CN113122256A - Nano material and preparation method thereof, light-emitting film and display device - Google Patents

Nano material and preparation method thereof, light-emitting film and display device Download PDF

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CN113122256A
CN113122256A CN201911394130.7A CN201911394130A CN113122256A CN 113122256 A CN113122256 A CN 113122256A CN 201911394130 A CN201911394130 A CN 201911394130A CN 113122256 A CN113122256 A CN 113122256A
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quantum dots
crown ether
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叶炜浩
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TCL Corp
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Abstract

The invention belongs to the technical field of display, and particularly relates to a nano material, a preparation method thereof, a light-emitting film and a display device. The invention provides a nano material, which comprises: the cation is combined with the quantum dot through complexing crown ether, and at least part of the cation is combined with two or more quantum dots. Therefore, the quantum dots are close to each other and generate close-range energy transfer, so that the quantum dots with smaller sizes can transfer energy to the quantum dots with larger sizes through non-radiative transition, the emission half-peak width of the nano material is reduced, and the quantum efficiency of the nano material is improved. Solves the problems of large half-peak width and low quantum efficiency of the existing nano material.

Description

Nano material and preparation method thereof, light-emitting film and display device
Technical Field
The invention belongs to the technical field of display, and particularly relates to a nano material, a preparation method thereof, a light-emitting film and a display device.
Background
Quantum dots, also known as semiconductor nanocrystals, refer to fine crystals, intermediate bulk materials and intermolecular species, all in the nanometer range of three-dimensional size, whereby their properties cannot be explained by either macroscopic or microscopic molecular or atomic theory. The size of the quantum dot is equal to or less than the de Broglie wavelength in three dimensional directions, and the energy of the electron is quantized in three dimensional directions, so that the quantum dot is endowed with special optical, electric, magnetic, catalytic and other properties.
The optical properties of quantum dots are closely related to quantum size effects. When the size of a quantum dot is reduced to a certain value, the electron energy level near its fermi level is changed from quasi-continuous to discrete, so that the continuous energy band of the semiconductor becomes a split energy level structure and the band gap is widened. When the particle size of the quantum dot is reduced, the band gap energy of the quantum dot is increased, so that the absorption spectrum is subjected to blue shift, and the emission spectrum is subjected to blue shift. The emission spectrum of a quantum dot can be controlled by its size due to the influence of quantum size effects and quantum confinement effects. The fluorescence emission wavelength depends on the size of the quantum dots, the larger the size is, the longer the fluorescence emission wavelength is, and the fluorescence wavelength can be made to cover the whole visible light region by changing the size and chemical composition of the quantum dots.
In the process of growing the quantum dots, the growth of the quantum dots mainly comprises two processes of focusing and defocusing due to the influence of various factors such as surface energy, monomer concentration in a solution, quantum dot size and the like. The metal and non-metal atoms on the crystal surface and the free ions in the solution always keep a thermodynamic equilibrium state in the growth process, and the small-size quantum dots with low thermal stability have higher reaction and easier coordination with the free ions due to higher specific surface area, and therefore can grow more quickly than the large-size quantum dots, so that the size distribution of the initially formed crystal nucleus is narrow, which is a 'focusing' process. With the continuous addition of free ions, the supply of the monomer makes the growth rate of larger-sized crystal nuclei larger than that of smaller-sized crystal nuclei, resulting in the gradual broadening of the size distribution of the quantum dots, which is called "defocusing". Due to the defocusing process, the emission half-peak width of the finally obtained nano material is wider, and the quantum efficiency is reduced.
Disclosure of Invention
The invention mainly aims to provide a nano material, and aims to solve the problems of large half-peak width and low quantum efficiency of the existing nano material.
The invention also aims to provide a preparation method of the nano material, and further aims to provide a quantum dot light-emitting film and a display device.
In order to achieve the purpose, the invention adopts the following technical scheme:
a nanomaterial comprising: the quantum dots are modified with crown ether on the surface, the cations are combined with the quantum dots through complexing the crown ether, and at least part of the cations are combined with two or more quantum dots.
The invention provides a nano material, which comprises: the quantum dots are characterized by comprising cations and the quantum dots with crown ether modified on the surfaces, wherein the cations are combined with the quantum dots through complexing crown ether, and at least part of the cations are combined with two or more than two quantum dots, so that the quantum dots are close to each other and generate close-range energy transfer, the quantum dots with smaller sizes can transfer energy to the quantum dots with larger sizes through non-radiative transition, and further the emission half-peak width of the nano material is reduced and the quantum efficiency of the nano material is improved.
Correspondingly, the preparation method of the nano material comprises the following steps:
providing quantum dots with crown ether modified on the surfaces;
dispersing the quantum dots with the surfaces modified with crown ethers and cations in a first solvent, so that the cations are combined with the quantum dots through complexing the crown ethers, and at least part of the cations are combined with two or more quantum dots.
According to the preparation method of the nano material provided by the invention, the quantum dots with crown ether modified on the surfaces are complexed with the cations in the first solvent, so that the quantum dots are close to each other and generate close-range energy transfer, and the quantum dots with smaller sizes can transfer energy to the quantum dots with larger sizes through non-radiative transition, so that the obtained nano material has smaller emission half-peak width and good quantum efficiency. The method is simple, simple and convenient to operate and easy for large-scale mass production.
Accordingly, a luminescent film, the material of the luminescent film comprising: the nano material or the nano material prepared by the preparation method.
The luminescent film provided by the invention comprises the nano material, is formed by complexing cations and crown ether modified on the surface of quantum dots, and has smaller emission half-peak width and good quantum efficiency.
Accordingly, a display device comprising: the above light-emitting film.
The display device provided by the invention comprises the light-emitting film, and has smaller emission half-peak width and good quantum efficiency.
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Fig. 1 is a flowchart of a method for preparing a nanomaterial provided in 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 of large half-peak width and low quantum efficiency of the existing nano material, the embodiment of the invention provides the following specific technical scheme:
a nanomaterial comprising: the quantum dots are modified with crown ether on the surface, the cations are combined with the quantum dots through complexing the crown ether, and at least part of the cations are combined with two or more quantum dots.
The nano material provided by the embodiment of the invention comprises: the quantum dots are characterized by comprising cations and the quantum dots of which the surfaces are modified with crown ether, wherein the cations are combined with the quantum dots through complexing crown ether, and at least part of the cations are combined with two or more than two quantum dots, so that the quantum dots are close to each other and generate close-range energy transfer, the quantum dots with smaller sizes can transfer energy to the quantum dots with larger sizes through non-radiative transition, and further the emission half-peak width of the quantum dots is reduced and the quantum efficiency of the quantum dots is improved.
Specifically, the quantum dots with crown ether modified on the surface refer to a class of quantum dots with crown ether connected on the surface, and serve as the luminescent main body of the nano material in the embodiment of the invention. The crown ether is a macrocyclic compound containing a plurality of oxygen atoms, and comprises but is not limited to 15-crown ether-5, 18-crown ether-6, 12-crown ether-4, 1',3' -phenylene dimethylene crown ether and the like.
In some embodiments, the crown ether is 15-crown-5, having the following molecular structure:
Figure BDA0002345824800000041
in some embodiments, the crown ether is 18-crown-6, having the following molecular structure:
Figure BDA0002345824800000042
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, and in some embodiments, the quantum dots include: 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.
In one embodiment, the quantum dots have a particle size of 3 to 15 nm. The emission peak wavelength of the quantum dots is related to the size of the quantum dots, when the particle size of the quantum dots is 3-13nm, the quantum dots can be prevented from agglomerating, the emission peak of the small-size quantum dots is overlapped with the excitation peak of the large-size quantum dots, and further energy transfer is realized, so that the small-size quantum dots can transfer energy to the large-size quantum dots through non-radiative transition. In some embodiments, the particle size of the quantum dots is preferably 5 to 15, ensuring that no agglomeration occurs between the quantum dots.
In the embodiment of the present invention, the crown ether may be connected to the surface of the quantum dot through a thiol, amino, hydroxyl, carboxyl, or other active group. Preferably, the crown ether is connected with the surface of the quantum dot through sulfydryl. The crown ether can be more firmly connected to the surface of the quantum dot through the sulfydryl group compared with other groups such as amino, hydroxyl, carboxyl and the like. In some embodiments, the quantum dots are aqueous phase quantum dots. Preferably, the surface of the aqueous phase quantum dot has a hydrophilic group capable of reacting and connecting with the thiol group, the hydrophilic group includes, but is not limited to, thiol group, carboxyl group, hydroxyl group, amino group, etc., and the crown ether can be tightly and firmly connected to the surface of the quantum dot by combining with the hydrophilic group.
In one embodiment, the crown ether is selected from mercapto crown ethers, which contain at least one mercapto group in their molecular structure. In some embodiments, the mercapto crown ether is obtained by esterification of a hydroxy crown ether with a mercapto or dithio heterocycle-containing carboxylic acid compound. In some embodiments, the preparation of the mercaptocrown ether comprises: according to the molar ratio of (1-3) to (2-4) of hydroxyl crown ether to carboxylic acid compounds containing sulfydryl or disulfide heterocycle, dispersing the hydroxyl crown ether and the carboxylic acid compounds containing sulfydryl or disulfide heterocycle in N, N-dimethylformamide, heating to 100-120 ℃, refluxing for 1-2h, and carrying out esterification reaction to obtain the sulfydryl crown ether. It is understood that the hydroxy crown ethers contain at least one hydroxyl group, including but not limited to 2-hydroxymethyl-15-crown-5, 2-hydroxymethyl-18-crown-6, 2-hydroxymethyl-12-crown-4, 2' -hydroxy-1 ',3' -phenylenedimethylene crown ether, and the like; the carboxylic acid compounds containing mercapto or dithio-heterocycle contain mercapto or dithio-heterocycle, including but not limited to 1, 2-dithiobutane-3-carboxylic acid, 1, 2-dithiocyclopentane-3-carboxylic acid, 1, 2-dithiocyclohexane-3, 6-dicarboxylic acid, mercaptopropionic acid, mercaptoacetic acid, 16-mercaptohexadecanoic acid, etc.
In the embodiment of the invention, the quantum dot modified with crown ether on the surface can be selected from commercial products and can also be prepared by adopting the conventional technical means in the field. In some embodiments, the quantum dot with the surface modified with a crown ether, the crown ether is attached to the surface of the quantum dot with a thiol group. In some embodiments, the crown ether is a mercapto crown ether, and the weight ratio of the mercapto crown ether to the quantum dot is (3-5): (1-2).
Specifically, the cation refers to a kind of positively charged ions capable of being complexed by crown ether, and in the embodiment of the present invention, the cation is combined with the quantum dot through complexing crown ether, and at least part of the cation is combined with two or more quantum dots. In some embodiments, in the nanomaterial, the cation is bound to two or more of the quantum dots; in other embodiments, a portion of the cations are bound to two or more of the quantum dots and another portion of the cations are bound to only one of the quantum dots in the nanomaterial. That is, in the nanomaterial, the crown ethers complexing the same cation are at least positioned on different quantum dots, so that the quantum dots are close to each other and perform close-range energy transfer, the quantum dots with smaller sizes can transfer energy to the quantum dots with larger sizes through non-radiative transition, and further the emission half-peak width of the quantum dots is reduced and the quantum efficiency of the quantum dots is improved. It can be understood that, in the nanomaterial, the number of crown ethers for connecting and modifying the quantum dots can be more than one, and the crown ethers complexing the same cation can be positioned on the same or different quantum dots, but due to larger steric hindrance, the crown ethers complexing the same cation are basically positioned on different quantum dots, so that a structure of quantum dot-crown ether-cation-crown ether-quantum dot is formed.
As an example of the manner in which the device may be used,the cations comprise alkali metal cations and/or alkaline earth metal cations, the sizes of the alkali metal cations and the alkaline earth metal cations are matched with the annular cavities of the crown ether, and the bonding force of the alkali metal cations and the alkaline earth metal cations with the crown ether is strong. If other subgroup cations are adopted, due to the complex energy level structure, an additional energy level can appear after the subgroup cations react with crown ether, molecules similar to organic fluorescent materials are easily formed, and a system formed by quantum dots, crown ether and cations is more complex, so that the luminous performance of the nano material is influenced. As a preferred embodiment, the cation is selected from K+、Ba2+、Mg2+And Ca2+In a hydrophilic first solvent, K+、Ba2+、Mg2+And Ca2+Is less hydrophilic and is more susceptible to complexation by crown ethers. In some embodiments, the cation is selected to be K+(ii) a In other embodiments, the cation is selected to be Ba2+、Mg2+Or Ca2+。
In one embodiment, in the nanomaterial, the ratio of the quantum dots with crown ether modified on the surface to the cations is (10-20) mg (0.01-0.05) mmol.
As an embodiment, in the nanomaterial, the ratio of the quantum dots with the crown ether modified on the surface to the cations is (10-20) mg, (0.01-0.05) mmol, and the mass ratio of the crown ether to the quantum dots in the quantum dots with the crown ether modified on the surface is (3-5) to (1-2) mmol. In the proportion range, the quantum dots can be prevented from agglomerating, and better performance is kept.
The following is a preparation method of the nanomaterial provided by the embodiment of the invention.
Accordingly, referring to fig. 1, a method for preparing the nanomaterial includes the following steps:
s01, providing quantum dots with crown ether modified on the surfaces;
s02, dispersing the quantum dots with the surfaces modified with crown ethers and cations in a first solvent, so that the cations are combined with the quantum dots through complexing the crown ethers, and at least part of the cations are combined with two or more quantum dots.
According to the preparation method of the nano material provided by the embodiment of the invention, the quantum dots with crown ether modified on the surfaces are complexed with the cations in the first solvent, so that the quantum dots are close to each other and generate close-range energy transfer, and the quantum dots with smaller sizes can transfer energy to the quantum dots with larger sizes through non-radiative transition, so that the obtained nano material has smaller emission half-peak width and good quantum efficiency. The method is simple, simple and convenient to operate and easy for large-scale mass production.
Specifically, in step S01, the quantum dot surface-modified with crown ether is substantially the same as the quantum dot surface-modified with crown ether described above.
As an embodiment, the method for preparing the quantum dot with the surface modified with crown ether comprises the following steps: and dispersing the mercapto crown ether and the quantum dot in a second solvent, and carrying out heating reaction under an alkaline condition to enable the mercapto crown ether to be connected with the surface of the quantum dot through mercapto.
The second solvent serves as a reaction solvent, and may be selected from organic solvents that are effective in dispersing and dissolving the quantum dots and the mercapto crown ether and are inert to the reaction, and in some embodiments, the second solvent is selected from at least one of ethanol, methanol, and water.
In some embodiments, the weight ratio of the mercapto-crown ether to the quantum dot is (3-5): 1-2, when the amount of the mercapto-crown ether is too much, the amount of crown ether connected to the surface of the quantum dot is too much, the steric hindrance is increased, and the small-sized quantum dot is difficult to approach the surface of the large-sized quantum dot, so that the capability transfer efficiency between the quantum dots is reduced, and the effect of narrowing the peak width is difficult to achieve; meanwhile, due to the fact that the amount of the crown ether is too large, under the action of cations, a large number of crown ether groups on the quantum dots can cause a large number of quantum dots to be close to each other to agglomerate, and more relaxation or non-radiative loss is caused.
In some embodiments, the heating is carried out at a temperature of 50-70 ℃ for a time of 10-16 hours. The mercapto crown ether can be promoted to react with the quantum dots by heating, and if the reaction temperature is too high or the reaction time is longer, other passivating groups such as carboxyl, amino and the like on the surfaces of the quantum dots can be replaced by a large amount of crown ether, so that the original luminescence performance of the quantum dots is influenced.
In some embodiments, in the step of dispersing the mercapto crown ether and the quantum dots in ethanol, a pH regulator is added to adjust the pH of the solution to 10-13, and hydrogen ions on the mercapto group are separated to form S under alkaline conditions-Ion, S-The ions have higher electronegativity and promote the reaction of the mercapto crown ether and the quantum dots. In some embodiments, the pH adjusting agent is selected from at least one of tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and tetrabutylammonium bromide.
In step S02, the quantum dots with the surface modified with crown ether and the cations are dispersed in a first solvent, so that the quantum dots with the surface modified with crown ether and the cations are uniformly mixed. During this mixing process, the crown ether complexes the cations such that the cations are bound to the quantum dots and the crown ether that complexes the same cation is located at least on a different quantum dot. In some embodiments, in the nanomaterial, the cation is bound to two or more of the quantum dots; in other embodiments, a portion of the cations are bound to two or more of the quantum dots and another portion of the cations are bound to only one of the quantum dots in the nanomaterial. As the crown ether has larger volume and larger steric hindrance, the crown ether complexed with the same cation is basically positioned on different quantum dots to form a structure of quantum dot-crown ether-cation-crown ether-quantum dot. It is understood that the step of dispersing the quantum dots with the surface modified crown ether and the cation in the first solvent is to add the cation to the first solvent as an inorganic salt or other substance capable of dissociating the cation in the first solvent.
Preferably, in the quantum dot with the surface modified with the crown ether, the crown ether is connected with the surface of the quantum dot through a sulfydryl group. Further, in the quantum dot modified with the crown ether on the surface, the crown ether is preferably mercapto crown ether, and the weight ratio of the mercapto crown ether to the quantum dot is preferably (3-5): 1-2.
Preferably, in the step of dispersing the quantum dots and the cation in the first solvent, the quantum dots and the cation are mixed in the first solvent in such a ratio that the mixing ratio of the quantum dots and the cation is (10-20) mg, (0.01-0.05) mmol. Further, after the step of dispersing the quantum dots and the cations in the first solvent, the final concentration of the quantum dots is 10-20mg/mL, so that the quantum dots are prevented from agglomerating due to excessive concentration of the quantum dots, and fluorescence quenching is prevented. Further, after the step of dispersing the quantum dots and the cation in the first solvent, the final concentration of the cation is 0.01 to 0.05 mol/mL.
Preferably, in the step of dispersing the quantum dots and the cations in the first solvent, the quantum dots and the cations are uniformly mixed at 20-35 ℃, so that the cations and the quantum dots are reacted under relatively mild conditions, and adverse effects such as partial agglomeration and the like caused by non-uniform reaction between the cations and the quantum dots due to instability of a reaction system caused by boiling or micro-boiling of the solvent at high temperature are avoided. In a specific embodiment, the quantum dots and the cations are homogeneously mixed at 20, 22, 23, 25, 26, 29, 30, 33, 35 ℃. In order to sufficiently mix the quantum dots and the cations, stirring and the like can be adopted. Further, in some embodiments, the quantum dots and the cations are stirred at 20-35 ℃ for 20-30 hours.
In embodiments of the present invention, the first solvent is a polar solvent including, but not limited to, water, alcohol, or a mixture of alcohol and water, such as in some embodiments, the first solvent is ethanol.
In summary, under the comprehensive effect of the optimized process conditions provided by the embodiments of the present invention, the nanomaterial obtained by the preparation method provided by the embodiments of the present invention has the advantages of optimal comprehensive performance, small emission half-peak width and high quantum efficiency.
Accordingly, a luminescent film, the material of the luminescent film comprising: the nano material or the nano material prepared by the preparation method.
The luminescent film provided by the embodiment of the invention comprises the nano material, is formed by complexing cations and crown ether modified on the surface of quantum dots, and has smaller emission half-peak width and good 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 smaller emission half-peak width and good quantum efficiency.
In order that the above implementation details and operations of the present invention can be clearly understood by those skilled in the art, and the advanced performance of the nanomaterial and the preparation method thereof, the light emitting thin film and the display device according to the embodiment of the present invention can be remarkably embodied, the implementation of the present invention is exemplified by the following embodiments.
Example 1
The embodiment provides a nano material, and the preparation method specifically comprises the following steps:
1. dissolving 2mmol of 2-hydroxymethyl-15-crown-5 in 10mL of N, N-dimethylformamide, adding 0.5mL of concentrated sulfuric acid while stirring, adding 2mmol of 1, 2-dithiobutane-3-carboxylic acid, heating to 100 ℃, refluxing for 1h, cleaning and drying to obtain 2-hydroxymethyl-15-crown-5 containing sulfydryl;
2. dissolving 35g of the 2-hydroxymethyl-15-crown-5 containing sulfydryl in 15mL of ethanol, adding tetramethylammonium hydroxide to adjust the pH value to 10, then adding 15mg of CdSe quantum dots, refluxing at 55 ℃ for 16h, cooling to room temperature, then cleaning with ethanol and ethyl acetate, and dispersing in methanol to prepare a CdSe quantum dot solution with the concentration of 15 mg/mL;
3. adding 0.01mmol K into the CdSe quantum dot solution+Stirring at room temperature for 25h to react the crown ether ring with K+And (3) coordinating to obtain the nano material with the structure of quantum dot-crown ether-cation-crown ether-quantum dot.
The quantum yield of the nano material prepared by the embodiment is 80% through testing;
compared with the CdSe quantum dots added in the step 2, the half-peak width of the nano-material of the embodiment is narrowed from 30nm to 24 nm.
Example 2
The embodiment provides a nano material, and the preparation method specifically comprises the following steps:
1. dissolving 1.5mmol of 2-hydroxymethyl-18-crown ether-6 in 10mL of N, N-dimethylformamide, adding 0.5mL of concentrated sulfuric acid while stirring, adding 3mmol of mercaptopropionic acid, heating to 110 ℃, refluxing for 1.5h, cleaning and drying to obtain 2-hydroxymethyl-18-crown ether-6 containing sulfydryl;
2. 45mg of the above mercapto-containing 2-hydroxymethyl-18-crown-6 are dissolved in 20mL of ethanol, tetrabutylammonium bromide is added to adjust the pH to 11, and then 20mg of CdSe are added1-xSx/CdSeyS1-yThe CdS quantum dots are refluxed for 10 to 16 hours at the temperature of 65 ℃, cooled to room temperature, cleaned by ethanol and ethyl acetate, and dispersed in methanol to prepare CdSe with the concentration of 20mg/mL1-xSx/CdSeyS1-yA CdS quantum dot solution;
to the above CdSe1-xSx/CdSeyS1-yAdding 0.03mmol Ca into the CdS quantum dot solution2+Stirring at room temperature for 30h to obtain crown ether ring and Ca2+And obtaining the nano material with the structure of quantum dot-crown ether-cation-crown ether-quantum dot.
The quantum yield of the nano material prepared by the embodiment is 90% through testing;
with CdSe added in step 2 above1-xSx/CdSeyS1-yCompared with CdS quantum dots, the half-peak width of the nano material of the embodiment is narrowed from 25nm to 20 nm.
Example 3
The embodiment provides a nano material, and the preparation method specifically comprises the following steps:
1. dissolving 2.5mmol of 2 '-hydroxy-1', 3 '-phenylene dimethylene crown ether in 10mL of N, N-dimethylformamide, adding 0.5mL of concentrated sulfuric acid while stirring, adding 4mmol of 16-mercaptohexadecanoic acid, heating to 120 ℃, refluxing for 2h, cleaning and drying to obtain 2' -hydroxy-1 ',3' -phenylene dimethylene crown ether containing sulfhydryl;
2. dissolving 30mg of the 2' -hydroxy-1 ',3' -phenylenedimethylene crown ether containing sulfydryl in 15mL of ethanol, adding tetrabutylammonium hydroxide to adjust the pH value to 13, then adding 20mg of CdSe/ZnSe/ZnS quantum dots, refluxing for 10h at 70 ℃, cooling to room temperature, cleaning with ethanol and ethyl acetate, and dispersing in methanol to prepare a CdSe/ZnSe/ZnS quantum dot solution with the concentration of 15 mg/mL;
3. adding 0.04mmol of Ba into the CdSe/ZnSe/ZnS quantum dot solution2+And stirring at room temperature for 20h, and coordinating the crown ether ring with alkali metal ions to obtain the nano material with the structure of quantum dot-crown ether-cation-crown ether-quantum dot.
The quantum yield of the nano material prepared by the embodiment is 89% through testing;
compared with the CdSe/ZnSe/ZnS quantum dots added in the step 2, the half-peak width of the nano-material of the embodiment is narrowed from 28nm to 21 nm.
Comparative example
The present comparative example provides a CdSe quantum dot without any surface modification treatment.
The quantum yield of the nanomaterial prepared in this comparative example was tested to be 70%.
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 (15)

1. A nanomaterial, comprising: the quantum dots are modified with crown ether on the surface, the cations are combined with the quantum dots through complexing the crown ether, and at least part of the cations are combined with two or more quantum dots.
2. Nanomaterial according to claim 1, characterized in that the cations comprise cations of alkali metals and/or alkaline earth metals.
3. The nanomaterial according to claim 1, wherein in the quantum dot with the surface modified with the crown ether, the crown ether is connected with the surface of the quantum dot through a mercapto group.
4. The nanomaterial of claim 3, wherein the crown ether is a mercapto crown ether, and the weight ratio of the mercapto crown ether to the quantum dots is (3-5): (1-2); and/or
In the nano material, the ratio of the quantum dots with crown ether modified on the surface to the cations is (10-20) mg (0.01-0.05) mmol.
5. The nanomaterial of any of claims 1 to 4, wherein the quantum dots comprise at least one of group II-VI compound quantum dots, group III-V compound quantum dots, and group IV-VI compound quantum dots; and/or
The quantum dots are water phase quantum dots.
6. The preparation method of the nano material is characterized by comprising the following steps of:
providing quantum dots with crown ether modified on the surfaces;
dispersing the quantum dots with the surfaces modified with crown ethers and cations in a first solvent, so that the cations are combined with the quantum dots through complexing the crown ethers, and at least part of the cations are combined with two or more quantum dots.
7. The method according to claim 6, wherein the crown ether is bonded to the surface of the quantum dot through a thiol group in the quantum dot with the surface modified with the crown ether.
8. The method according to claim 7, wherein the crown ether is a mercapto crown ether, and the weight ratio of the mercapto crown ether to the quantum dot is (3-5): (1-2).
9. The preparation method of claim 6, wherein the preparation method of the quantum dot with the surface modified with crown ether comprises the following steps: and dispersing the mercapto crown ether and the quantum dot in a second solvent, and carrying out heating reaction under an alkaline condition to enable the mercapto crown ether to be connected with the surface of the quantum dot through mercapto.
10. The production method according to claim 6, wherein in the step of dispersing the quantum dots and the cation in the first solvent, the quantum dots and the cation are mixed in the first solvent in a ratio of a mixing ratio of the quantum dots and the cation to (10-20) mg of (0.01-0.05) mmol.
11. The production method according to claim 6, wherein in the step of dispersing the quantum dot and the cation in the first solvent, the quantum dot and the cation are mixed at 20 to 35 ℃.
12. The method of any one of claims 6 to 11, wherein the cations comprise alkali metal cations and/or alkaline earth metal cations.
13. The production method according to any one of claims 6 to 11, wherein the quantum dot includes at least one of a group II-VI compound quantum dot, a group III-V compound quantum dot, and a group IV-VI compound quantum dot; and/or
The quantum dots are water phase quantum dots.
14. A luminescent film, wherein a material of the luminescent film comprises: nanomaterial according to any one of claims 1 to 5, or nanomaterial obtained by the preparation method according to any one of claims 6 to 13.
15. A display device, comprising: the light emitting film of claim 14.
CN201911394130.7A 2019-12-30 2019-12-30 Nano material and preparation method thereof, light-emitting film and display device Pending CN113122256A (en)

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Publication number Priority date Publication date Assignee Title
CN114621759A (en) * 2022-01-31 2022-06-14 福建师范大学 Green light regulation and control of perovskite quantum dot film, and preparation method and application thereof
CN114621759B (en) * 2022-01-31 2023-09-22 福建师范大学 Perovskite quantum dot film green light regulation and control and preparation method and application thereof

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