阅读说明：本技术 一种有机-无机杂化金属卤化物发光材料及制备方法 (Organic-inorganic hybrid metal halide luminescent material and preparation method thereof ) 是由 刘坤杰 赵静 刘泉林 于 2021-02-02 设计创作，主要内容包括：本发明公开了一种有机-无机杂化金属卤化物发光材料及制备方法,所述发光材料是基于4-叔丁基环己胺的杂化金属卤化物发光材料,化学组成式为(C-(10)H-(22)N)-6MX-9或(C-(10)H-(22)N)-6MX-9·H-2O,M为三价阳离子,如In、Sb、Bi中的任意一种或几种,X为Cl、Br、I中的一种或几种,C-(10)H-(22)N为4-叔丁基环己胺的阳离子。本发明是以有机物4-叔丁基环己胺为有机配体的发光材料,激发波长范围为200-450nm,发射波长覆盖450-850nm,发射峰值位于600-660nm左右。本发明的制备方法工艺简单,成本低、易于大规模技术推广,该材料具有较宽的激发和发射带,发光效率高。该发光材料可用于制造发光器件,以及应用于荧光粉、光谱转换、示踪标记和防伪等领域。(The invention discloses an organic-inorganic hybrid metal halide luminescent material and a preparation method thereof, wherein the luminescent material is a hybrid metal halide luminescent material based on 4-tert-butylcyclohexylamine, and the chemical composition formula is (C) 10 H 22 N) 6 MX 9 Or (C) 10 H 22 N) 6 MX 9 ·H 2 O, M is trivalent cation, such as one or more of In, Sb and Bi, X is one or more of Cl, Br and I, C 10 H 22 N is the cation of 4-tert-butylcyclohexylamine. The invention relates to a luminescent material taking organic 4-tert-butylcyclohexylamine as an organic ligand, wherein the excitation wavelength range is 200-450nm, the emission wavelength covers 450-850nm, and the emission peak value is about 600-660 nm. The preparation method of the invention has simple process, low cost,The material is easy to popularize in large-scale technology, has wider excitation and emission bands and high luminous efficiency. The luminescent material can be used for manufacturing luminescent devices and applied to the fields of fluorescent powder, spectrum conversion, tracing marking, anti-counterfeiting and the like.)

1. An organic-inorganic hybrid metal halide luminescent material is characterized in that the luminescent material is an organic-inorganic hybrid metal halide luminescent material based on 4-tert-butylcyclohexylamine ligand, and the molecular formula is (C)₁₀H₂₂N)₆MX₉Or (C)₁₀H₂₂N)₆MX₉·H₂O (X ═ Cl, Br, I), M is a trivalent cation; x is one or a mixture of Cl, Br and I, (C)₁₀H₂₂N) is the cation of 4-tert-butylcyclohexylamine.

2. An organic-inorganic hybrid metal halide luminescent material as claimed In claim 1, wherein M is one or more of In, Sb and Bi.

3. The organic-inorganic hybrid metal halide luminescent material as claimed in claim 1, wherein the luminescent material has an excitation wavelength of 200-450nm, an emission wavelength of 460-850nm, and an emission peak of 600-660 nm.

4. A method for preparing an organic-inorganic hybrid metal halide light-emitting material as claimed in claim 1, comprising the steps of:

(1) weighing materials: according to the chemical composition formula (C)₁₀H₂₂N)₆MX₉Mixing, weighing MX-containing₃Measuring organic 4-tert-butylcyclohexylamine (C)₁₀H₂₁N) and HX acid;

(2) organic 4-tert-butylcyclohexylamine (C)₁₀H₂₁N) and MX₃Mixing and dissolving in a container;

(3) adding N, N-dimethylformamide into a container in which the mixture obtained in the step (2) is positioned, and then adding HX acid corresponding to X;

(4) heating the mixed solution obtained in the step (3) and continuously stirring until the mixture in the mixed solution is completely dissolved to obtain a clear solution;

(5) putting the solution obtained in the step (4) into an oven, setting the initial temperature of the oven to the temperature when the solution is completely dissolved after the stirring in the step (4), setting the program of the oven to slowly cool the solution for 1 to 7 days to obtain (C)₁₀H₂₂N)₆MX₉Or (C)₁₀H₂₂N)₆MX₉·H₂O crystal, filtering and drying the obtained reaction liquid and the crystal in sequence to obtain the organic-inorganic hybrid metal halide (C) based on the 4-tert-butyl cyclohexylamine ligand₁₀H₂₂N)₆MX₉The crystal of (4).

5. The method for preparing an organic-inorganic hybrid metal halide light-emitting material according to claim 4, wherein the MX-containing component in the step (1)₃The molar ratio of the compound (1) to the 4-tert-butylcyclohexylamine is 1:1 to 1: 3.2.

6. The method for preparing an organic-inorganic hybrid metal halide luminescent material according to claim 4, wherein the HX acid in step (3) is hydrochloric acid, hydrobromic acid, hydroiodic acid or a mixture thereof.

7. The method for preparing an organic-inorganic hybrid metal halide luminescent material according to claim 4, wherein the temperature of the solution in the step (4) is 40-120 ℃ during stirring and heating reaction.

8. The organic-inorganic hybrid metal halide luminescent material as claimed in claim 1, wherein the crystal is used in the field of optoelectronics, such as illumination, light emitting diodes, lasers, solar cells, phototransistors, phosphors and photodetectors.

Technical Field

The invention relates to the technical field of photoelectric materials, in particular to an organic-inorganic hybrid metal halide based on a 4-tert-butyl cyclohexylamine ligand, a preparation method thereof and application thereof in the photoelectric field.

Background

In the last decade, organic-inorganic hybrid metal halides have not only made significant progress as a new semiconductor material in photovoltaic applications, but also have received great attention in the fields of luminescence, display, photoelectric conversion, high-energy ray detection, etc. due to their special defect tolerance, compositional adjustability and simple synthesis process. Organic-inorganic hybrid metal halides have undergone unprecedented rapid developments due to their excellent optoelectronic properties and inexpensive preparation costs, such as: organic-inorganic hybrid metal halide solar cells have efficiencies as high as 25% and lifetimes that have increased from the first hours scale to thousands of hours. However, their inherent instability to moisture, light and heat remains a problem to be solved before commercialization is achieved.

The organic-inorganic hybrid metal halide is generally formed by self-assembly of organic molecules and inorganic molecules, and metal halide materials with different dimensions (three-dimensional, two-dimensional, one-dimensional and zero-dimensional) can be obtained by adjusting components of organic ligands and inorganic polyhedrons. The organic group in the crystal has a quantum constraint effect on the metal halide polyhedron, and the reduction of the structural dimension can be caused by introducing larger organic cations, so that the crystal has more excellent stability and structural diversity. Low-dimensional organic-inorganic hybrid compounds are widely studied as broadband, bright emitters in the visible spectral range. It is worth pointing out that the low-dimensional organic-inorganic hybrid halide material defined herein refers to the low dimension at the crystal structure level, which is completely different from the morphological low-dimensional materials based on three-dimensional materials in the traditional sense, such as nanowires, nanosheets and quantum dots. In addition, the strong coupling effect of electrons and phonons and the characteristic of soft crystal lattices enable the material to easily generate self-trap excitons, thereby leading to high-efficiency broadband fluorescence emission. However, there are relatively few studies on low-dimensional organic-inorganic hybrid metal halides. Therefore, the development of the hybrid metal halide material with strong stability and high luminous intensity has important application prospect.

Disclosure of Invention

In order to realize the purpose, the invention prepares the organic-inorganic hybrid metal halide luminescent material with strong stability and high luminous intensity by introducing macrocyclic organic cation 4-tert-butylcyclohexylamine as an organic ligand, wherein an emission band covers 450-660 nm, an emission peak is positioned at about 600-660nm, and an excitation wavelength range is 200-450 nm.

The invention also aims to provide the preparation method of the organic-inorganic hybrid metal halide luminescent material with the 4-tert-butylcyclohexylamine as the ligand, which has simple preparation process and is easy for large-scale technical popularization.

The purpose of the invention is realized by the following technical scheme:

an organic-inorganic hybrid metal halide luminescent material is an organic-inorganic hybrid metal halide luminescent material based on a 4-tert-butylcyclohexylamine ligand, and the molecular formula is (C)₁₀H₂₂N)₆MX₉Or (C)₁₀H₂₂N)₆MX₉·H₂O (X ═ Cl, Br, I), M is a trivalent cation; x is one or a mixture of Cl, Br and I, (C)₁₀H₂₂N) is the cation of 4-tert-butylcyclohexylamine.

Further, M is one or a mixture of more of In, Sb and Bi.

Furthermore, the excitation wavelength of the luminescent material covers 200-450nm, the emission wavelength range is 460-850nm, and the emission peak is around 600-660 nm.

The preparation method of the organic-inorganic hybrid metal halide luminescent material comprises the following steps:

(1) weighing materials: according to the chemical composition formula (C)₁₀H₂₂N)₆MX₉Mixing, weighing MX-containing₃Measuring organic 4-tert-butylcyclohexylamine (C)₁₀H₂₁N) and HX acid;

(2) organic 4-tert-butylcyclohexylamine (C)₁₀H₂₁N) and MX₃Mixing and dissolving in a container;

(3) adding N, N-dimethylformamide into a container in which the mixture obtained in the step (2) is positioned, and then adding HX acid corresponding to X;

(4) heating the mixed solution obtained in the step (3) and continuously stirring until the mixture in the mixed solution is completely dissolved to obtain a clear solution;

(5) putting the solution obtained in the step (4) into an oven, setting the initial temperature of the oven to the temperature when the solution is completely dissolved after the stirring in the step (4), setting the program of the oven to slowly cool the solution for 1 to 7 days to obtain (C)₁₀H₂₂N)₆MX₉Or (C)₁₀H₂₂N)₆MX₉·H₂O crystal, filtering and drying the obtained reaction liquid and the crystal in sequence to obtain the organic-inorganic hybrid metal halide (C) based on the 4-tert-butyl cyclohexylamine ligand₁₀H₂₂N)₆MX₉The crystal of (4).

Further, MX-containing molecules described in step (1)₃The molar ratio of the compound (1) to the 4-tert-butylcyclohexylamine is 1:1 to 1: 3.2.

Further, the HX acid in step (3) may be hydrochloric acid, hydrobromic acid, hydroiodic acid or a mixture thereof.

Further, the solution in the step (4) is stirred and heated to react at the temperature of 40-120 ℃.

The organic-inorganic hybrid metal halide crystal based on the 4-tert-butyl cyclohexylamine ligand is mainly applied to the photoelectric field, wherein the photoelectric field comprises the fields of illumination, light-emitting diodes, lasers, solar cells, photosensitive transistors, fluorescent powder, photoelectric detectors and the like.

The key points of the technology of the invention are as follows:

the invention realizes the combination with halide based on M (In, Sb and Bi) elements through the introduced macrocyclic organic 4-tert-butylcyclohexylamine, and prepares a novel organic-inorganic hybrid metal halide material.

Compared with the prior art, the invention has the following advantages and beneficial effects:

(1) the fluorescence conversion efficiency is high;

(2) the emission spectrum coverage range is wide;

(3) the luminescent material has high luminous efficiency and excellent thermal stability;

(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 applied to the fields of spectrum conversion, tracing marks, anti-counterfeiting and the like.

Drawings

Fig. 1 is a powder X-ray diffraction (XRD) pattern of samples prepared in example 1, example 2 and example 3 of the present invention.

FIG. 2 is a graph of the excitation spectrum of a sample prepared in example 1 of the present invention.

FIG. 3 is a graph of the emission spectrum of a sample prepared in example 1 of the present invention.

FIG. 4 is a graph of the excitation spectrum of a sample prepared in example 2 of the present invention.

Fig. 5 is an emission spectrum of a sample prepared in example 2 of the present invention.

FIG. 6 is a graph of the excitation spectrum of a sample prepared in example 3 of the present invention.

FIG. 7 is a graph of the emission spectrum of a sample prepared in example 3 of the present invention.

Detailed Description

The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1

The chemical composition formula of the embodiment is (C)₁₀H₂₂N)₆SbBr₉The preparation method of the organic-inorganic hybrid metal halide luminescent material comprises the following steps:

proportioning according to stoichiometric ratio, and respectively weighing high-purity SbBr₃Taking compound powder as raw material, and measuring organic 4-tert-butylcyclohexylamine (C)₁₀H₂₁N), measuring HBr acid. Weighing the organic 4-tert-butyl cyclohexylamine solution and SbBr₃Mixing the powder raw materials of the compound and dissolving in a containerAdding a certain amount of N, N-dimethylformamide solution into the organic 4-tert-butylcyclohexylamine solution and SbBr₃The powdered feed was placed in a vessel and then a measured amount of HBr acid was added. Heating the obtained mixed solution to 50-80 deg.C, stirring to dissolve the mixture completely to obtain clear solution, placing the clear solution in oven at 50-80 deg.C, and cooling for 1-7 days to obtain the desired product (C)₁₀H₂₂N)₆SbBr₉·H₂O or (C)₁₀H₂₂N)₆SbBr₉Crystals and residual solution, filtering and drying the obtained reaction liquid and the crystals in sequence to obtain (C) based on the 4-tert-butylcyclohexylamine ligand₁₀H₂₂N)₆SbBr₉And (4) crystals.

The powder X-ray diffraction (XRD) pattern, the excitation spectrum and the emission spectrum of the organic-inorganic hybrid metal halide luminescent material prepared in this example are shown in fig. 1, fig. 2 and fig. 3, respectively. The excitation wavelength range is 200-445nm, 3 excitation peaks are respectively located at 250-345nm, 345-375nm and 375-445nm, the emission band is located at 470-800nm, and the emission peak is located at 630 nm. The organic-inorganic hybrid metal halide luminescent material can realize broadband emission.

Example 2

The chemical composition formula of the embodiment is (C)₁₀H₂₂N)₆SbCl₉The preparation method of the organic-inorganic hybrid metal halide luminescent material comprises the following steps:

proportioning according to stoichiometric ratio, and respectively weighing high-purity SbCl₃Taking compound powder as raw material, and measuring organic 4-tert-butylcyclohexylamine (C)₁₀H₂₁N), measuring HBr acid. Weighing the organic 4-tert-butyl cyclohexylamine solution and SbCl₃Mixing the powder raw materials of the compound, dissolving the mixture in a container, adding a certain amount of N, N-dimethylformamide solution into the organic 4-tert-butylcyclohexylamine solution and SbCl₃The powdered raw material is placed in a container, and then a measured amount of HCl acid is added. Heating the obtained mixed solution to 70-90 deg.C under stirringStirring until the mixture is completely dissolved to obtain clear solution, placing the clear solution into an oven at 70-90 deg.C, and cooling for 1-7 days to obtain the desired product (C)₁₀H₂₂N)₆SbCl₉·H₂O or (C)₁₀H₂₂N)₆SbCl₉Crystals and residual solution, filtering and drying the obtained reaction liquid and the crystals in sequence to obtain (C) based on the 4-tert-butylcyclohexylamine ligand₁₀H₂₂N)₆SbCl₉And (4) crystals.

The powder X-ray diffraction (XRD) pattern, the excitation spectrum and the emission spectrum of the organic-inorganic hybrid metal halide luminescent material prepared in this example are shown in fig. 1, fig. 4 and fig. 5, respectively. The excitation wavelength range is 200-400nm, 2 excitation peaks are respectively positioned at 245-304nm and 304-400nm, the emission band is positioned at 455-800nm, and the emission peak is positioned at 651 nm. The organic-inorganic hybrid metal halide luminescent material can realize broadband emission.

Example 3

The chemical composition formula of the embodiment is (C)₁₀H₂₂N)₆InBr₉The preparation method of the organic-inorganic hybrid metal halide luminescent material comprises the following steps:

proportioning according to stoichiometric ratio, and respectively weighing high-purity InBr₃Taking compound powder as raw material, and measuring organic 4-tert-butylcyclohexylamine (C)₁₀H₂₁N), measuring HBr acid. Weighing the organic 4-tert-butyl cyclohexylamine solution and InBr₃Mixing the powder raw materials of the compound, dissolving the mixture in a container, adding a certain amount of N, N-dimethylformamide solution into the organic matter 4-tert-butylcyclohexylamine solution and InBr₃The powdered raw material is placed in a container, and then a measured amount of HCl acid is added. Heating the obtained mixed solution to 60-90 deg.C, stirring to dissolve the mixture completely to obtain clear solution, placing the clear solution in 60-90 deg.C oven, and cooling for 1-7 days to obtain the desired product (C)₁₀H₂₂N)₆InBr₉·H₂O or (C)₁₀H₂₂N)₆InBr₉Crystals and residual solution, filtering and drying the obtained reaction liquid and the crystals in sequence to obtain (C) based on the 4-tert-butylcyclohexylamine ligand₁₀H₂₂N)₆InBr₉And (4) crystals.

The powder X-ray diffraction (XRD) pattern, the excitation spectrum and the emission spectrum of the organic-inorganic hybrid metal halide luminescent material prepared in this example are shown in fig. 1, fig. 6 and fig. 7, respectively. The excitation wavelength range is 200-400nm, 2 excitation peaks are respectively positioned at 254-338nm and 338-400nm, the emission band is positioned at 440-800nm, and the emission peak is positioned at 640 nm. The organic-inorganic hybrid metal halide luminescent material can realize broadband emission.

Examples 4 to 9 desired raw materials were weighed according to the chemical composition formulas and stoichiometric ratios in table 1, the preparation method thereof was the same as that of example 1, and the relative brightness and emission main peak wavelength of the synthesized samples are shown in table 1.

TABLE 1

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.