CN114656364B - 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 43
- 150000005309 metal halides Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 21
- 229910052748 manganese Inorganic materials 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 16
- -1 N-methyl dicyclohexylamine cation Chemical class 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
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- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 6
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- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
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- GSCCALZHGUWNJW-UHFFFAOYSA-N N-Cyclohexyl-N-methylcyclohexanamine Chemical compound C1CCCCC1N(C)C1CCCCC1 GSCCALZHGUWNJW-UHFFFAOYSA-N 0.000 abstract description 10
- 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
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- BWRRWBIBNBVHQF-UHFFFAOYSA-N 4-(3-pyridin-2-yl-1,2,4-oxadiazol-5-yl)butanoic acid Chemical compound O1C(CCCC(=O)O)=NC(C=2N=CC=CC=2)=N1 BWRRWBIBNBVHQF-UHFFFAOYSA-N 0.000 description 2
- IUNCEDRRUNZACO-UHFFFAOYSA-N butyl(trimethyl)azanium Chemical compound CCCC[N+](C)(C)C IUNCEDRRUNZACO-UHFFFAOYSA-N 0.000 description 2
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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 materials comprise four types, and the chemical formulas are (C) 13 H 26 N) 3 MnBr 5 ，(C 13 H 26 N) 2 MnCl 4 ，(C 7 H 18 N) 2 MnBr 4 ，(C 7 H 18 N) 2 MnCl 4 . The invention uses N-methyl dicyclohexylamine and butyl trimethyl ammonium chloride 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 peak is 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 process is simple, has extremely low cost and is extremely easy to popularize in large-scale technology. The luminescent material can be used for manufacturing a luminescent device, 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-methyl dicyclohexylamine and butyl trimethyl ammonium chloride ligand, a preparation method thereof and application thereof in the photoelectric field.
Background
Organic-inorganic metal halides have received considerable attention in the field of solid state lighting and display backlighting due to their tunable emission. Especially low-dimensional metal halides, are hot spots for white light emitting diode research due to their bright and stable emission properties.
By appropriate combination of the organic cation and the metal halide, the half-width of the organic-inorganic metal halide and the size thereof can be controlled from high dimension to low dimension. The narrow half-width can ensure that the fluorescent material has high color purity, and can further show higher color gamut to be applied to the field of display backlight. The inorganic part of the zero-dimensional organic-inorganic metal halide is isolated by large organic cations, has a unique electronic structure and isolated anionic metal halide polyhedral structural units, and can therefore show the photophysical properties of single metal halides, and has high photoluminescence quantum efficiency and long decay life. Most zero-dimensional metal halides 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. The cost of the near ultraviolet light chip is much higher than that of the blue light chip, and the luminous efficiency is lower than that of the blue light chip. Therefore, the most ideal excitation light source for a white LED device is a blue light chip, rather than an ultraviolet chip. Based on this, the search for blue-excited luminescent materials is an important point of future research.
Compared with the traditional organic-inorganic hybrid metal halide, the zero-dimensional Mn-based metal halide can realize efficient emission under ideal blue light excitation due to the unique d-d transition. In addition, mn-based metal halides have many advantages such as simple preparation process, high efficiency, low toxicity, low price, etc. This results in Mn 2+ Organic-inorganic hybrid metal halide materials that are metal cations have been widely studied.
Disclosure of Invention
In order to achieve the aim, the manganese-based hybridized metal halide narrow-band green luminescent material with good thermal quenching resistance and high luminous intensity is prepared by introducing two different organic cations of N-methyl dicyclohexylamine cations and butyl trimethyl ammonium chloride as organic ligands, wherein the emission peak is about 520nm, and the optimal excitation wavelength is 450nm.
The invention also aims to provide a low-cost, simple-to-prepare and high-luminous-intensity narrow-band green light fluorescent material, and the preparation process of the manganese-based organic-inorganic hybrid metal halide luminescent material taking N-methyl dicyclohexylamine cations and butyl trimethyl ammonium chloride as ligands is simple, has extremely low cost and is easy for large-scale technical popularization.
A manganese-based organic-inorganic hybrid metal halide luminescent material, characterized in that the luminescent material comprises four materials, each of which has a chemical formula (C 13 H 26 N) 3 MnBr 5 ，(C 13 H 26 N) 2 MnCl 4 ，(C 7 H 18 N) 2 MnBr 4 ， (C 7 H 18 N) 2 MnCl 4 Wherein: c (C) 13 H 26 N + Is N-methyl dicyclohexylamine cation, C 7 H 18 N + Is butyl trimethyl ammonium chloride cation.
Further, in the luminescent material, (C) 13 H 26 N) 3 MnBr 5 Belongs to an orthorhombic system, the space group is Pbca, (C) 13 H 26 N) 2 MnCl 4 Belonging to monoclinic system, the space group is P21C, (C) 7 H 18 N) 2 MnBr 4 Belongs to an orthorhombic system, the space group is P21C, (C) 7 H 18 N) 2 MnCl 4 Belonging to monoclinic system, the space group is C2/C.
Further, the luminescent material is excited with 250-480nm light, there is green fluorescence emission, wherein the optimal excitation is 450nm blue excitation; the emission peak is located at 520nm, and shows ideal narrow-band green light emission; the half-widths of the four compounds were 43nm,48nm,51nm and 60nm, respectively.
Further, the luminescent material has good thermal quenching resistance at high temperature; (C) 13 H 26 N) 3 MnBr 5 The emission intensity at 420K was still maintained at 82.7%, (C) 13 H 26 N) 2 MnCl 4 The emission intensity at 420K was still maintained at 64.4%, (C) 7 H 18 N) 2 MnBr 4 Can still be used at 380KMaintaining 74.8% of emission intensity at ordinary temperature (C) 7 H 18 N) 2 MnCl 4 The emission intensity at 380K can still be kept at 53.0% at normal temperature.
The preparation method of the manganese-based organic-inorganic hybrid metal halide luminescent material comprises the following steps of:
solid phase milling method:
1) -weighing the material: weighing the required raw material C 13 H 25 N、C 7 H 18 NCl, manganese-containing compound and a small amount of acid (HCl or HBr), the raw materials are added to a mortar;
2) Grinding and mixing: grinding and mixing the raw materials thoroughly to obtain (C) 13 H 26 N) 3 MnBr 5 ， (C 13 H 26 N) 2 MnCl 4 ，(C 7 H 18 N) 2 MnBr 4 ，(C 7 H 18 N) 2 MnCl 4 And (3) powder. And (3) cooling crystallization method:
3) Weighing materials: weighing the required raw materials C in sequence 13 H 25 N、C 7 H 18 NCl, manganese-containing compound, adding raw materials into a reaction vessel;
4) Stirring and dissolving: adding a certain organic solvent and acid serving as solvents into a reaction container, heating to 50-90 ℃ and stirring to obtain a clear solution;
5) Crystallization precipitation: putting the solution obtained in the step 2) into a baking oven, wherein the initial temperature of the baking oven is the temperature when the solution is stirred to be completely dissolved in the step 2), setting a baking oven program to slowly cool, and cooling for 1-10 days to obtain (C) 13 H 26 N) 3 MnBr 5 ，(C 13 H 26 N) 2 MnCl 4 ， (C 7 H 18 N) 2 MnBr 4 ，(C 7 H 18 N) 2 MnCl 4 And (3) filtering and drying the obtained reaction liquid and the obtained crystal in sequence to obtain the organic-inorganic hybrid metal halide crystal of the dried N-methyl dicyclohexylamine cation and butyl trimethyl ammonium chloride cation ligand.
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 ℃ through stirring and heating reaction.
Further, the organic-inorganic hybrid metal halide crystal of the N-methyl dicyclohexylamine cation and the butyl trimethyl ammonium chloride cation ligand is applied to the fields of illumination, display backlight and laser.
The technical key points of the invention are as follows:
compared with the prior art, the invention has the following advantages and beneficial effects:
(1) Has excellent thermal quenching resistance and high luminous efficiency;
(2) Has narrow half peak width, and can be compared with commercial narrow-band green light fluorescent powder beta-Sialon Eu 2+ ；
(3) The price of the luminescent material is extremely low;
(4) The physical and chemical properties are stable;
(5) The preparation method is simple and is easy to popularize on a large scale. 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 in example 1 of the present invention compared with that of a single crystal.
Fig. 2 is a powder X-ray diffraction (XRD) pattern of a sample prepared in example 2 of the present invention compared to a single crystal XRD pattern.
Fig. 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.
Fig. 4 is a powder X-ray diffraction (XRD) pattern of a sample prepared in example 4 of the present invention compared to a single crystal XRD pattern.
FIG. 5 is a graph showing the excitation emission spectrum of the sample prepared in example 1 of the present invention.
FIG. 6 is a graph showing the excitation emission spectrum of the sample prepared in example 2 of the present invention.
FIG. 7 is a graph showing the excitation emission spectrum of the sample prepared in example 3 of the present invention.
FIG. 8 is a graph showing the excitation emission spectrum of the sample prepared in example 4 of the present invention.
FIG. 9 is a graph showing the temperature change spectrum of the sample prepared in example 1 of the present invention.
FIG. 10 is a graph showing the temperature change spectrum of the sample prepared in example 2 of the present invention.
FIG. 11 is a graph showing the temperature change spectrum of the sample prepared in example 3 of the present invention.
FIG. 12 is a graph showing the temperature change spectrum of the sample prepared in example 4 of the present invention.
Detailed Description
The invention will now be described in further detail with reference to the following examples, which are intended to be illustrative and not limiting.
Example 1
The chemical composition formula of the embodiment is (C 13 H 26 N) 3 MnBr 5 The 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 MnBr 2 Raw material of compound powder, and measured organic N-methyl dicyclohexylamine (C) 13 H 25 N), and measuring HBr acid. The measured organic N-methyl dicyclohexylamine (C 13 H 25 N) solution and MnBr 2 The powder raw materials of the compound are mixed and dissolved in a container, and a certain amount of N, N-dimethylformamide solution is added into the organic methyl dicyclohexylamine (C) 13 H 25 N) solution and MnBr 2 The powder feed is placed in a vessel and then the HBr acid is added in an amount. Heating the obtained mixed solution to 50-90 ℃ and continuously stirring until the mixture therein is completely dissolved to obtain a clarified solution, placing the obtained clarified solution into a 50-90 ℃ oven, setting a program to cool for 2-4 days to obtain the required (C) 13 H 26 N) 3 MnBr 5 Crystals and residual solution, and the resulting reaction solution and crystals are sequentially filtered and dried to give (C) based on N-methyldicyclohexylamine ligand 13 H 26 N) 3 MnBr 5 And (5) a crystal.
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 was 450nm, the emission peak was 515nm, and the half-width was 43nm. It is explained that 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 13 H 26 N) 2 MnCl 4 The 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 MnCl 2 Raw material of compound powder, and measured organic N-methyl dicyclohexylamine (C) 13 H 25 N), taking the HCl acid. The measured organic N-methyl dicyclohexylamine (C 13 H 25 N) solution and MnCl 2 The powder raw materials of the compound are mixed and dissolved in a container, and a certain amount of N, N-dimethylformamide solution is added into the above organic N-methyldicyclohexylamine (C) 13 H 25 N) solution and MnCl 2 The powder material was placed in a container and then the HCl acid was added in an amount. Heating the obtained mixed solution to 90-95 ℃ and continuously stirring until the mixture therein is completely dissolved to obtain a clarified solution, placing the obtained clarified solution into a baking oven with the temperature of 90-95 ℃, and setting a program to cool for 2-4 days to obtain the required (C) 13 H 26 N) 2 MnCl 4 Crystals and residual solution, and the resulting reaction solution and crystals are sequentially filtered and dried to give (C) based on N-methyldicyclohexylamine ligand 13 H 26 N) 2 MnCl 4 And (5) a crystal.
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 was 450nm, the emission peak was 515nm, and the half-width was 48nm. It is explained that 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 7 H 18 N) 2 MnBr 4 The preparation method of the manganese-based organic-inorganic hybrid metal halide luminescent material comprises the following steps:
stoichiometric ratio is used for proportioning, and high-purity MnBr is respectively weighed 2 Raw materials of compound powder, organic butyl trimethyl ammonium chloride (C) 7 H 18 NCl), HBr acid was measured. Weighing the organic matter butyl trimethyl ammonium chloride and MnBr 2 The powder starting materials of the compounds are mixed and dissolved in a container, and then the HBr acid is added in an amount. Heating the obtained mixed solution to 60-90 ℃ and continuously stirring until the mixture therein is completely dissolved to obtain a clarified solution, placing the obtained clarified solution into a baking oven at 60-90 ℃, setting a program to cool for 2-3 days to obtain the required (C) 7 H 18 N) 2 MnBr 4 Crystals and residual solution, and the resulting reaction solution and crystals were sequentially filtered and dried to obtain (C) based on a butyl trimethylammonium ligand 7 H 18 N) 2 MnBr 4 And (5) a crystal.
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 521nm, and the half-width is 51nm. It is explained that 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 7 H 18 N) 2 MnCl 4 The preparation method of the manganese-based organic-inorganic hybrid metal halide luminescent material comprises the following steps:
stoichiometric proportions are used for proportioning, and high-purity MnC is respectively weighedl 2 Raw materials of compound powder, organic butyl trimethyl ammonium chloride (C) 7 H 18 NCl), HCl acid is measured. Weighing the organic matter butyl trimethyl ammonium chloride and MnCl 2 The powder raw materials of the compound are mixed and dissolved in a container, and then the HCl acid is added in an amount. Heating the obtained mixed solution to 60-90 ℃ and continuously stirring until the mixture therein is completely dissolved to obtain a clarified solution, placing the obtained clarified solution into a baking oven at 60-90 ℃, setting a program to cool for 2-3 days to obtain the required (C) 7 H 18 N) 2 MnCl 4 Crystals and residual solution, and the resulting reaction solution and crystals were sequentially filtered and dried to obtain (C) based on a butyl trimethylammonium ligand 7 H 18 N) 2 MnCl 4 And (5) a crystal.
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 525nm, and the half-width is 60nm. It is explained that the organic-inorganic hybrid metal halide luminescent material can realize narrow-band green light emission.
The embodiments described above are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the embodiments described above, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Examples 5-8 four manganese-based organic-inorganic hybrid perovskite materials were prepared by a cooling crystallization method as examples, and the organic-inorganic hybrid materials (C 13 H 26 N) 3 MnBr 5 ，(C 13 H 26 N) 2 MnCl 4 ，(C 7 H 18 N) 2 MnBr 4 ， (C 7 H 18 N) 2 MnCl 4 Half-width and luminous efficiency to measure the application of the organic-inorganic hybrid perovskite material in the field of luminescence.
TABLE 1
| Examples | Chemical composition type | Half width of peak | Quantum efficiency |
| 5 | (C 13 H 26 N) 3 MnBr 5 | 43nm | 77.8％ |
| 6 | (C 13 H 26 N) 2 MnCl 4 | 48nm | 79.3％ |
| 7 | (C 7 H 18 N) 2 MnBr 4 | 51nm | 33.4％ |
| 8 | (C 7 H 18 N) 2 MnCl 4 | 60nm | 76.5％ |
Examples 9 to 12 for CoolingFour kinds of manganese-based organic-inorganic hybrid perovskite materials were prepared by crystallization, and the organic-inorganic hybrid material (C 13 H 26 N) 3 MnBr 5 ，(C 13 H 26 N) 2 MnCl 4 ，(C 7 H 18 N) 2 MnBr 4 ， (C 7 H 18 N) 2 MnCl 4 The luminous intensity at different temperatures is used for measuring the thermal quenching resistance of the organic-inorganic hybrid perovskite material.
TABLE 2
| Examples | Chemical composition type | Measuring temperature | Percentage (relative room temperature strength) |
| 9 | (C 13 H 26 N) 3 MnBr 5 | 420K | 82.7％ |
| 10 | (C 13 H 26 N) 2 MnCl 4 | 420K | 64.4％ |
| 11 | (C 7 H 18 N) 2 MnBr 4 | 380K | 74.8％ |
| 12 | (C 7 H 18 N) 2 MnCl 4 | 380K | 53.0％ |
Examples 13-16 four manganese-based organic-inorganic hybrid perovskite materials were prepared by a cooling crystallization method, and the organic-inorganic hybrid materials (C 13 H 26 N) 3 MnBr 5 ，(C 13 H 26 N) 2 MnCl 4 ，(C 7 H 18 N) 2 MnBr 4 ， (C 7 H 18 N) 2 MnCl 4 Respectively with K 2 SiF 6 :Mn 4+ The red fluorescent powder and the InGaN blue light chip are packaged into an LED backlight plate so as to measure the application of the organic-inorganic hybridization perovskite material in the aspect of liquid crystal backlight display.
TABLE 3 Table 3
Claims (7)
1. A Mn-based organic-inorganic hybrid metal halide luminescent material is characterized in that the luminescent material is four materials with chemical formulas (C) 13 H 26 N) 3 MnBr 5 ，(C 13 H 26 N) 2 MnCl 4 ，(C 7 H 18 N) 2 MnBr 4 ，(C 7 H 18 N) 2 MnCl 4 Wherein: c (C) 13 H 26 N + Is N-methyl dicyclohexylamine cation, C 7 H 18 N + Is butyl trimethyl ammonium chloride cation;
in the luminescent material, (C) 13 H 26 N) 3 MnBr 5 Belongs to an orthorhombic system, the space group is Pbca, (C) 13 H 26 N) 2 MnCl 4 Belonging to monoclinic system, the space group is P21C, (C) 7 H 18 N) 2 MnBr 4 Belongs to an orthorhombic system, the space group is P21C, (C) 7 H 18 N) 2 MnCl 4 Belonging to monoclinic system, the space group is C2/C.
2. The manganese-based organic-inorganic hybrid metal halide luminescent material according to claim 1, wherein the luminescent material is excited with 250-480nm light, there is green fluorescence emission, wherein the optimal excitation is 450nm blue excitation; the emission peak is located at 520nm, exhibiting narrow-band green emission; the half-peak widths of the four compounds were 43nm,48nm,51nm and 60nm, respectively.
3. The manganese-based organic-inorganic hybrid metal halide luminescent material according to claim 1, wherein the luminescent material has thermal quenching resistance at high temperature; (C) 13 H 26 N) 3 MnBr 5 82.7% of emission intensity at 420K at room temperature (C 13 H 26 N) 2 MnCl 4 64.4% of the emission intensity at 420K at room temperature (C 7 H 18 N) 2 MnBr 4 At 380K, 74.8% of the emission intensity at normal temperature (C 7 H 18 N) 2 MnCl 4 At 380K, 53.0% of the emission intensity at normal temperature.
4. A method for preparing the manganese-based organic-inorganic hybrid metal halide luminescent material according to any one of claims 1 to 3, wherein the luminescent material is prepared by a cooling crystallization method and a solid-phase grinding method, and comprises the following steps:
solid phase milling method:
1) Weighing materials: weighing the required raw material C 13 H 25 N、C 7 H 18 NCl, 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) 13 H 26 N) 3 MnBr 5 ，
(C 13 H 26 N) 2 MnCl 4 ，(C 7 H 18 N) 2 MnBr 4 ，(C 7 H 18 N) 2 MnCl 4 A powder;
and (3) cooling crystallization method:
1) Weighing materials: weighing the required raw materials C in sequence 13 H 25 N、C 7 H 18 NCl, a manganese-containing compound,
adding raw materials into a reaction vessel;
2) Stirring and dissolving: adding a certain organic solvent and acid serving as solvents into a reaction container, heating to 50-90 ℃ and stirring to obtain a clear solution;
3) Crystallization precipitation: putting the solution obtained in the step 2) into a baking oven, wherein the initial temperature of the baking oven is the temperature when the solution is stirred to be completely dissolved in the step 2), setting a baking oven program to slowly cool, and cooling for 1-10 days to obtain (C) 13 H 26 N) 3 MnBr 5 ，(C 13 H 26 N) 2 MnCl 4 ，(C 7 H 18 N) 2 MnBr 4 ，
(C 7 H 18 N) 2 MnCl 4 And (3) filtering and drying the obtained reaction liquid and the obtained crystal in sequence to obtain the organic-inorganic hybrid metal halide crystal of the dried N-methyl dicyclohexylamine cation and butyl trimethyl ammonium chloride cation ligand.
5. The method for preparing a manganese-based organic-inorganic hybrid metal halide luminescent material according to claim 4, wherein the organic solvent in the step (2) is N, N-dimethylformamide and the acid in the step (2) is hydrochloric acid or hydrobromic acid.
6. The method for preparing a manganese-based organic-inorganic hybrid metal halide luminescent material according to claim 4, wherein the temperature of the solution stirring and heating reaction in the step (2) in the cooling crystallization method is 50-90 ℃.
7. The manganese-based organic-inorganic hybrid metal halide luminescent material according to claim 1, wherein the organic-inorganic hybrid metal halide crystal of N-methyl dicyclohexylamine cation, butyl trimethylammonium chloride cation ligand is applied in the fields of lighting, display backlight and laser.
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