CN114656364A - Mn-based organic-inorganic hybrid metal halide luminescent material and preparation method thereof - Google Patents
Mn-based organic-inorganic hybrid metal halide luminescent material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 61
- 229910001507 metal halide Inorganic materials 0.000 title claims abstract description 45
- 150000005309 metal halides Chemical class 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000005284 excitation Effects 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 238000010791 quenching Methods 0.000 claims abstract description 6
- 230000000171 quenching effect Effects 0.000 claims abstract description 6
- 238000005286 illumination Methods 0.000 claims abstract description 4
- 239000011572 manganese Substances 0.000 claims description 27
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 24
- 229910052748 manganese Inorganic materials 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 16
- -1 N-methyldicyclohexylamine cation Chemical class 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003446 ligand Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000004570 mortar (masonry) Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 14
- OTOMCGZQGBZDMC-UHFFFAOYSA-N 5-fluoro-2-methoxypyridine-4-carbaldehyde Chemical compound COC1=CC(C=O)=C(F)C=N1 OTOMCGZQGBZDMC-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000013110 organic ligand Substances 0.000 abstract description 2
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- GSCCALZHGUWNJW-UHFFFAOYSA-N N-Cyclohexyl-N-methylcyclohexanamine Chemical compound C1CCCCC1N(C)C1CCCCC1 GSCCALZHGUWNJW-UHFFFAOYSA-N 0.000 description 9
- 238000000295 emission spectrum Methods 0.000 description 8
- 238000000634 powder X-ray diffraction Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 5
- 229910021568 Manganese(II) bromide Inorganic materials 0.000 description 5
- 239000011565 manganese chloride Substances 0.000 description 5
- 238000000695 excitation spectrum Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- IUNCEDRRUNZACO-UHFFFAOYSA-N butyl(trimethyl)azanium Chemical compound CCCC[N+](C)(C)C IUNCEDRRUNZACO-UHFFFAOYSA-N 0.000 description 2
- 150000002892 organic cations Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910020440 K2SiF6 Inorganic materials 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000010583 slow cooling Methods 0.000 description 1
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Abstract
The invention discloses a Mn-based hybrid metal halide luminescent material and a preparation method thereof, belonging to the field of photoelectric materials. The photoelectric material comprises four materials, and the chemical general formulas are respectively (C)13H26N)3MnBr5，(C13H26N)2MnCl4，(C7H18N)2MnBr4，(C7H18N)2MnCl4. The invention is to provideN-methyl dicyclohexylamine and butyl trimethyl ammonium chloride are used as luminescent materials of organic ligands, the excitation wavelength ranges of the four compounds are 200-480nm, the optimal excitation is blue light excitation of about 450nm, the emission peaks are all located near 520nm, the optimal narrow-band green light emission is presented, the luminous efficiency is high, and the thermal quenching resistance is good. The preparation method has the advantages of simple preparation process, extremely low cost and easy large-scale technical popularization. The luminescent material can be used for manufacturing luminescent devices and is used in the fields of display, illumination and the like.
Description
Technical Field
The invention relates to the technical field of solid-state lighting and liquid crystal display backlight, in particular to an organic-inorganic hybrid metal halide based on N-methyldicyclohexylamine and butyltrimethylammonium chloride ligands, a preparation method thereof and application thereof in the photoelectric field.
Background
Organic-inorganic metal halides have received much attention in the fields of solid state lighting and display backlighting due to their tunable emission. Especially low-dimensional metal halides, have been the focus of research for white light emitting diodes due to their bright and stable emission properties.
By appropriate combination of organic cations and metal halides, the half-width of the organic-inorganic metal halide can be controlled and its size can be made from high to low dimensions. The narrow half-peak width can ensure that the fluorescent material has high color purity, and further can show higher color gamut to be applied to the field of display backlight. The inorganic part in the zero-dimensional organic-inorganic metal halide is isolated by large organic cations, has a unique electronic structure and isolated anion metal halide polyhedral structure units, and can show the photophysical properties of a single metal halide, high photoluminescence quantum efficiency and long decay life. Most zero-dimensional metal halides, however, exhibit fluorescence emission based on self-trapping excitons, with large stokes shifts, which makes them difficult to use in white LED devices under blue excitation. Compared with a blue light chip, the cost of the near ultraviolet light chip is much higher than that of the blue light chip, and the luminous efficiency is lower. Therefore, the most desirable excitation light source for a white LED device is a blue chip, rather than an ultraviolet chip. Based on this, the search for blue-excited light-emitting materials is the focus of future research.
Compared with the traditional organic-inorganic hybrid metal halide, the zero-dimensional Mn-based metal halide enables efficient emission under ideal blue light excitation due to the unique d-d transition. In addition, the Mn-based metal halide has many advantages such as simple preparation process, high efficiency, low toxicity, low price, etc. This makesBy the addition of Mn2+Organic-inorganic hybrid metal halide materials that are metal cations have been extensively studied.
Disclosure of Invention
In order to realize the purpose, the manganese-based hybrid metal halide narrow-band green luminescent material with good heat-resisting quenching performance and high luminous intensity is prepared by introducing two different organic cations N-methyl dicyclohexylamine cation and using butyltrimethylammonium chloride as an organic ligand, the emission peak of the manganese-based hybrid metal halide narrow-band green luminescent material is about 520nm, and the optimal excitation wavelength is 450 nm.
The invention also aims to provide a low-price, simple-preparation and high-luminous-intensity narrow-band green-light fluorescent material, and a manganese-based organic-inorganic hybrid metal halide luminous material taking N-methyl dicyclohexylamine cations and butyl trimethyl ammonium chloride as ligands has the advantages of simple preparation process, extremely low cost and easiness in large-scale technical popularization.
The manganese-based organic-inorganic hybrid metal halide luminescent material is characterized by comprising four materials with chemical formulas of (C)13H26N)3MnBr5，(C13H26N)2MnCl4，(C7H18N)2MnBr4， (C7H18N)2MnCl4Wherein: c13H26N+Is N-methyldicyclohexylamine cation, C7H18N+Is butyltrimethylammonium chloride cation.
Further, in the light-emitting material, (C)13H26N)3MnBr5Belongs to an orthorhombic system, and the space group is Pbca, (C)13H26N)2MnCl4Belongs to monoclinic system, and has space group P21C (C)7H18N)2MnBr4Belongs to an orthorhombic system, and has a space group of P21C (C)7H18N)2MnCl4Belongs to monoclinic system, and space group is C2/C.
Further, the luminescent material is excited by using light of 250-480nm, and green fluorescence emission exists, wherein the optimal excitation is excitation of blue light of 450 nm; the emission peak is positioned at 520nm, and ideal narrow-band green light emission is presented; the half-peak widths of the four compounds are 43nm,48nm,51nm and 60nm respectively.
Further, the luminescent material has good thermal quenching resistance at high temperature; (C)13H26N)3MnBr5Can still maintain 82.7% of emission intensity at normal temperature under 420K, (C)13H26N)2MnCl4Can still maintain 64.4% of emission intensity at normal temperature under 420K, (C)7H18N)2MnBr4Can still maintain 74.8% of the emission intensity at the normal temperature at 380K (C)7H18N)2MnCl453.0% of the emission intensity at normal temperature can still be maintained at 380K.
The preparation method of the manganese-based organic-inorganic hybrid metal halide luminescent material adopts a cooling crystallization method or a solid phase grinding method, and comprises the following steps:
solid phase grinding method:
1) -weighing the materials: weighing the required raw materials C13H25N、C7H18NCl, manganese-containing compound and a small amount of acid (HCl or HBr), and adding the raw materials into a mortar;
2) grinding and mixing: grinding and mixing the raw materials thoroughly to obtain (C)13H26N)3MnBr5， (C13H26N)2MnCl4，(C7H18N)2MnBr4，(C7H18N)2MnCl4And (3) powder. A cooling crystallization method:
3) weighing materials: weighing the required raw materials C in sequence13H25N、C7H18NCl, manganese-containing compound, adding raw materials into a reaction vessel;
4) stirring and dissolving: adding a certain organic solvent and acid as solvents into a reaction vessel, heating to 50-90 ℃, and stirring to obtain a clear solution;
5) and (3) crystallization and precipitation: putting the solution obtained in the step 2) into an ovenThe initial temperature of the oven is the temperature when the mixture is stirred to be completely dissolved in the step 2), the procedure of the oven is set for slow cooling, and the temperature is reduced for 1 to 10 days to obtain (C)13H26N)3MnBr5，(C13H26N)2MnCl4， (C7H18N)2MnBr4，(C7H18N)2MnCl4And (3) crystals, and sequentially filtering and drying the obtained reaction liquid and the crystals to obtain dried organic-inorganic hybrid metal halide crystals of N-methyldicyclohexylamine cations and butyltrimethylammonium chloride cation ligands.
Further, in the cooling crystallization method, the organic solvent in the step (2) is N, N-dimethylformamide, and the HX acid in the step (3) is hydrochloric acid, hydrobromic acid or other acids.
Further, in the cooling crystallization method, the temperature of the solution in the step (2) is 50-90 ℃ for stirring, heating and reacting.
Further, the organic-inorganic hybrid metal halide crystal of the N-methyldicyclohexylamine cation and the butyltrimethylammonium chloride cation ligand is applied to the fields of illumination, display backlight and laser.
The key points of the technology of the invention are as follows:
compared with the prior art, the invention has the following advantages and beneficial effects:
(1) has excellent heat quenching resistance and high luminous efficiency;
(2) has narrow half-peak width, and can be compared with the beta-Sialon Eu of the commercial narrow-band green-light fluorescent powder2+；
(3) The luminescent material has extremely low price;
(4) the physical and chemical properties are stable;
(5) the preparation method is simple and easy for large-scale popularization. The luminescent material can be used for manufacturing luminescent devices, and can be applied to the fields of illumination, liquid crystal display backlight and the like.
Drawings
FIG. 1 is a powder X-ray diffraction (XRD) pattern of a sample prepared according to example 1 of the present invention compared to a single crystal XRD pattern.
Figure 2 is a powder X-ray diffraction (XRD) pattern compared to a single crystal XRD pattern for a sample prepared in example 2 of the present invention.
Figure 3 is a powder X-ray diffraction (XRD) pattern of a sample prepared in example 3 of the present invention compared to a single crystal XRD pattern.
Figure 4 is a powder X-ray diffraction (XRD) pattern compared to a single crystal XRD pattern for a sample prepared in example 4 of the present invention.
FIG. 5 is a graph of the excited emission spectrum of a sample prepared in example 1 of the present invention.
FIG. 6 is a graph of the excited emission spectrum of a sample prepared in example 2 of the present invention.
FIG. 7 is a graph of the excited emission spectrum of a sample prepared in example 3 of the present invention.
FIG. 8 is a graph of the excited emission spectrum of a sample prepared in example 4 of the present invention.
Fig. 9 is a graph of temperature swing spectra of samples prepared in example 1 of the present invention.
FIG. 10 is a plot of temperature swing spectra for samples prepared in example 2 of the present invention.
FIG. 11 is a plot of temperature swing spectra for samples prepared in example 3 of the present invention.
FIG. 12 is a plot of temperature swing spectra for samples prepared in example 4 of the present invention.
Detailed Description
The present invention will be described in further detail below with reference to examples for better describing the invention, which are illustrative and not restrictive, and the embodiments of the present invention are not limited thereto.
Example 1
The chemical composition formula of the embodiment is (C)13H26N)3MnBr5The preparation method of the manganese-based organic-inorganic hybrid metal halide luminescent material comprises the following steps:
proportioning according to stoichiometric ratio, and respectively weighing high-purity MnBr2Compound powder raw material, weighing organic N-methyl dicyclohexyl amine (C)13H25N) and measuring HBr acid. The weighed organic matter N-methyl dicyclohexyl amine (C)13H25N) solution with MnBr2Mixing the powder raw materials of the compound, dissolving in a container, adding a certain amount of N, N-dimethylformamide solution to the above organic matter methyl dicyclohexylamine (C)13H25N) solution with MnBr2The powdered feed was placed in a vessel and then a measured amount of HBr acid was added. Heating the obtained mixed solution to 50-90 ℃, continuously stirring until the mixture in the mixed solution is completely dissolved to obtain a clear solution, putting the obtained clear solution into a 50-90 ℃ oven, setting a program to cool for 2-4 days to obtain the required (C)13H26N)3MnBr5Crystals and a residual solution, and filtering and drying the obtained reaction solution and the crystals in sequence to obtain (C) based on the N-methyldicyclohexylamine ligand13H26N)3MnBr5And (4) crystals.
The powder X-ray diffraction (XRD) pattern of the organic-inorganic hybrid metal halide luminescent material prepared in this example is shown in fig. 1, and the excitation spectrum emission spectrum is shown in fig. 5. The optimal excitation wavelength is 450nm, the emission peak is located at 515nm, and the half-peak width is 43 nm. The organic-inorganic hybrid metal halide luminescent material can realize narrow-band green light emission.
Example 2
The chemical composition formula of the embodiment is (C)13H26N)2MnCl4The preparation method of the manganese-based organic-inorganic hybrid metal halide luminescent material comprises the following steps:
proportioning according to stoichiometric ratio, and respectively weighing high-purity MnCl2Compound powder raw material, weighing organic N-methyl dicyclohexyl amine (C)13H25N), measuring HCl acid. Measuring the organic matter N-methyl dicyclohexyl amine (C)13H25N) solution with MnCl2Mixing the powder raw materials of the compound, dissolving in a container, adding a certain amount of N, N-dimethylformamide solution to the above organic substance N-methyl dicyclohexylamine (C)13H25N) solution with MnCl2The powdered raw material is placed in a container, and then a measured amount of HCl acid is added. Then the obtained mixed solution is added intoHeating to 90-95 ℃, continuously stirring until the mixture in the mixture is completely dissolved to obtain a clear solution, putting the obtained clear solution into a drying oven at 90-95 ℃, setting a program to cool for 2-4 days to obtain the required (C)13H26N)2MnCl4Crystals and residual solution, filtering and drying the obtained reaction liquid and crystals in turn to obtain (C) based on the N-methyldicyclohexylamine ligand13H26N)2MnCl4And (4) crystals.
The powder X-ray diffraction (XRD) pattern of the organic-inorganic hybrid metal halide luminescent material prepared in this example is shown in fig. 2, and the excitation spectrum emission spectrum is shown in fig. 6. The optimal excitation wavelength is 450nm, the emission peak is 515nm, and the half-peak width is 48 nm. The organic-inorganic hybrid metal halide luminescent material can realize narrow-band green light emission.
Example 3
The chemical composition formula of the embodiment is (C)7H18N)2MnBr4The preparation method of the manganese-based organic-inorganic hybrid metal halide luminescent material comprises the following steps:
proportioning according to stoichiometric ratio, and respectively weighing high-purity MnBr2Compound powder raw material, organic substance butyl trimethyl ammonium chloride (C)7H18NCl) powder, HBr acid was taken off. Weighing organic substances of butyltrimethylammonium chloride and MnBr2The powdered starting materials of the compounds were mixed and dissolved in a vessel, and then the measured amount of HBr acid was added. Heating the obtained mixed solution to 60-90 ℃, continuously stirring until the mixture in the mixed solution is completely dissolved to obtain a clear solution, putting the obtained clear solution into a drying oven at 60-90 ℃, setting a program to cool for 2-3 days to obtain the required (C)7H18N)2MnBr4Crystals and a residual solution, and filtering and drying the obtained reaction solution and the crystals in sequence to obtain (C) based on the butyltrimethylammonium ligand7H18N)2MnBr4And (4) crystals.
The powder X-ray diffraction (XRD) pattern of the organic-inorganic hybrid metal halide luminescent material prepared in this example is shown in fig. 3, and the excitation spectrum emission spectrum is shown in fig. 7. The optimal excitation wavelength is 450nm, the emission peak is located at 521nm, and the half-peak width is 51 nm. The organic-inorganic hybrid metal halide luminescent material can realize narrow-band green light emission.
Example 4
The chemical composition formula of the embodiment is (C)7H18N)2MnCl4The preparation method of the manganese-based organic-inorganic hybrid metal halide luminescent material comprises the following steps:
proportioning according to stoichiometric ratio, and respectively weighing high-purity MnCl2Compound powder raw material, organic substance butyl trimethyl ammonium chloride (C)7H18NCl) and measuring HCl acid. Weighing organic substances of butyltrimethylammonium chloride and MnCl2The powdered starting materials of the compounds are mixed and dissolved in a vessel, and then the metered HCl acid is added. Heating the obtained mixed solution to 60-90 ℃, continuously stirring until the mixture in the mixed solution is completely dissolved to obtain a clear solution, putting the obtained clear solution into a drying oven at 60-90 ℃, setting a program to cool for 2-3 days to obtain the required (C)7H18N)2MnCl4Crystals and a residual solution, and filtering and drying the obtained reaction solution and the crystals in sequence to obtain (C) based on the butyltrimethylammonium ligand7H18N)2MnCl4And (4) crystals.
The powder X-ray diffraction (XRD) pattern of the organic-inorganic hybrid metal halide luminescent material prepared in this example is shown in fig. 4, and the excitation spectrum emission spectrum is shown in fig. 8. The optimal excitation wavelength is 450nm, the emission peak is located at 525nm, and the half-peak width is 60 nm. The organic-inorganic hybrid metal halide luminescent material can realize narrow-band green light emission.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which are made without departing from the spirit and principle of the present invention should be regarded as equivalent replacements within the protection scope of the present invention.
Examples 5 to 8 preparation of four manganese-based organic-inorganic hybrid perovskite materials by temperature-lowering crystallization method as an example, organic-inorganic hybrid materials (C) were examined13H26N)3MnBr5，(C13H26N)2MnCl4，(C7H18N)2MnBr4， (C7H18N)2MnCl4The half-peak width and the luminous efficiency are used for measuring the application of the organic-inorganic hybrid perovskite material in the field of luminescence.
TABLE 1
| Examples | Chemical composition formula | Half peak width | Quantum efficiency |
| 5 | (C13H26N)3MnBr5 | 43nm | 77.8％ |
| 6 | (C13H26N)2MnCl4 | 48nm | 79.3％ |
| 7 | (C7H18N)2MnBr4 | 51nm | 33.4％ |
| 8 | (C7H18N)2MnCl4 | 60nm | 76.5％ |
Examples 9-12 preparation of four manganese-based organic-inorganic hybrid perovskite materials by temperature-reducing crystallization method, detection of organic-inorganic hybrid materials (C)13H26N)3MnBr5，(C13H26N)2MnCl4，(C7H18N)2MnBr4， (C7H18N)2MnCl4The luminous intensity at different temperatures is used for measuring the heat quenching resistance of the organic-inorganic hybrid perovskite material.
TABLE 2
| Examples | Chemical composition formula | Measuring temperature | Percent (relative normal temperature strength) |
| 9 | (C13H26N)3MnBr5 | 420K | 82.7％ |
| 10 | (C13H26N)2MnCl4 | 420K | 64.4％ |
| 11 | (C7H18N)2MnBr4 | 380K | 74.8％ |
| 12 | (C7H18N)2MnCl4 | 380K | 53.0％ |
Examples 13-16 preparation of four manganese-based organic-inorganic hybrid perovskite materials by temperature-reducing crystallization method13H26N)3MnBr5，(C13H26N)2MnCl4，(C7H18N)2MnBr4， (C7H18N)2MnCl4Are each independently of K2SiF6:Mn4+The red fluorescent powder and the InGaN blue light chip are packaged into an LED backlight plate to measure the application of the organic-inorganic hybrid perovskite material in the aspect of liquid crystal backlight display.
TABLE 3
Claims (8)
1. Manganese-based organic-an inorganic hybrid metal halide luminescent material, characterized in that the luminescent material comprises four materials, each of the formulae (C)13H26N)3MnBr5，(C13H26N)2MnCl4，(C7H18N)2MnBr4，(C7H18N)2MnCl4Wherein: c13H26N+Is N-methyldicyclohexylamine cation, C7H18N+Is butyltrimethylammonium chloride cation.
2. The manganese-based organic-inorganic hybrid metal halide light-emitting material according to claim 1, wherein in the light-emitting material, (C)13H26N)3MnBr5Belongs to an orthorhombic system, and the space group is Pbca, (C)13H26N)2MnCl4Belongs to monoclinic system, and has space group P21C (C)7H18N)2MnBr4Belongs to an orthorhombic system, and has a space group of P21C (C)7H18N)2MnCl4Belongs to monoclinic system, and space group is C2/C.
3. The manganese-based organic-inorganic hybrid metal halide luminescent material according to claim 1, wherein the luminescent material, excited with 250-480nm light, exhibits green fluorescence emission, wherein the optimal excitation is 450nm blue light excitation; the emission peak is positioned at 520nm, and ideal narrow-band green light emission is presented; the half-peak widths of the four compounds are 43nm,48nm,51nm and 60nm respectively.
4. The manganese-based organic-inorganic hybrid metal halide light-emitting material according to claim 1, wherein the light-emitting material has good thermal quenching resistance at high temperature; (C)13H26N)3MnBr5Can still maintain 82.7% of emission intensity at normal temperature under 420K (C)13H26N)2MnCl4Can still maintain 64.4% of emission intensity at normal temperature under 420K, (C)7H18N)2MnBr4Can still maintain 74.8% of the emission intensity at the normal temperature at 380K (C)7H18N)2MnCl453.0% of the emission intensity at normal temperature can still be maintained at 380K.
5. A method for preparing manganese-based organic-inorganic hybrid metal halide luminescent material according to any one of claims 1 to 4, wherein the luminescent material is prepared by a cooling crystallization method and a solid phase grinding method, comprising the following steps:
solid phase grinding method:
1) weighing materials: weighing the required raw materials C13H25N、C7H18NCl, a manganese-containing compound and a small amount of acid, wherein the acid is HCl and HBr, and the raw materials are added into a mortar;
2) grinding and mixing: grinding and mixing the raw materials thoroughly to obtain (C)13H26N)3MnBr5，(C13H26N)2MnCl4，(C7H18N)2MnBr4，(C7H18N)2MnCl4Powder;
a cooling crystallization method:
1) weighing materials: weighing the required raw materials C in sequence13H25N、C7H18NCl, manganese-containing compound, adding raw materials into a reaction vessel;
2) stirring and dissolving: adding a certain organic solvent and acid as solvents into a reaction vessel, heating to 50-90 ℃, and stirring to obtain a clear solution;
3) and (3) crystallization and precipitation: putting the solution obtained in the step 2) into an oven, setting the initial temperature of the oven to the temperature when the solution is completely dissolved in the step 2), setting the procedure of the oven to slowly cool the solution for 1 to 10 days to obtain (C)13H26N)3MnBr5，(C13H26N)2MnCl4，(C7H18N)2MnBr4，(C7H18N)2MnCl4Crystals obtained byAnd sequentially filtering and drying the obtained reaction liquid and crystals to obtain dried N-methyl dicyclohexylamine cations and organic-inorganic hybrid metal halide crystals of the butyl trimethyl ammonium chloride cation ligand.
6. The method for preparing manganese-based organic-inorganic hybrid metal halide luminescent material according to claim 5, wherein the organic solvent in step (2) is N, N-dimethylformamide and the HX acid in step (3) is hydrochloric acid, hydrobromic acid or other acids in a temperature-reducing crystallization method.
7. The preparation method of the manganese-based organic-inorganic hybrid metal halide luminescent material as claimed in claim 5, wherein the temperature of the solution in the step (2) in the cooling crystallization method is 50-90 ℃ through stirring and heating reaction.
8. The manganese-based organic-inorganic hybrid metal halide light-emitting material according to claim 1, wherein the organic-inorganic hybrid metal halide crystal of N-methyldicyclohexylamine cation, butyltrimethylammonium chloride cation ligand is applied to the fields of illumination, display backlight and laser.
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