CN112538354A - Quantum dot composite material, preparation method thereof, light-emitting film and display device - Google Patents
Quantum dot composite material, preparation method thereof, light-emitting film and display device Download PDFInfo
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Abstract
The invention belongs to the technical field of display, and particularly relates to a quantum dot composite material, a preparation method thereof, a luminescent film and a display device. The preparation method of the quantum dot composite material provided by the invention comprises the following steps: obtaining a mixed solution containing a metal organic framework material, a sensitizer and quantum dots, wherein the metal organic framework material has a porous structure and unsaturated metal sites, and the sensitizer is at least partially connected with the unsaturated metal sites in a matching manner; and heating the mixed solution to enable the quantum dots to be at least partially loaded in the porous structure. The quantum dot composite material prepared by the method has good dispersibility, light stability, light-emitting performance and quantum efficiency. The method solves the problems that the prior quantum dots are easy to agglomerate and the luminous performance of the prior quantum dots is easy to be influenced by environmental change.
Description
Technical Field
The invention belongs to the technical field of display, and particularly relates to a quantum dot composite material, a preparation method thereof, a luminescent film and a display device.
Background
Semiconductor quantum dots, as a new type of nano-material, have received increasing attention as the research on synthesis and performance thereof has been increasingly advanced in recent years. The quantum dots have very considerable application prospect due to the unique performance of the quantum dots. Quantum dots have also found great potential in optoelectronic devices, being a valuable light converting and luminescent material in display and lighting, especially for white light emitting diodes currently referred to as "fourth generation illumination sources".
However, quantum dots as luminescent materials are prone to agglomeration during application, resulting in significant decay of fluorescence properties. To solve this technical problem, some organic ligands are often used to surface-modify the quantum dots to reduce the quantum dot agglomeration. Researches prove that part of organic ligands such as mercaptan, amine, phosphate and the like interact with the quantum dots, and the fluorescence luminescence intensity of the quantum dots can be improved to a certain extent. However, since most of these ligands have a small molecular structure, the ligands are bonded to the surface of the quantum dot to suppress aggregation to some extent, but are easily detached due to environmental changes, and finally, the luminescence property of the quantum dot deteriorates with time.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a quantum dot composite material, and aims to solve the problems that the existing quantum dots are easy to agglomerate and the luminous performance of the existing quantum dots is easily influenced by environmental changes.
Another object of the present invention is to provide a quantum dot composite material, and still another object is to provide a light emitting thin film and a display device.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a quantum dot composite material comprises the following steps:
obtaining a mixed solution containing a metal organic framework material, a sensitizer and quantum dots, wherein the metal organic framework material has a porous structure and unsaturated metal sites, and the sensitizer is at least partially connected with the unsaturated metal sites in a matched manner;
heating the mixed solution so that the quantum dots are at least partially supported in the porous structure.
According to the preparation method of the quantum dot composite material, the metal organic framework material, the sensitizer and the quantum dot liquid phase system are heated, so that the sensitizer and the quantum dot are loaded on the metal organic framework material, on one hand, the quantum dot is loaded in the porous structure of the metal organic framework material, the quantum dot can be prevented from being agglomerated in the application process, and good light stability and light emitting performance are ensured; on the other hand, the sensitizer is matched and connected with the unsaturated metal sites of the metal organic framework material, so that the luminescence property of the quantum dots can be further improved. The method is simple, simple and convenient to operate and easy for large-scale mass production.
Accordingly, a quantum dot composite, comprising: the quantum dot-organic composite material comprises a metal-organic framework material, a sensitizer and quantum dots, wherein the metal-organic framework material is provided with a porous structure and unsaturated metal sites, the quantum dots are at least partially loaded in the porous structure, and the sensitizer is at least partially matched and connected with the unsaturated metal sites.
The quantum dot composite material provided by the invention is formed by compounding the metal organic framework material, the sensitizer and the quantum dots, the quantum dots are loaded in the pore structure of the metal organic framework material, the agglomeration of the quantum dots in the application process can be avoided, meanwhile, the instability of the luminous performance caused by the influence of the external environment change can be prevented, the quantum dot composite material has good light stability, and the luminous performance of the quantum dots is effectively improved by the domain-limited effect of the pore structure on the quantum dots; the sensitizer is connected with the unsaturated metal sites of the metal organic framework material in a matched mode, and through the interaction of the sensitizer and the quantum dots, close-range efficient energy transfer is generated, so that the luminous performance of the quantum dots is further improved, and the quantum efficiency of the quantum dot composite material is improved.
Accordingly, a luminescent film, the material of the luminescent film comprising: the quantum dot composite material prepared by the preparation method or the quantum dot composite material.
The luminescent film provided by the invention comprises the quantum dot composite material, and is formed by compounding the metal organic framework material, the sensitizer and the quantum dots, so that the quantum dots can be effectively prevented from being agglomerated in the application process, and the luminescent film has good light stability, luminescent performance and quantum efficiency.
Accordingly, a display device comprising: the above light-emitting film.
The display device provided by the invention comprises the light-emitting thin film and has good light stability, light-emitting performance and quantum efficiency.
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Fig. 1 is a flowchart of a method for preparing a quantum dot composite material according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In order to solve the problems that the existing quantum dots are easy to agglomerate and the luminous performance of the quantum dots is easy to be influenced by environmental changes, the embodiment of the invention provides the following specific technical scheme:
referring to fig. 1, a method for preparing a quantum dot composite material includes:
s01, obtaining a mixed solution containing a metal organic framework material, a sensitizer and quantum dots, wherein the metal organic framework material has a porous structure and unsaturated metal sites, and the sensitizer is at least partially matched and connected with the unsaturated metal sites;
s02, heating the mixed solution to enable the quantum dots to be at least partially loaded in the porous structure.
According to the preparation method of the quantum dot composite material provided by the embodiment of the invention, the metal organic framework material, the sensitizer and the quantum dot liquid phase system are mixed and heated, so that the sensitizer and the quantum dot are loaded on the metal organic framework material; on the other hand, the sensitizer is matched and connected with the unsaturated metal sites of the metal organic framework material, so that the luminescence property of the quantum dots can be further improved. The method is simple, simple and convenient to operate and easy for large-scale mass production.
In step S01, the metal-organic framework material is a porous material having a porous structure and unsaturated metal sites, and is a multi-dimensional structure formed by self-assembly of organic ligands containing oxygen, nitrogen, etc. and metal centers through coordination bonds. It is understood that the unsaturated metal sites are distributed in the porous structure of the metal-organic framework material, and also on the surface of the metal-organic framework material; meanwhile, the porous structure comprises pores and pore channels with adjustable sizes and a pore cage consisting of micropore panes, and the quantum dots can be loaded in the pores, the pore channels or the pore cage in the metal organic framework material. In the quantum dot composite material prepared by the embodiment of the invention, the metal organic framework material provides a multidimensional framework for the quantum dot composite material, so that the quantum dot is loaded in a pore structure in the multidimensional framework, and the sensitizer is loaded in the multidimensional framework through matching and connecting with the unsaturated metal site.
As an embodiment, the metal-organic framework material includes at least one of a zinc-based metal-organic framework material, a copper-based metal-organic framework material, and a cobalt-based metal-organic framework material. Based on the three types of metal organic framework material structures, the metal organic framework material structure has more mesoporous structures and larger specific surface area, on one hand, more quantum dots can be adsorbed to enter the mesoporous structures to form a compound; on the other hand, the three metal organic framework materials do not affect the energy transfer between the quantum dots and the sensitizer. In some embodiments, the metal-organic framework material is selected to be a zinc-based metal-organic framework material, preferably MOF-5 and/or MOF-177. Further, MOF-5 is composed of a metal cluster Zn4O(CO2)6And isophthalic acid production; MOF-177 is made of metal cluster Zn4O and trimesic acid. In further embodiments, the metal-organic framework material is selected from copper-based metal-organic framework materials, preferably Cu2(1, 4-naphthalenedicarboxylic acid) 2(1,2, 4-triazol-1-yl) propane. Further, Cu2(1, 4-naphthalenedicarboxylic acid) 2(1,2, 4-triazol-1-yl) propane made from Cu (NO)3)2·3H2O, 1, 4-naphthalenedicarboxylic acid and (1,2, 4-triazol-1-yl) propane. In still further embodiments, the metal organic framework material is selected to be a cobalt-based metal organic framework material, preferably Co (benzodithiophene cyclic dicarboxylic acid) (1, 3-bipyridine-propane). Further, Co (benzodithiophene cyclic dicarboxylic acid) (1, 3-bipyridine-propane) was prepared from CoCl2·6H2O, benzodithiophene cyclic dicarboxylic acid, and 1, 3-bipyridine-propane.
Specifically, the quantum dots are used as a light-emitting material and loaded in a porous structure of a metal organic framework material through reaction. In the metal organic framework material, the porous structure comprises pores with adjustable sizes, pore channels and a pore cage consisting of micropore panes, and in the quantum dot composite material, the quantum dots are positioned in the pores, the pore channels or the pore cage in the metal organic framework material. The quantum dots are loaded in the porous structure of the metal organic framework material, so that the quantum dots can be prevented from being agglomerated in the application process. Compared with the prior art of modifying ligand micromolecules on the surface of the quantum dot, the quantum dot is not easy to fall off due to the influence of environmental change, and has good light stability. And moreover, the luminescent performance of the quantum dots is effectively improved through the domain-limited effect of the pore structure on the quantum dots.
As an embodiment, the quantum dot includes a group II-VI compound quantum dot, a group III-V compound quantum dot, or a group IV-VI compound quantum dot. Further, the quantum dot includes: binary phase, ternary phase and quaternary phase quantum dots. Wherein the binary phase quantum dots include, but are not limited to, CdSe, ZnSe, PbSe, CdTe, ZnO, InP, GaN, GaP, AlP, InN, ZnTe, InAs, GaAs, CaF2Etc., the ternary phase quantum dots include but are not limited to Cd1-xZnxS/ZnS、Cd1-xZnxSe/ZnSe、CdSe1-xSx/CdSeyS1-y/CdS、Cd1-xZnxS、Cd1-xZnxSe、CdSeyS1-y、PbSeyS1-y、CdSe/Cd1-xZnxSe/CdyZn1-ySe/ZnSe、ZnxCd1-XTe、Cd1-xZnxSe/CdyZn1-ySe/ZnSe、CdS/Cd1-xZnxS/CdyZn1-yS/ZnS、NaYF4、CdS/ZnS、NaCdF4Etc., the quaternary phase quantum dots include but are not limited to Cd1-xZnxSeyS1-y、CdSe/ZnS、Cd1- xZnxSe/ZnS, CdSe/CdS/ZnS, CdSe/ZnSe/ZnS, etc. Furthermore, the particle size of the quantum dots is 5-10nm, so that the composite efficiency between the quantum dots and the metal organic framework material is improved, and the overall luminous performance is improved and reduced as a whole.
Specifically, the sensitizer is coordinated with the unsaturated metal site through reaction and loaded on the metal organic framework material, when an electric field is applied to the quantum dot composite material, the sensitizer is excited by the electric field, electrons are transferred from a ground state to high energy through short-distance efficient energy transfer, and the energy is transferred to the quantum dot in a charge mode, so that the quantum dot obtains more energy to generate radiation transition, the light emitting performance of the quantum dot is further improved, and the quantum efficiency of the quantum dot composite material is further improved. It will be appreciated that the sensitizer is most preferred when it is supported on the surface of the porous structure of the metal organic framework material. In one embodiment, the sensitizer comprises at least one of ruthenium terpyridyl, cobalt terpyridyl, osmium terpyridyl, copper tetrakis (tris) hydroxymethyl aminomethane, and copper 2-ethylimidazole. The sensitizers have the characteristics of repeatable excitation, high luminous efficiency, good stability and the like; meanwhile, in the electrifying and exciting process, the sensitizer generates oxidation-reduction reaction to generate a large amount of free radical intermediates, the free radical intermediates transfer more energy to the quantum dots in a close-distance energy transfer mode, and the transfer efficiency is higher due to the fact that the free radicals are used for transferring energy, so that the luminous efficiency of the quantum dots is higher.
In one embodiment, the weight ratio of the metal organic framework material to the sensitizer in the mixed solution is preferably (2-5): (5-7). Further, the weight ratio of the quantum dot to the sensitizer is preferably (3-5): 10-20), so that the sensitizer can transfer transition energy to the quantum dot as much as possible, and the luminous efficiency of the quantum dot is improved. When the amount of the quantum dots is too much to exceed the above weight ratio range, relaxation between quantum dots of different sizes may occur, and light emitted from a part of the quantum dots is absorbed by another quantum dot to cause a decrease in luminous efficiency; when the dosage of the sensitizer exceeds the weight ratio range, the luminescent performance of the composite material is mainly dominated by the sensitizer, and light emitted by the quantum dots can be absorbed by the excessive sensitizer, so that the original luminescent performance is lost.
The step of obtaining the mixed solution containing the metal organic framework material, the sensitizer and the quantum dots can refer to the conventional operation in the field, and finally the mixed system simultaneously comprises the metal organic framework material, the sensitizer and the quantum dots. It will be appreciated that due to the characteristics of the metal organic framework material, the sensitizer and the quantum dots themselves, in this mixed system, part of the sensitizer and/or quantum dots are or are composited with the metal organic framework material.
As a preferred embodiment, the step of obtaining a mixed solution containing a metal-organic framework material, a sensitizer and quantum dots comprises:
s011, providing a metal precursor, an organic ligand and a sensitizer, dissolving the metal precursor, the organic ligand and the sensitizer in a solvent, and reacting under a heating condition to obtain a reaction solution containing a metal organic framework material and the sensitizer, wherein the sensitizer is at least partially matched and connected with unsaturated metal sites of the metal organic framework material;
and S012, providing quantum dots, and dispersing the quantum dots in the reaction liquid containing the metal organic framework material and the sensitizer to obtain a mixed solution containing the metal organic framework material, the sensitizer and the quantum dots.
As an embodiment, in step S011, the metal precursor is preferably at least one of a zinc salt, a copper salt, and a cobalt salt. Wherein the zinc salt provides zinc ions for the reaction, preferably Zn4O(CO2)6And/or Zn4O; the copper salt provides copper ions for the reaction, preferably Cu (NO)3)2·3H2O; the cobalt salt provides cobalt ions for the reaction, preferably CoCl2·6H2And O. The organic ligand comprises at least one of pyromellitic acid, trimesic acid, 1, 4-naphthalenedicarboxylic acid, (1,2, 4-triazol-1-yl) propane, benzodithiophene cyclic dicarboxylic acid and 1, 3-bipyridine-propane. In the process of reaction, the metal precursor and the organic ligand self-assemble to form the metal organic framework material through the action of coordination bonds. In some embodiments, the metal-organic framework material is selected as MOF-5, and the metal precursor thereof is selected as the metal cluster Zn4O(CO2)6The organic ligand is selected from phthalic acid; in other embodiments, the metal organic framework material is selected as MOF-177, and the metal precursor thereof is selected as metal cluster Zn4O, wherein the organic ligand of the O is trimesic acid; in still other embodiments, the metal-organic framework material is selected to be Cu2(1, 4-naphthalenedicarboxylic acid) 2(1,2, 4-triazol-1-yl) propane, the metal precursor of which is selected from Cu (NO)3)2·3H2O, the organic ligand of which is selected from 1, 4-naphthalenedicarboxylic acid and (1,2, 4-triazol-1-yl) propane; in still other embodiments, the metal-organic framework material is selected from Co (benzodithiophene cyclic dicarboxylic acid) (1, 3-bipyridine-propane), and the metal precursor thereof is selected from CoCl2·6H2O, the organic ligand of which is selected from benzodithiophene cyclic dicarboxylic acid and 1, 3-bipyridine-propane.
As an embodiment, in the step of performing the reaction, the reaction temperature is preferably 100-150 ℃ and the heating time is preferably 10-20 hours. In some embodiments, the reaction temperature is 100, 105, 110, 113, 120, 125, 127, 130, 132, 135, 136, 138, 141, 145, 148, 150 ℃ and the heating time is 10, 13, 15, 17, 19, 20 hours.
The metal precursor, the organic ligand and the sensitizer are dissolved in the solvent, so that the sensitizer can be continuously compounded with the metal-organic framework material in the synthesis process of the metal-organic framework material, the sensitizer can enter the metal-organic framework material more deeply, for example, enter and be loaded on the surface of a porous structure of the metal-organic framework material, and the compounding efficiency of the sensitizer and the metal-organic framework material is greatly improved. After the reaction is finished, the reaction solution contains a metal organic framework material and a sensitizing agent, and the sensitizing agent is basically matched and connected with the unsaturated metal sites.
As an embodiment, the metal precursor and the organic ligand are dissolved in a solvent, and the molar ratio of the metal precursor, the organic ligand and the sensitizer is (2-5): (0.5-1.5): (5-7).
In one embodiment, the solvent comprises at least one of water, alcohol, N-dimethylformamide, dimethylsulfoxide, and N-methylpyrrolidone. Further, in the step of dissolving the metal precursor and the organic ligand with the sensitizer in a solvent, the solvent has a capacity at least sufficient to dissolve the metal precursor, the organic ligand and the sensitizer.
The step of dissolving the metal precursor and the organic ligand and the sensitizer in the solvent may refer to the conventional operation in the art, such as dispersing by stirring and/or ultrasound, so that the metal precursor, the organic ligand and the sensitizer are well mixed and dissolved in the solvent.
In step S012, the step of dispersing the quantum dots in the reaction liquid containing the metal organic framework material and the sensitizer may be performed by referring to conventional operations in the art, for example, by stirring and/or ultrasonic methods, so that the quantum dots are sufficiently uniformly dispersed in the solvent system. Based on the analysis of the step S011, it can be understood that, in the reaction solution containing the metal-organic framework material and the sensitizer, the sensitizer is fully compounded with the metal-organic framework material, and on the premise that the mass ratio of the quantum dots to the metal-organic framework material compounded with the sensitizer in the reaction solution is preferably (3-5): (10-20).
Specifically, in step S02, the mixed solution is heated so that the sensitizer and the quantum dots are supported on the metal-organic framework material. The metal organic framework material has a porous structure, and a sensitizer and the quantum dots are synchronously or asynchronously adsorbed by the porous structure in the heating process and loaded on the metal organic framework material; meanwhile, as the heating process is carried out, the unsaturated metal sites of the metal organic framework material are exposed, so that the sensitizer is further loaded on the metal organic framework material through the matching connection with the unsaturated metal sites.
In one embodiment, the step of heating the mixed solution is performed at a heating temperature of 40 to 60 ℃ for 1 hour or more to accelerate the reaction. In specific embodiments, the heating temperature is 40, 42, 45, 46, 49, 50, 52, 53, 55, 56, 59, 60 ℃ and the heating time is 1h, 2h, 3h or 4 h.
In one embodiment, in the step of heating the mixed solution, a linking agent is added for mixing and heating; the linking agent comprises at least one of 3- (2-aminoethylamino) propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and 3- [2- (2-aminoethylamino) ethylamino ] propyl-trimethoxysilane. And adding a linking agent in the step of heating the mixed solution, so that the quantum dots and the metal-organic framework material can be further promoted to be compounded.
In summary, under the combined effect of the optimized process and the plurality of optimized parameters provided by the embodiment of the present invention, the quantum dot composite material obtained by the preparation method provided by the embodiment of the present invention has the advantages of optimal comprehensive performance, stable luminescent performance, optimal luminescent performance and optimal quantum efficiency.
The following is a quantum dot composite material prepared by the preparation method provided by the embodiment of the invention.
Correspondingly, the quantum dot composite material prepared by the preparation method comprises the following steps: the quantum dot-organic composite material comprises a metal-organic framework material, a sensitizer and quantum dots, wherein the metal-organic framework material is provided with a porous structure and unsaturated metal sites, the quantum dots are at least partially loaded in the porous structure, and the sensitizer is at least partially matched and connected with the unsaturated metal sites.
The quantum dot composite material provided by the embodiment of the invention is formed by compounding the metal organic framework material, the sensitizer and the quantum dots, the quantum dots are loaded in the pore structure of the metal organic framework material, the aggregation of the quantum dots in the application process is avoided, meanwhile, the instability of the luminous performance caused by the influence of the external environment change can be prevented, the quantum dot composite material has good light stability, and the luminous performance of the quantum dots is effectively improved by the domain limiting effect of the pore structure on the quantum dots; the sensitizer is connected with the unsaturated metal sites of the metal organic framework material in a matched mode, the sensitizer interacts with the quantum dots to generate close-range efficient energy transfer, the light emitting performance of the quantum dots is further improved, and the quantum efficiency of the quantum dot composite material is improved.
Specifically, the functions and specific types of the metal organic framework material, the sensitizer and the quantum dot are substantially the same as those described above, and are not repeated herein for the sake of brevity.
In one embodiment, the quantum dot composite material comprises 85 to 88 parts of the metal organic framework material, 9 to 13 parts of the sensitizer and 2 to 3 parts of the quantum dot, based on 100 parts of the total weight of the quantum dot composite material.
Accordingly, a luminescent film, the material of the luminescent film comprising: the quantum dot composite material or the quantum dot composite material prepared by the preparation method.
The luminescent film provided by the embodiment of the invention comprises the quantum dot composite material, and is formed by compounding the metal organic framework material, the sensitizer and the quantum dots, so that the quantum dots can be effectively prevented from being agglomerated in the application process, and the luminescent film has good light stability, luminescent performance and quantum efficiency.
Accordingly, a display device comprising: the above light-emitting film.
The display device provided by the embodiment of the invention comprises the light-emitting film, and has good light stability, light-emitting performance and quantum efficiency.
Preferably, the display device includes: a color filter or a quantum dot light emitting diode.
In some embodiments, the display device is a color filter, the color filter includes a color filter layer, the color filter layer includes a plurality of pixel regions, the pixel regions have a plurality of sub-pixel filter layers arranged, and a material of at least one sub-pixel filter layer includes: the above light-emitting film.
In other embodiments, the display device is a quantum dot light emitting diode, the quantum dot light emitting diode includes a cathode and an anode which are oppositely arranged, a quantum dot light emitting film is arranged between the cathode and the anode, and the material of the quantum dot light emitting film includes: the above light-emitting film.
In order that the above-described details and operation of the embodiments of the present invention will be clearly understood by those skilled in the art, and the advanced performance of a quantum dot composite material, a method of manufacturing the same, a light emitting thin film and a display device according to the embodiments of the present invention will be remarkably shown, the embodiments of the present invention will be exemplified by the following examples.
Example 1
The embodiment provides a quantum dot composite material, which specifically comprises the following steps:
2mmol of Zn4O(CO2)6And 0.5mmol of isophthalic acid were dissolved in 15mL of N, N-dimethylformamide, 7mmol of ruthenium terpyridyl was added thereto, and after ultrasonic dissolution, the mixed solution was transferred to a 50mL stainless steel autoclave containing polytetrafluoroethylene. Heating to 120 ℃ in a program oven, preserving the heat for 10h, and naturally cooling to room temperature. After the reaction is finished, filtering to obtain MOF-5 of the composite terpyridyl ruthenium;
dispersing 1mL of 3- (2-aminoethylamino) propyltrimethoxysilane, 1mg of MOF-5 compounded with terpyridyl ruthenium and 6mg of CdSe in ethanol, stirring and mixing at 45 ℃ for 2 hours, standing, cleaning and drying to obtain CdSe @ terpyridyl ruthenium/MOF-5.
The quantum dot composite material prepared by the present example had a quantum efficiency of 80%, and the quantum dot efficiency after 15 days of standing was 76%.
Example 2
The embodiment provides a quantum dot composite material, which specifically comprises the following steps:
3mmol of Zn4Dissolving O and 1mmol of trimesic acid in 15mL of N, N-dimethylformamide, adding 6mmol of cobalt terpyridyl, ultrasonically dissolving, and transferring the mixed solution to a stainless steel high-pressure reaction kettle of 50mL of polytetrafluoroethylene. Heating to 140 ℃ in a program oven, preserving the heat for 15h, and naturally cooling to room temperature. After the reaction is finished, filtering to obtain MOF-177 of the composite terpyridyl cobalt;
taking 1.5mL of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 1.6mg of MOF-177 of composite terpyridyl cobalt and 8mg of CdSe1-xSx/CdSeyS1-yDispersing CdS in ethanol, stirring and mixing at 55 deg.C for 1.6h, standing, cleaning, and oven drying to obtain CdSe1-xSx/CdSeyS1-y/CdS @ Cobaltosite/MOF-177.
The quantum dot composite material prepared by the present example had a quantum efficiency of 90%, and the quantum dot efficiency after 15 days of standing was 87%.
Example 3
The embodiment provides a quantum dot composite material, which specifically comprises the following steps:
4mmol of Cu (NO)3)23H2O and 1.5mmol of 1, 4-naphthalenedicarboxylic acid) and (1,2, 4-triazol-1-yl) propane were dissolved in 15mL of N, N-dimethylformamide, 6.5mmol of 2-ethylimidazolium copper was added, and after ultrasonic dissolution, the mixed solution was transferred to a stainless autoclave of 50mL of polytetrafluoroethylene. Heating to 145 ℃ in a programmed oven, preserving the temperature for 18h, and naturally cooling to room temperature. After the reaction is finished, filtering to obtain the Cu of the compound 2-ethylimidazole copper2(1, 4-naphthalenedicarboxylic acid)2(1,2, 4-triazol-1-yl) propane;
1.3mL of 3- [2- (2-aminoethylamino) ethylamino]Propyl-trimethoxysilane, 1.7mg of Cu complex with 2-ethylimidazole copper2(1, 4-naphthalenedicarboxylic acid)2(1,2, 4-triazol-1-yl) propane and 3mg of PbSeyS1-yDispersing in ethanol, stirring and mixing at 55 deg.C for 2h, standing, cleaning, and oven drying to obtain PbSeyS1-y@ 2-ethylimidazole copper/Cu2(1, 4-naphthalenedicarboxylic acid)2(1,2, 4-triazol-1-yl) propane.
The quantum efficiency of the quantum dot composite material prepared by the present example was 85%, and the quantum dot efficiency after 15 days of standing was 80%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (14)
1. A preparation method of a quantum dot composite material is characterized by comprising the following steps:
obtaining a mixed solution containing a metal organic framework material, a sensitizer and quantum dots, wherein the metal organic framework material has a porous structure and unsaturated metal sites, and the sensitizer is at least partially connected with the unsaturated metal sites in a matched manner;
heating the mixed solution so that the quantum dots are at least partially supported in the porous structure.
2. The method according to claim 1, wherein the weight ratio of the metal-organic framework material to the sensitizer in the mixed solution is (2-5): (5-7); and/or
In the mixed solution, the weight ratio of the quantum dots to the sensitizer is (3-5) to (10-20).
3. The method according to claim 1, wherein the step of heating the mixed solution is performed at a temperature of 40 to 60 ℃ for 1 hour or more.
4. The method of manufacturing according to claim 1, wherein the metal-organic framework material comprises at least one of a zinc-based metal-organic framework material, a copper-based metal-organic framework material, and a cobalt-based metal-organic framework material; and/or
The sensitizer comprises at least one of terpyridyl ruthenium, terpyridyl cobalt, terpyridyl osmium, tetra (tris) copper and 2-ethylimidazole copper; and/or
The quantum dots include at least one of group II-VI compound quantum dots, group III-V compound quantum dots, and group IV-VI compound quantum dots.
5. The production method according to any one of claims 1 to 4, wherein in the step of heating the mixed solution, a linking agent is added for mixing and heating;
the linking agent comprises at least one of 3- (2-aminoethylamino) propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and 3- [2- (2-aminoethylamino) ethylamino ] propyl-trimethoxysilane.
6. The production method according to any one of claims 1 to 4, wherein the step of obtaining a mixed solution containing the metal-organic framework material, the sensitizer, and the quantum dot includes:
providing a metal precursor, an organic ligand and a sensitizer, dissolving the metal precursor, the organic ligand and the sensitizer in a solvent, and reacting under a heating condition to obtain a reaction solution containing a metal organic framework material and the sensitizer, wherein the sensitizer is at least partially connected with unsaturated metal sites of the metal organic framework material in a matching manner;
providing quantum dots, and dispersing the quantum dots in the reaction liquid containing the metal organic framework material and the sensitizer to obtain a mixed solution containing the metal organic framework material, the sensitizer and the quantum dots.
7. The method as set forth in claim 6, wherein the step of carrying out the reaction under heating is carried out at a reaction temperature of 100 ℃ and 150 ℃ for a heating time of 10 to 20 hours.
8. The production method according to claim 6, characterized in that in the step of dissolving the metal precursor and the organic ligand with the sensitizer in a solvent, the molar ratio of the metal precursor, the organic ligand and the sensitizer is (2-5): (0.5-1.5): (5-7).
9. The method according to claim 6, wherein the metal precursor is at least one of a zinc salt, a copper salt, and a cobalt salt; and/or
The organic ligand comprises at least one of pyromellitic acid, trimesic acid, 1, 4-naphthalenedicarboxylic acid, (1,2, 4-triazol-1-yl) propane, benzodithiophene cyclic dicarboxylic acid and 1, 3-bipyridine-propane; and/or
The solvent includes at least one of water, alcohol, N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone.
10. A quantum dot composite, comprising: the quantum dot-organic composite material comprises a metal-organic framework material, a sensitizer and quantum dots, wherein the metal-organic framework material is provided with a porous structure and unsaturated metal sites, the quantum dots are at least partially loaded in the porous structure, and the sensitizer is at least partially matched and connected with the unsaturated metal sites.
11. The quantum dot composite of claim 10, wherein the metal organic framework material comprises at least one of a zinc-based metal organic framework material, a copper-based metal organic framework material, and a cobalt-based metal organic framework material; and/or
The sensitizer comprises at least one of terpyridyl ruthenium, terpyridyl cobalt, terpyridyl osmium, tetra (tris) copper and 2-ethylimidazole copper; and/or
The quantum dots include at least one of group II-VI compound quantum dots, group III-V compound quantum dots, and group IV-VI compound quantum dots.
12. The quantum dot composite material according to claim 10 or 11, wherein the metal organic framework material is 85-88 parts, the sensitizer is 9-13 parts, and the quantum dot is 2-3 parts, based on 100 parts of the total weight of the quantum dot composite material.
13. A luminescent film, wherein a material of the luminescent film comprises: a quantum dot composite material produced by the production method described in any one of claims 1 to 9, or a quantum dot composite material described in any one of claims 10 to 12.
14. A display device, comprising: the light emitting film of claim 13.
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