in density and thickness between the internal parts of the object. When X-rays penetrate different structures inside the object, the degree of absorption is different, so the amount of X-rays reaching the screen is different. Thus, the images with different light and dark or black and white contrasts are formed on the screen. When the X-rays pass through the electronic key and the circuit board with the (C 19 H 18 P)2MnBr4crystal, the internal chips and circuits will appear, that is, the imaging effect.

[0080] Example 2:

[0081] S201, under room temperature, 10mmol of triphenyl methyl phosphonium bromide (C 19 H 18 PBr) powder and 5mmol of manganese acetate powder are added into a 100mL two-necked flask, and then 5mL of hydrobromic acid is added. The mixture is uniformly mixed at room temperature, and is heated to 120℃ while stirring, so that the precursor in the flask is completely dissolved until the mixed solution is clear and transparent, obtaining a precursor solution.

[0082] S202, after the precursor solution prepared in S201 is reacted at 120℃ for 30min, it is naturally cooled to room temperature to obtain a reaction solution. The reaction solution is washed with ethanol to obtain stable (C 19 H 18 P)2MnBr4block crystal.

[0083] Example 3:

[0084] S301, under room temperature, 10mmol of triphenyl methyl phosphonium bromide (C 19 H 18 PBr) powder and 5mmol of manganese acetate powder are added into a 100mL two-necked flask, and then 5mL of hydrobromic acid is added. The mixture is uniformly mixed at room temperature, and is heated to 120℃ while stirring, so that the precursor in the flask is completely dissolved until the mixed solution is clear and transparent, obtaining a precursor solution.

[0085] S302, after the precursor solution prepared in S301 is reacted at a constant temperature of 120 DEG C for 40 minutes, the reaction solution is naturally cooled to room temperature to obtain a reaction solution, and the reaction solution is washed with ethanol to obtain stable (C 19 H 18 P)2MnBr4 block crystals.

[0086] The above has exemplarily illustrated the specific embodiments of the present application through examples. However, the protection scope of the present application is not limited to the above exemplified embodiments. Any modification, equivalent replacement, improvement, etc. made by those skilled in the art within the spirit and principle of the present application shall be included in the protection scope of the claims of the present application.

Claims

1. An organic-inorganic hybrid manganese halide, characterized in that, The chemical formula of the organic-inorganic hybrid manganese halide is (C 19 H 18 P)2MnBr4, with a chemical formula weight of 929 g / mol; the (C) 19 H 18 P)2MnBr4 is a crystal, and the (C) 19 H 18 The space group of P)2MnBr4 crystal is R-3c, and the cell parameters are a=b=10.9024. c=58.1940 , α = β = 90°, γ = 120°, Z= 6, C 19 H 18 P stands for triphenylmethylphosphine.

2. The organic-inorganic hybrid manganese halide according to claim 1, characterized in that, The (C) 19 H 18 P)2MnBr4 crystal has a tetrahedral structure, with Mn at the center of the tetrahedron. 2+ Statistical distribution occurs when extending in opposite directions along the c-axis.

3. The organic-inorganic hybrid manganese halide according to claim 1, characterized in that, The (C) 19 H 18 P)2MnBr4 crystal is a pure phase.

4. The organic-inorganic hybrid manganese halide according to claim 1, characterized in that, The (C) 19 H 18 The P)2MnBr4 crystal has the structure shown in Figure 1.

5. The organic-inorganic hybrid manganese halide according to claim 1, characterized in that, The (C) 19 H 18 The P)2MnBr4 crystal has the X-ray powder diffraction pattern shown in Figure 2.

6. The organic-inorganic hybrid manganese halide according to claim 1, characterized in that, The (C) 19 H 18 The P)2MnBr4 crystal has the X-ray photoelectron spectrum shown in Figure 3.

7. The organic-inorganic hybrid manganese halide according to claim 1, characterized in that, The (C) 19 H 18 The P)2MnBr4 crystal has the infrared spectrum shown in Figure 4.

8. The organic-inorganic hybrid manganese halide according to claim 1, characterized in that, Under excitation light at 363 nm, the (C) 19 H 18 The P)2MnBr4 crystal has the emission spectrum shown in Figure 5.

9. The organic-inorganic hybrid manganese halide according to claim 1, characterized in that, The (C) 19 H 18 The P)2MnBr4 crystal has the thermogravimetric spectrum shown in Figure 6.

10. The organic-inorganic hybrid manganese halide according to any one of claims 1-9, characterized in that, The (C) 19 H 18 The thermal decomposition temperature of P)2MnBr4 crystal is greater than 350℃; the (C)2MnBr4 crystal has a thermal decomposition temperature greater than 350℃; 19 H 18 The thermal quenching temperature of P)2MnBr4 crystal is greater than 150℃; the (C)2MnBr4 crystal has a thermal quenching temperature greater than 150℃; 19 H 18 The air stability of P)2MnBr4 crystal is greater than 6 months.

11. A method for preparing the organic-inorganic hybrid manganese halide according to any one of claims 1-10, characterized in that, This includes preparation using room temperature evaporation crystallization or co-precipitation methods.

12. The preparation method according to claim 11, characterized in that, (C) was prepared by co-precipitation method 19 H 18 P)2MnBr4 crystal formation involves the following steps: S1. Mix and dissolve manganese compound, triphenylmethylphosphine bromide and solvent to obtain precursor solution; S2. React the precursor solution at a temperature of 80-140 ℃ for 20-120 min to obtain the reaction solution.

13. The preparation method according to claim 12, characterized in that, In step S1, the molar ratio of manganese compound to triphenylmethylphosphine bromide is 1: (1-3).

14. The preparation method according to claim 12, characterized in that, The manganese compound is selected from at least one of manganese carbonate, manganese oxalate, manganese nitrate, manganese acetate, manganese acetylacetone, manganese bromide, manganese chloride, and manganese iodide.

15. The preparation method according to claim 12, characterized in that, Step S1 includes the following steps: mixing manganese compound, triphenylmethylphosphine bromide and solvent, and heating to 80~140 °C until the solution is clear and transparent.

16. The preparation method according to claim 12, characterized in that, Step S2 is followed by the following step: cooling the reaction solution to obtain a solid product.

17. The preparation method according to claim 16, characterized in that, Step S2 is followed by the following steps: separating the cooled reaction liquid into solid and liquid phases, and washing the solid product.

18. The preparation method according to claim 17, characterized in that, The washing process further includes the following step: drying the washing product to obtain (C) 19 H 18 P)2MnBr4 crystals, the drying temperature is 30~80℃.

19. Use of an organic-inorganic hybrid manganese halide according to any one of claims 1-10 or an organic-inorganic hybrid manganese halide prepared by the method according to any one of claims 11-18 as a luminescent material.

20. The use according to claim 19, wherein the luminescent material is a photoluminescent device.

21. A luminescent material, the luminescent material comprising the organic-inorganic hybrid manganese halide of any one of claims 1-10 or the organic-inorganic hybrid manganese halide prepared by the method of any one of claims 11-18.

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