CN111384245A - Composite material, preparation method thereof and quantum dot light-emitting diode - Google Patents
Composite material, preparation method thereof and quantum dot light-emitting diode Download PDFInfo
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Abstract
The invention belongs to the field of materials, and particularly relates to a composite material, a preparation method thereof and a quantum dot light-emitting diode. The composite material comprises n-type metal oxide nanoparticles and [6,6] -phenyl-C61-butyric acid bonded on the surface of the n-type metal oxide nanoparticles. The composite material is used for an electron transmission layer of a quantum dot light-emitting diode, and can passivate the interface of a quantum dot light-emitting layer and the electron transmission layer, so that defect recombination of electric charges in the transmission process is reduced, the electron transmission efficiency is improved, and the luminous efficiency and the display performance of a device are enhanced finally.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a composite material, a preparation method thereof and a quantum dot light-emitting diode.
Background
Semiconductor materials have become increasingly known since the 18 th century after electrical phenomena have been discovered by some researchers. There are many kinds of semiconductor materials, which can be classified into an intrinsic semiconductor, a P-type semiconductor, and an N-type semiconductor according to the characteristics of carriers; they can be subdivided into elemental semiconductors, compound semiconductors, and organic semiconductors according to their chemical composition. Among the many types of semiconductor materials that are available,the transition metal oxide semiconductor material not only has the characteristic physicochemical basic performance of the transition metal oxide, but also can exert the advantages of the semiconductor material characteristics to show unique acoustic, optical, thermal, electrical and other performances. It is therefore an especially important component in functional materials. At present, ZnO, NiO, TiO2、MoO3Semiconductor materials and their applications have been the focus of research on functional materials, and such semiconductor materials are widely used in applications of semiconductor optoelectronic devices (such as solar cells and light emitting diodes). Meanwhile, in order to better highlight the effect of the oxide in the application of the semiconductor optoelectronic device, the surface modification work of the oxide is also concerned by the majority of researchers.
Quantum dot light emitting diodes (QLEDs) are expected to become a new generation of excellent display technology due to their advantages of high light emitting efficiency, high color purity, narrow light emission spectrum, adjustable emission wavelength, and the like, and the technical level of each aspect is also continuously improved. The optimization of the device structure is a large direction for improving the performance of the QLED, and how to improve the luminous efficiency of the light-emitting layer by optimizing the charge transport layer is the most important link.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a composite material, a preparation method thereof and a quantum dot light-emitting diode, and aims to solve the technical problem that the existing electron transmission material has surface defects and thus has low electron transmission efficiency.
In order to achieve the purpose, the invention adopts the following technical scheme:
the present invention provides, in one aspect, a composite material comprising n-type metal oxide nanoparticles and [6,6] -phenyl-C61-butyric acid bound to the surface of the n-type metal oxide nanoparticles.
The invention provides a composite material, which comprises n-type metal oxide nanoparticles and [6,6] -phenyl-C61-butyric acid bound on the surfaces of the n-type metal oxide nanoparticles. [6,6] -phenyl-C61-butyric acid is bidentate bonded with one or two metal atoms through carboxyl to modify the surface of the metal oxide nanoparticle, in the [6,6] -phenyl-C61-butyric acid, a carboxylate ion has a multi-electron pi bond and forms conjugation with the carboxyl after receiving an electron provided by a metal atom so as to be tightly matched with the surface of the metal oxide nanoparticle, and the other end of the [6,6] -phenyl-C61-butyric acid is an organic matter of an alkyl chain and a benzene ring, so that the solubility and the dispersibility of the metal oxide nanoparticle in a solvent can be improved, meanwhile, the [6,6] -phenyl-C61-butyric acid has high electron mobility, therefore, the [6,6] -phenyl-C61-butyric acid is modified on the surface of the n-type metal oxide nanoparticle, the surface defects of n-type metal oxide nanoparticles can be reduced, the composite material is used for an electron transmission layer of a quantum dot light-emitting diode, and the interface of a quantum dot light-emitting layer and the electron transmission layer can be passivated, so that the defect recombination of charges in the transmission process is reduced, the electron transmission efficiency is improved, and the light-emitting efficiency and the display performance of a device are finally enhanced.
The invention also provides a preparation method of the composite material, which comprises the following steps:
providing a metal salt and [6,6] -phenyl-C61-butyric acid isopropyl ester;
dissolving the metal salt in a first solvent, and carrying out heating treatment under a first alkaline condition to obtain a first solution;
dissolving the [6,6] -phenyl-C61-butyric acid isopropyl ester in a second solvent, and heating under a second alkaline condition to obtain a second solution;
mixing the first solution and the second solution to obtain a precursor solution;
and depositing the precursor solution on a substrate, and carrying out annealing treatment to obtain the composite material.
The composite material consisting of n-type metal oxide nano particles and [6,6] -phenyl-C61-butyric acid combined on the surfaces of the n-type metal oxide nano particles is prepared by a simple sol-gel method, and the preparation method has the advantages of simple process and low cost, and is suitable for large-area and large-scale preparation. The finally obtained composite material is used for an electron transmission layer of a quantum dot light-emitting diode, and can passivate the interface of a quantum dot light-emitting layer and the electron transmission layer, so that defect recombination of charges in the transmission process is reduced, the electron transmission efficiency is improved, and the luminous efficiency and the display performance of a device are finally enhanced.
Finally, the invention provides a quantum dot light-emitting diode, which comprises an anode, a cathode and a quantum dot light-emitting layer arranged between the anode and the cathode, wherein an electron transmission layer is also arranged between the cathode and the quantum dot light-emitting layer, and the material of the electron transmission layer is the composite material.
In the quantum dot light-emitting diode device provided by the invention, the specific composite material is used as the electron transmission layer, so that the interface of the quantum dot light-emitting layer and the electron transmission layer can be passivated, the defect recombination of charges in the transmission process is reduced, the electron transmission efficiency is improved, and the light-emitting efficiency and the display performance of the device are finally enhanced.
Drawings
Fig. 1 is a schematic structural diagram of a quantum dot light-emitting diode according to embodiment 4 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 one aspect, embodiments of the present invention provide a composite material including n-type metal oxide nanoparticles and [6,6] -phenyl-C61-butyric acid bound to the surface of the n-type metal oxide nanoparticles.
The composite material provided by the embodiment of the invention comprises n-type metal oxide nanoparticles and [6,6] -phenyl-C61-butyric acid bound on the surfaces of the n-type metal oxide nanoparticles. [6,6] -phenyl-C61-butyric acid is bidentate bonded with one or two metal atoms through carboxyl to modify the surface of the metal oxide nanoparticle, in the [6,6] -phenyl-C61-butyric acid, a carboxylate ion has a multi-electron pi bond and forms conjugation with the carboxyl after receiving an electron provided by a metal atom so as to be tightly matched with the surface of the metal oxide nanoparticle, and the other end of the [6,6] -phenyl-C61-butyric acid is an organic matter of an alkyl chain and a benzene ring, so that the solubility and the dispersibility of the metal oxide nanoparticle in a solvent can be improved, meanwhile, the [6,6] -phenyl-C61-butyric acid has high electron mobility, therefore, the [6,6] -phenyl-C61-butyric acid is modified on the surface of the n-type metal oxide nanoparticle, the surface defects of n-type metal oxide nanoparticles can be reduced, the composite material is used for an electron transmission layer of a quantum dot light-emitting diode, and the interface of a quantum dot light-emitting layer and the electron transmission layer can be passivated, so that the defect recombination of charges in the transmission process is reduced, the electron transmission efficiency is improved, and the light-emitting efficiency and the display performance of a device are finally enhanced.
[6,6] -Phenyl-C61-butyric Acid isopropyl Ester ([6,6] -Phenyl-C61-butyl Acid Methyl Ester, PCBM) is a fullerene derivative, which inherits the conjugated cage-shaped carbon molecular structure of fullerene, so that the fullerene has excellent electron holding capacity and high electron mobility. The fullerene is introduced with a benzene ring, a carbon chain and an ester group, so that the fullerene has better solubility. PCBM is hydrolyzed to [6,6] -Phenyl-C61-butyric acid ([6,6] -Phenyl-C61-butyricAcid, PCBA) under alkaline conditions. PCBA can be subjected to bidentate bonding with one or two metal atoms through carboxyl, so that the PCBA is modified on the surface of the metal oxide nanoparticles, the solubility and the dispersity of the metal oxide nanoparticles in a solvent can be improved, and meanwhile [6,6] -phenyl-C61-butyric acid has high electron mobility, so that the [6,6] -phenyl-C61-butyric acid is modified on the surface of the n-type metal oxide nanoparticles, and the surface defects of the n-type metal oxide nanoparticles can be reduced.
Further, the composite material is used as an electron transport material of a quantum dot light emitting diode.
Further, in the composite material according to the embodiment of the present invention, the n-type metal oxide nanoparticles are at least one selected from the group consisting of zinc oxide nanoparticles, tin oxide nanoparticles, titanium oxide nanoparticles, and zirconium oxide nanoparticles.
More preferably, the molar ratio of the [6,6] -phenyl-C61-butyric acid to the metal element in the n-type metal oxide nanoparticles is (1-2): 1. within the proportion range, PCBA can be well modified on the surface of the metal oxide nano-particles.
On the other hand, the embodiment of the invention also provides a preparation method of the composite material, which comprises the following steps:
s01: providing a metal salt and [6,6] -phenyl-C61-butyric acid isopropyl ester;
s02: dissolving the metal salt in a first solvent, and carrying out heating treatment under a first alkaline condition to obtain a first solution;
s03: dissolving the [6,6] -phenyl-C61-butyric acid isopropyl ester in a second solvent, and heating under a second alkaline condition to obtain a second solution;
s04: mixing the first solution and the second solution to obtain a precursor solution;
s05: and depositing the precursor solution on a substrate, and carrying out annealing treatment to obtain the composite material.
The embodiment of the invention prepares the composite material consisting of n-type metal oxide nano particles and [6,6] -phenyl-C61-butyric acid combined on the surfaces of the n-type metal oxide nano particles by a simple sol-gel method, and the preparation method has the advantages of simple process and low cost, and is suitable for large-area and large-scale preparation. The finally obtained composite material is used for an electron transmission layer of a quantum dot light-emitting diode, and can passivate the interface of a quantum dot light-emitting layer and the electron transmission layer, so that defect recombination of charges in the transmission process is reduced, the electron transmission efficiency is improved, and the luminous efficiency and the display performance of a device are finally enhanced.
Further, in step S01: the metal salt is at least one selected from zinc salt, tin salt, titanium salt and zirconium salt. For example, the zinc salt is a soluble inorganic zinc salt or an organic zinc salt, such as zinc acetate, zinc nitrate, zinc chloride, zinc sulfate, zinc acetate dihydrate, and the like, but not limited thereto. The tin salt is a soluble inorganic tin salt or an organic tin salt, and is not limited thereto, such as tin nitrate, tin chloride, tin sulfate, tin methane sulfonate, tin ethane sulfonate, tin propane sulfonate, and the like. The titanium salt is soluble inorganic titanium salt or organic titanium salt, such as titanium acetate, titanium nitrate, titanium chloride, titanium sulfate, titanium bromide, etc., but not limited thereto. The zirconium salt is a soluble inorganic zirconium salt or an organic zirconium salt, such as zirconium acetate, zirconium nitrate, zirconium chloride, zirconium sulfate, etc., but not limited thereto.
Further, in step S02: the temperature for heating treatment under the first alkaline condition is 60-90 ℃; the first solvent is selected from at least one of methanol, ethanol, propanol, acetone, butanol, pentanol, hexanol, ethylene glycol methyl ether and propylene glycol methyl ether. The pH of the first alkaline condition is 12-13, and the alkaline condition is provided by alkaline solution, such as ammonia, potassium hydroxide, sodium hydroxide, lithium hydroxide, ethanolamine, ethylene glycol, diethanolamine, triethanolamine, ethylenediamine, etc., but not limited thereto.
Specifically, in the embodiment of the invention, metal salt reacts with alkali liquor to generate hydroxide (M (OH) x), and M (OH) x undergoes polycondensation reaction and is dehydrated to generate MOx. Therefore, the dosage of the alkali liquor is specifically adjusted according to the valence state of the metal ions. Such as when the metal ion is +2 (Zn)2+) The mol ratio of the alkali liquor to the metal ions is 2: 1, so that the molar ratio of the alkali liquor to the metal ions is kept between 1.8 and 2.5: 1, oxide nanoparticles can be generated. Such as when the metal ion is +4 (Ti)4+、Sn4+、Zr4+) The mol ratio of the alkali liquor to the metal ions is 4: 1, so that the molar ratio of the alkali liquor to the metal ions is kept between (3.5 and 4.5): 1, oxide nanoparticles can be generated. When the molar ratio of the alkali liquor to the metal ions is less than 1.8: 1 or 3.5: 1, pH<When 12 hours, alkali liquor is insufficient, metal salt is excessive, and reaction is insufficient; greater than 2.5: 1 or 4.5: 1, pH>At 13, too high a pH will result in a slow hydrolysis and polycondensation rate of the sol in the system. Optimally, the molar ratio of the alkali liquor to the metal ions is kept between 1.8 and 4.5: 1.
further, in step S03: the temperature for heating treatment under the second alkaline condition is 60-90 ℃; the second solvent is selected from at least one of methanol, ethanol, propanol, acetone, butanol, pentanol, hexanol, ethylene glycol methyl ether and propylene glycol methyl ether. The second alkaline condition has a pH of 12-13, and the alkaline condition is provided by alkaline solution, such as ammonia, potassium hydroxide, sodium hydroxide, lithium hydroxide, ethanolamine, ethylene glycol, diethanolamine, triethanolamine, ethylenediamine, etc., but not limited thereto.
The molar ratio of the alkali liquor to the PCBM is (1-1.5): at 1, PCBM may be hydrolyzed to PCBA. When the molar ratio is small, the PCBM is excessive and can not be hydrolyzed into PCBA fully; when the molar ratio is too large, the alkali solution is excessive, and the rate of the hydrolysis reaction is slowed down. Optimally, the molar ratio of the alkali liquor to the PCBM is kept to be (1-1.5): 1.
further, in step S04: the molar ratio of PCBA to metal ions is (1-2): mixing the first solution and the second solution, so that the PCBA can be well modified on the surface of the oxide. According to theoretical calculations, it is precisely when the molar ratio of PCBA to metal ion is 1: 1. When the molar ratio is small, the concentration of the PCBA is smaller and smaller along with the progress of the raw material reaction, the counter strain is slow, and the PCBA cannot be completely adsorbed on the surface of the nano-particles; when the molar ratio is too large, on the one hand the reaction proceeds too fast and, on the other hand, upon high temperature annealing, too much PCBA is removed and may remain. Optimally, the molar ratio of PCBA to metal ions is kept between (1 and 2): 1.
further, in step S05, the temperature of the annealing treatment is 300-350 ℃. In order to remove the solvent and make the material more crystalline, the annealing temperature is selected to be 300-350 ℃.
Finally, the embodiment of the invention provides a quantum dot light emitting diode, which comprises an anode, a cathode and a quantum dot light emitting layer arranged between the anode and the cathode, wherein an electron transmission layer is also arranged between the cathode and the quantum dot light emitting layer, and the material of the electron transmission layer is the composite material of the embodiment of the invention.
In the quantum dot light-emitting diode device provided by the embodiment of the invention, the specific composite material is used as the electron transport layer, so that the interface of the quantum dot light-emitting layer and the electron transport layer can be passivated, the defect recombination of charges in the transmission process is reduced, the electron transport efficiency is improved, and the light-emitting efficiency and the display performance of the device are finally enhanced.
In one embodiment, a method for manufacturing a QLED device includes:
a: firstly, growing a hole transport layer on an ITO substrate;
b: then depositing quantum dots on the hole injection layer;
c: and finally, depositing an electron transmission layer on the quantum dot light-emitting layer, and evaporating a cathode on the electron transmission layer to obtain the light-emitting diode.
Wherein the material of the electron transport layer is PCBA modified metal oxide nano material.
The hole transport layer of the present invention can be made of hole transport materials that are conventional in the art, including but not limited to TFB, PVK, Poly-TPD, TCTA, CBP, PEDOT: PSS, etc., or any combination thereof, as well as other high performance hole transport materials. Hole transport layer: placing the ITO substrate on a spin coater, and spin-coating a prepared solution of a hole transport material to form a film; the film thickness is controlled by adjusting the concentration of the solution, the spin-coating speed and the spin-coating time, and then a thermal annealing process is performed at an appropriate temperature.
In the preparation method of the device, the quantum dots of the quantum dot light-emitting layer are one of red, green and blue. Can be at least one of CdS, CdSe, CdTe, ZnSe, ZnTe, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs, InP, InSb, AlAs, AlP, CuInS, CuInSe and various core-shell structure quantum dots or alloy structure quantum dots. Then the quantum dots can be any one of the three common red, green and blue quantum dots or other yellow light, and the quantum dots can be cadmium-containing or cadmium-free. The quantum dot light emitting layer of the material has the characteristics of wide and continuous excitation spectrum distribution, high emission spectrum stability and the like. Preparing a quantum dot light-emitting layer: and (3) placing the substrate on which the hole transport layer is coated on a spin coater, coating the prepared luminescent material solution with a certain concentration on the spin coater to form a film, controlling the thickness of the luminescent layer to be about 20-60 nm by adjusting the concentration of the solution, the spin coating speed and the spin coating time, and drying at a proper temperature.
The electron transport layer is a PCBA modified metal oxide nano material in the embodiment of the invention: placing a substrate on which a quantum dot light emitting layer is spin-coated on a spin coater, spin-coating a PCBA modified metal oxide nano material precursor solution with a certain concentration to form a film, firstly controlling the thickness of the quantum dot light emitting layer to be about 20-60 nm by adjusting the concentration of the solution, the spin-coating speed (preferably, the rotating speed is 2000-6000 rpm) and the spin-coating time, and then annealing the PCBA modified metal oxide nano material precursor solution at the temperature of 300-350 ℃ (such as 320 ℃) to form the film. The step can be annealing in air or in nitrogen atmosphere, and the annealing atmosphere is selected according to actual needs.
And then, the substrate deposited with the functional layers is placed in an evaporation bin, and a layer of 15-30nm metal silver or aluminum is thermally evaporated through a mask plate to serve as a cathode, or a nano Ag wire or a Cu wire is used, so that a carrier can be smoothly injected due to the small resistance.
Further, the obtained QLED is subjected to a packaging process, and the packaging process may be performed by a common machine or by a manual method. Preferably, the oxygen content and the water content in the packaging treatment environment are both lower than 0.1ppm so as to ensure the stability of the device.
The invention is described in further detail with reference to a part of the test results, which are described in detail below with reference to specific examples.
Example 1
The details will be described by taking titanium acetate, ethanol, potassium hydroxide, and PCBM as examples.
1) An appropriate amount of titanium acetate was added to 50ml of ethanol to form a solution having a total concentration of 0.5M. Dissolved at 70 ℃ with stirring. Adding a solution of potassium hydroxide dissolved in 10ml of ethanol (the molar ratio of potassium hydroxide to titanium ions is 3.5-4.5: 1, the pH value is 12), and continuing stirring at 70 ℃ for 4 hours to form a precursor solution A.
2) Dispersing a proper amount of PCBM into 10ml of ethanol, adding a solution of potassium hydroxide dissolved in 10ml of ethanol (the molar ratio of sodium hydroxide to PCBM is 1-1.5: pH 12) at 70 ℃ for 2h to form a PCBA solution. (molar ratio: PCBA: Ti)4+＝1～2:1)。
3) And (3) uniformly mixing the precursor solution A and the PCBA solution, and continuing stirring at 70 ℃ for 2h to form a precursor solution B.
4) Subsequently, after the solution was cooled, the treated ITO was spin-coated with a spin coater and annealed at 350 ℃.
Example 2
The details will be described by taking zinc nitrate, methanol, ethanolamine, and PCBM as examples.
1) An appropriate amount of zinc nitrate was added to 50ml of methanol to form a solution having a total concentration of 0.5M. Dissolved at 60 ℃ with stirring. Adding a solution of ethanolamine dissolved in 10ml of methanol (the molar ratio of ethanolamine to zinc ions is 1.8-2.5: 1, the pH value is 12), and continuing stirring at 60 ℃ for 4h to form a precursor solution A.
2) Dispersing a proper amount of PCBM into 10ml of methanol, adding a solution of ethanolamine dissolved in 10ml of methanol (the molar ratio of ethanolamine to PCBM is 1-1.5: pH 12) at 60 ℃ for 2h to form a PCBA solution. (molar ratio: PCBA: Zn)2+＝1～2:1)。
3) And (3) uniformly mixing the precursor solution A and the PCBA solution, and continuing stirring at 60 ℃ for 2h to form a precursor solution B.
4) Subsequently, after the solution was cooled, the treated ITO was spin-coated with a spin coater and annealed at 350 ℃.
Example 3
The details will be described by taking tin chloride, ethylene glycol monomethyl ether, lithium hydroxide, and PCBM as examples.
1) An appropriate amount of tin chloride was added to 50ml of ethylene glycol methyl ether to form a solution having a total concentration of 0.5M. Dissolved at 60 ℃ with stirring. Adding a solution of lithium hydroxide dissolved in 10ml of ethylene glycol monomethyl ether (the molar ratio of lithium hydroxide to tin ions is 3.5-4.5: 1, and the pH value is 12), and continuously stirring at 80 ℃ for 4 hours to form a precursor solution A.
2) Dispersing a proper amount of PCBM into 10ml of ethylene glycol monomethyl ether, adding a solution of lithium hydroxide dissolved in 10ml of ethylene glycol monomethyl ether (the molar ratio of the lithium hydroxide to the PCBM is 1-1.5: pH 12) was added to the solution, and stirred at 80 ℃ for 2h to form a PCBA solution. (molar ratio: PCBA: Sn)4+＝1～2:1)。
3) And (3) uniformly mixing the precursor solution A and the PCBA solution, and continuing stirring at 80 ℃ for 2h to form a precursor solution B.
4) Subsequently, after the solution was cooled, the treated ITO was spin-coated with a spin coater and annealed at 350 ℃.
Example 4
As shown in fig. 1, a schematic structural diagram of a quantum dot light emitting diode, the method for manufacturing the device includes the following steps:
a: firstly, growing a hole transport layer on an ITO substrate;
b: then depositing a quantum dot light-emitting layer on the hole transport layer;
c: and finally, depositing an electron transport layer on the quantum dot light-emitting layer, wherein the electron transport layer is made of PCBA modified oxide nanoparticles, and evaporating a cathode on the electron transport layer to obtain the light-emitting diode.
Fig. 1 is a schematic structural diagram of a QLED device according to the present invention, and the QLED device sequentially includes a substrate 1, an anode 2, a hole transport layer 3, a quantum dot light emitting layer 4, an electron transport layer 5, and a cathode 6 from bottom to top. The substrate 1 is made of a glass sheet, the anode 2 is made of an ITO (indium tin oxide) substrate, the hole transport layer 3 is made of TFB, the electron transport layer 5 is made of PCBA modified oxide nano material, and the cathode 6 is made of Al.
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 (10)
1. A composite material comprising n-type metal oxide nanoparticles and [6,6] -phenyl-C61-butyric acid bound to the surface of the n-type metal oxide nanoparticles.
2. The composite material of claim 1, wherein the composite material is used as an electron transport material for a quantum dot light emitting diode.
3. The composite material of claim 1, wherein the n-type metal oxide nanoparticles are selected from at least one of zinc oxide nanoparticles, tin oxide nanoparticles, titanium oxide nanoparticles, and zirconium oxide nanoparticles.
4. The composite material of claim 1, wherein the molar ratio of [6,6] -phenyl-C61-butyric acid to the metal element in the n-type metal oxide nanoparticles in the composite material is (1-2): 1.
5. the preparation method of the composite material is characterized by comprising the following steps:
providing a metal salt and [6,6] -phenyl-C61-butyric acid isopropyl ester;
dissolving the metal salt in a first solvent, and carrying out heating treatment under a first alkaline condition to obtain a first solution;
dissolving the [6,6] -phenyl-C61-butyric acid isopropyl ester in a second solvent, and heating under a second alkaline condition to obtain a second solution;
mixing the first solution and the second solution to obtain a precursor solution;
and depositing the precursor solution on a substrate, and carrying out annealing treatment to obtain the composite material.
6. The method according to claim 5, wherein the temperature at which the heat treatment is performed under the first alkaline condition is 60 to 90 ℃; and/or
The temperature of the heat treatment under the second alkaline condition is 60 to 90 ℃.
7. The method as claimed in claim 5, wherein the annealing temperature is 300-350 ℃.
8. The method of claim 5, wherein the first alkaline condition has a pH of 12 to 13; and/or
The second alkaline condition has a pH of 12 to 13.
9. The production method according to any one of claims 5 to 8, wherein the metal salt is at least one selected from the group consisting of zinc salts, tin salts, titanium salts, and zirconium salts; and/or
The first solvent and the second solvent are respectively and independently selected from at least one of methanol, ethanol, propanol, acetone, butanol, pentanol, hexanol, ethylene glycol methyl ether and propylene glycol methyl ether.
10. A quantum dot light-emitting diode, comprising an anode, a cathode and a quantum dot light-emitting layer arranged between the anode and the cathode, wherein an electron transport layer is arranged between the cathode and the quantum dot light-emitting layer, and the electron transport layer is made of the composite material of any one of claims 1 to 4.
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