CN113809248B - 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 PDF

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CN113809248B
CN113809248B CN202010546265.7A CN202010546265A CN113809248B CN 113809248 B CN113809248 B CN 113809248B CN 202010546265 A CN202010546265 A CN 202010546265A CN 113809248 B CN113809248 B CN 113809248B
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composite material
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organic semiconductor
semiconductor material
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CN113809248A (en
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聂志文
张旋宇
刘文勇
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TCL Technology Group Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H10K50/155—Hole transporting layers comprising dopants
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/326—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising gallium
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/381—Metal complexes comprising a group IIB metal element, e.g. comprising cadmium, mercury or zinc
    • H—ELECTRICITY
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    • H10K85/60—Organic compounds having low molecular weight

Abstract

The invention belongs to the technical field of luminescent device materials, and particularly relates to a composite material, a preparation method thereof and a quantum dot light emitting diode. The composite material comprises an organic semiconductor material, an organic molecule and a metal ion, wherein the organic molecule has a structure shown in the following formula I, and a carboxyl group on the organic molecule is coordinated with the metal ion and is connected to the organic semiconductor material through the metal ion; r in formula I 1 Is- (CH) 2 ) n -n is an integer greater than or equal to 1. The composite material shortens the molecular distance of the organic semiconductor material, enhances the intermolecular conjugated resonance effect, improves the intermolecular conduction capacity of holes in the organic semiconductor material, thereby improving the hole mobility, and simultaneously can effectively improve the crystallinity of the composite material through the doping of the organic molecules, thereby reducing the resistance of the composite material and further enhancing the hole transmission capacity of the composite material.

Description

Composite material, preparation method thereof and quantum dot light emitting diode
Technical Field
The invention belongs to the technical field of luminescent device materials, and particularly relates to a composite material, a preparation method thereof and a quantum dot light emitting diode.
Background
Quantum Dots (QDs), also known as semiconductor nanocrystals, typically consist of group II-VI or III-V elements with particle sizes less than or near the exciton bohr radius. The development of the current quantum dot synthesis technology is significantly broken through, wherein the research of II-VI group quantum dots represented by CdSe is intended to be perfect, such as: the photoluminescence efficiency is close to 100%, the peak width is as narrow as 20-30 nm, and the device efficiency and the device service life of the red-green quantum dot are close to the commercial application requirements. Because the high-quality quantum dots are all prepared by adopting a full-solution synthesis method, the quantum dots are very suitable for being prepared into films by adopting solution processing modes such as spin coating, printing and the like. Quantum dot light emitting diodes (QLEDs) using quantum dot materials as quantum dot light emitting layers are expected to be powerful competitors to the next generation of new display technologies.
However, the electroluminescent device of the quantum dot still has the problems of low efficiency, short service life and the like, and the device for constructing the high-efficiency QLED is usually prepared by a solution method, and an organic semiconductor material is usually used as a Hole Transport Layer (HTL) of the QLED. The organic semiconductor material generally has the problems of low carrier mobility, large resistance and poor matching between HOMO energy level and quantum dots, so that hole injection is difficult, interface potential barrier of a hole transmission layer/a quantum dot light-emitting layer is large, and charge interfaces accumulate much, thereby having adverse effects on the efficiency and service life of the QLED device.
Accordingly, the prior art is in need of improvement.
Disclosure of Invention
An object of the present invention is to overcome the above-mentioned drawbacks of the prior art, and to provide a composite material and a method for preparing the same, which aims to solve the technical problem of non-ideal hole transport properties of organic semiconductor materials.
In order to achieve the above purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a composite material, which comprises an organic semiconductor material, an organic molecule and a metal ion, wherein the organic molecule has a structure shown in the following formula I, and a carboxyl group on the organic molecule is coordinated with the metal ion and is connected to the organic semiconductor material through the metal ion;
wherein R is 1 Is- (CH) 2 ) n -n is an integer greater than or equal to 1.
The composite material provided by the invention comprises an organic semiconductor material, and organic molecules and metal ions, wherein the organic molecules are shown in a formula I and are connected with the organic semiconductor material, and carboxyl groups of the organic molecules are coordinated with the metal ions, and the metal ions are simultaneously coordinated with functional groups of the organic semiconductor material, so that the organic molecules are connected with the organic semiconductor material, and as the organic molecules are dicarboxylic acid small molecules, the organic molecules can be respectively connected with the organic semiconductor material through carboxyl groups at two ends, the organic semiconductor materials are connected with each other, the molecular distance of the organic semiconductor can be shortened, the intermolecular conjugated resonance effect is enhanced, the intermolecular conduction capability of holes in the organic semiconductor material is improved, the hole mobility is improved, the crystallinity of the composite material can be effectively improved through doping of the organic molecules, the resistance of the composite material is reduced, and the hole transmission capability of the composite material is further enhanced.
In another aspect, the present invention provides a method for preparing a composite material, comprising the steps of:
providing an organic semiconductor material, a dicarboxylic acid monoester organic compound shown in the following formula II and a metal ion precursor;
dissolving the organic semiconductor material, the dicarboxylic acid monoester organic matter and the metal ion precursor in a nonpolar solvent, and performing heating treatment to obtain a mixed solution;
carrying out solid-liquid separation on the mixed solution to obtain the composite material;
wherein R is 1 Is- (CH) 2 ) n -，R 2 is-O (CH) 2 ) m CH 3 N is an integer greater than or equal to 1, and m is an integer greater than or equal to 0.
According to the preparation method of the composite material, the organic semiconductor material, the dicarboxylic acid monoester organic matters shown in the formula II and the metal ion precursors are dissolved in the nonpolar solvent for heating treatment, the dicarboxylic acid monoester organic matters shown in the formula II are hydrolyzed to form organic molecules shown in the formula I, and the metal ion precursors are dissolved to form metal ions, so that in the composite material obtained by subsequent solid-liquid separation, the organic molecules can coordinate with the metal ions through two end carboxyl groups and coordinate with the organic semiconductor material by utilizing the metal ions, the organic molecules and the organic semiconductor material are mutually connected, the molecular distance of the organic semiconductor material is shortened, the intermolecular conjugated resonance effect is enhanced, the intermolecular conductivity is improved, the hole mobility is improved, meanwhile, the crystallinity of the composite material can be effectively improved by doping the organic molecules, the resistance of the composite material is reduced, and the hole transmission capability of the composite material is further enhanced.
Another object of the present invention is to provide a quantum dot light emitting diode, which aims to solve the technical problem of non-ideal hole transmission performance of the quantum dot light emitting diode. In order to achieve the above purpose, the invention adopts the following technical scheme:
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 a hole transport layer is arranged between the anode and the quantum dot light emitting layer, and the hole transport layer consists of the composite material or the composite material obtained by the preparation method of the composite material.
The hole transmission layer in the quantum dot light-emitting diode provided by the invention is composed of the special composite material or the special composite material prepared by the preparation method, the composite material has good electrical property of a crystal structure, the hole mobility can be improved, the hole injection is enhanced, the HOMO energy level of the composite material is well matched with that of the quantum dot light-emitting layer, the effective recombination of electrons and holes in the quantum dot light-emitting layer can be promoted, the charge accumulation of the interface of the quantum dot light-emitting layer and the hole transmission layer is reduced, and the light-emitting efficiency and the service life of the device are improved.
Drawings
FIG. 1 is a flow chart of a method for preparing a composite material according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a quantum dot light emitting diode according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In one aspect, an embodiment of the present invention provides a composite material, where the composite material includes an organic semiconductor material, an organic molecule, and a metal ion, the organic molecule has a structure shown in formula I below, and a carboxyl group on the organic molecule coordinates with the metal ion and is connected to the organic semiconductor material through the metal ion;
wherein R is 1 Is- (CH) 2 ) n -n is an integer greater than or equal to 1.
The organic semiconductor material comprises an organic semiconductor material, and organic molecules and metal ions, wherein the organic molecules are shown in a formula I and are connected with the organic semiconductor material, carboxyl groups of the organic molecules are coordinated with the metal ions, and the metal ions are coordinated with functional groups of the organic semiconductor material at the same time, so that the organic molecules are connected with the organic semiconductor material, and because the organic molecules are dicarboxylic acid micromolecules, the organic molecules can be connected with the two organic semiconductor materials through carboxyl groups, the organic semiconductor materials are connected with each other, the molecular distance between the organic semiconductor materials can be shortened, the intermolecular conjugated resonance effect is enhanced, the intermolecular conduction capacity of holes in the organic semiconductor material is improved, the hole mobility is improved, the crystallinity of the composite material can be effectively improved through doping of the organic molecules, the resistance of the composite material is reduced, and the hole transmission capacity of the composite material is further enhanced.
In one embodiment, R of the organic molecule 1 Is- (CH) 2 ) n -, wherein n=2 to 20; an unbranched linear carbon chain R in the number range of carbon atoms 1 The organic semiconductor material can be better connected. Specifically, n=4 to 9.
In one embodiment, the mass ratio of the organic molecules to the organic semiconductor material is (0.1-1): 30; the organic molecules shown in the formula I are doped in the mass ratio range, so that the hole transport performance of the composite material can be better improved. Specifically, the mass ratio of the organic molecules to the organic semiconductor material is 1:30.
in one embodiment, the molar ratio of the organic molecule to the metal ion is (1-3): 1. within this molar ratio range, the organic molecules and the metal ions can coordinate more effectively.
In one embodiment, the organic semiconductor material is an organic hole transport material, further, the organic semiconductor material is selected from organic hole transport materials containing amine groups, and the functional group amine groups can coordinate with metal ions better, so as to be connected with the organic molecules. Specifically, the organic semiconductor material is selected from one or more of poly (9, 9-dioctyl-fluorene-co-N- (4-butylphenyl) -diphenylamine) (TFB), polyarylamine, poly (N-vinylcarbazole), polyaniline, polypyrrole, N ' -tetrakis (4-methoxyphenyl) -benzidine (TPD), 4-bis [ N- (1-naphthyl) -N-phenyl-amino ] biphenyl (α -NPD), 4',4 "-tris [ phenyl (m-tolyl) amino ] triphenylamine (m-MTDATA), 4',4" -tris (N-carbazolyl) -triphenylamine (TCTA), and 1, 1-bis [ (di-4-tolylamino) phenylcyclohexane (TAPC); the metal ion is selected from one or more of zinc ion, titanium ion, aluminum ion, indium ion, tin ion, zirconium ion and gallium ion. The metal ions can coordinate with carboxyl groups of the organic molecules shown in the formula I and functional groups of amino groups in the organic hole transport material, and two carboxyl groups in the formula I can coordinate with metal ions, so that one organic molecule can be connected with two organic hole transport material molecules, and the organic hole transport materials are connected with each other.
In one embodiment, the composite material of the present embodiment is composed of the above-described organic semiconductor material, organic molecules, and metal ions.
On the other hand, the embodiment of the invention also provides a preparation method of the composite material, as shown in fig. 1, comprising the following steps:
s01: providing an organic semiconductor material, a dicarboxylic acid monoester organic substance shown in a formula II and a metal ion precursor;
s02: dissolving the organic semiconductor material, the dicarboxylic acid monoester organic matter and the metal ion precursor in a nonpolar solvent, and performing heating treatment to obtain a mixed solution;
s03: carrying out solid-liquid separation on the mixed solution to obtain the composite material;
wherein R is 1 Is- (CH) 2 ) n -，R 2 is-O (CH) 2 ) m CH 3 N is an integer greater than or equal to 1, and m is an integer greater than or equal to 0.
According to the preparation method of the composite material, disclosed by the embodiment of the invention, the organic semiconductor material, the dicarboxylic acid monoester organic matters shown in the formula II and the metal ion precursors are dissolved in the nonpolar solvent for heating treatment, the dicarboxylic acid monoester organic matters shown in the formula II are hydrolyzed to form organic molecules shown in the formula I, and the metal ion precursors are dissolved to form metal ions, so that in the composite material obtained by subsequent solid-liquid separation, the organic molecules coordinate with the metal ions through carboxyl groups and utilize the metal ions to coordinate with functional groups of the organic semiconductor material, so that the organic molecules are connected with the organic semiconductor material, the molecular distance of the organic semiconductor material is shortened, the conjugated resonance effect among molecules is enhanced, the intermolecular conductivity is improved, the hole mobility is improved, and meanwhile, the crystallinity of the composite material can be effectively improved through doping of the organic molecules, and the resistance of the composite material is reduced, and the hole transmission capability of the composite material is further enhanced.
In one embodiment, the composite material provided by the embodiment of the invention is obtained by the preparation method, and comprises an organic semiconductor material, an organic molecule shown in a formula I and a metal ion, wherein the organic molecule is connected with the organic semiconductor material, and two carboxyl groups on the organic molecule are connected with the organic semiconductor material through coordination with the metal ion; the specific preparation steps are shown above.
In the above step S01, a dicarboxylic acid monoester organic compound represented by formula II, R 1 N=2 to 20; r is R 2 M=2 to 20. An unbranched linear chain R in the carbon number range 1 The organic semiconductor material can be better connected. An unbranched linear chain R in the carbon number range 2 The organic molecules forming the bipolar group of formula I can be better hydrolyzed. The organic semiconductor material is an organic hole transport material, in particular, the organic hole transport material is selected from poly (9, 9-dioctyl-fluorene-co-N- (4-butylphenyl) -diphenylamine), polyarylamine, poly (N-vinylcarbazole), polyaniline, polypyrrole, N, N, N ', N' -tetra (4-methoxyphenyl) -benzidine, 4-bis [ N- (1-naphthyl) -N-phenyl-amino]Biphenyl, 4' -tris [ phenyl (m-tolyl) amino group]One or more of triphenylamine, 4',4 "-tris (N-carbazolyl) -triphenylamine, and 1, 1-bis [ (di-4-tolylamino) phenylcyclohexane; the metal ion precursor is selected from one or more of zinc ion precursor, titanium ion precursor, aluminum ion precursor, indium ion precursor, tin ion precursor, zirconium ion precursor and gallium ion precursor. The zinc ion precursor includes: at least one of dimethyl zinc, diethyl zinc, zinc acetate, zinc acetylacetonate, zinc iodide, zinc bromide, zinc chloride, zinc fluoride, zinc carbonate, zinc cyanide, zinc nitrate, zinc oxide, zinc peroxide, zinc perchlorate, zinc sulfate, zinc oleate, zinc stearate, and the like, but is not limited thereto. The titanium ion precursor includes: titanium oxysulfate, titanium acetate, titanium tetrachloride, titanium tetrabromide, titanium trichloride, titanium triisopropoxide chloride, titanium tetrachloride bis (tetrahydrofuran) and bis (mercaptocyclopentane) titanium tetrachloride, etcBut is not limited thereto. The aluminum ion precursor includes: at least one of aluminum phosphate, aluminum acetate, aluminum acetylacetonate, aluminum iodide (aluminum iodide), aluminum bromide, aluminum chloride, aluminum fluoride, aluminum carbonate, aluminum cyanide, aluminum nitrate, aluminum oxide, aluminum peroxide, aluminum sulfate (aluminum sulfate), aluminum oleate, aluminum stearate, aluminum tetradecanoate, aluminum hexadecanoate, and the like, but not limited thereto. The indium ion precursor includes: at least one of indium phosphate, indium acetate, indium acetylacetonate, indium iodide, indium bromide, indium chloride, indium fluoride, indium carbonate, indium cyanide, indium nitrate, indium oxide, indium peroxide, indium sulfate, indium oleate, indium stearate, indium myristate, indium palmitate, and the like, but is not limited thereto. The tin ion precursor includes: at least one of stannous acetate, stannous tetrachloride, stannous chloride, stannous oxalate, triethyltin bromide, tin stearate, tin stannate, tin iodide, tin methanesulfonate, tin fluorophosphate, tin sulfate, tin ethoxide, and the like, but is not limited thereto. The zirconium ion precursor comprises: at least one of zirconium acetate, zirconium acetylacetonate, zirconium chloride, zirconium bromide, zirconium nitrate, zirconium sulfate, zirconium carbonate, and the like, but is not limited thereto. The gallium ion precursor comprises: at least one of gallium phosphate, gallium acetate, gallium acetylacetonate, gallium iodide, gallium bromide, gallium chloride, gallium fluoride, gallium carbonate, gallium cyanide, gallium nitrate, gallium oxide, gallium peroxide, gallium sulfate, gallium oleate, gallium stearate, gallium tetradecanoate, gallium hexadecanoate, and the like, but is not limited thereto.
In the step S02, the organic semiconductor material, the dicarboxylic acid monoester organic matter and the metal ion precursor are heated and dissolved in a nonpolar solvent to obtain a mixed solution, and the dicarboxylic acid monoester organic matter is hydrolyzed to form the organic molecule of the bipolar group shown in the formula I, wherein the heating treatment conditions include: the temperature is 60-120 ℃ and the time is 30 min-4 h, and the dicarboxylic monoester organic matters can be hydrolyzed better under the conditions. For example, the mixed solution is a fatty acid solution of monomethyl suberate and zinc acetate, and after thermal hydrolysis, monomethyl suberate is converted to suberic acid, which is then coordinated to the metal ion. Wherein the nonpolar solvent comprises one or more of chloroform, chlorobenzene, n-hexane, n-octane, n-heptane and toluene.
In one embodiment, the mass ratio of the dicarboxylic acid monoester organic matter to the organic semiconductor material added is (0.1 to 1): 30; the hole transport property of the composite material can be better improved within the mass ratio range. Further, the molar ratio of the dicarboxylic acid monoester organic matter added to the metal ion precursor is (1-3): 1.
in the step S03, the step of solid-liquid separation includes annealing crystallization treatment, for example, the step of solid-liquid separation includes annealing crystallization at a temperature of 140 to 160 ℃, and the further annealing time is 20 to 40 minutes. In one embodiment, in order to obtain the composite film, the mixed solution is deposited on a substrate and subjected to annealing crystallization treatment, so as to obtain a composite film layer, which can be used as a hole transport film layer.
The film layer of the composite material obtained after annealing can improve the film forming crystallinity of the composite material, thereby improving hole transmission. If the conventional hole transport layer HTL is not doped with any other material, when the QLED device is manufactured, the HTL is deposited on the hole injection layer HIL and then is subjected to heating treatment to complete the crystallization reaction of the HTL film layer, and the resistance of the film is larger in the crystallization process of the HTL made of the organic semiconductor material, so that the hole transport is not facilitated. By adopting the small molecule doped organic semiconductor material of the bipolar group, the problem of HTL crystallinity can be effectively improved, and the formed composite material can be used: organic semiconductor material-metal ion-structural representation of organic molecule-metal ion-organic semiconductor material of formula I.
For the organic semiconductor material molecules, the organic semiconductor material molecules are in a chain structure, larger branched chains exist in the repeated structure, the molecules are preferentially expanded transversely when crystallized, the branched chains are large in steric hindrance in the longitudinal direction, and the molecular chains are folded and move in the crystallization process, so that the space between the molecules is further increased (like a plurality of bent lines, the occupied space is far larger than a plurality of overlapped straight lines) due to the lack of constraint of molecular forces in the longitudinal direction. In the composite material obtained by the preparation method, after organic molecules shown in the formula I are doped, the organic semiconductor materials can be better connected in a chain structure, so that the distance between adjacent organic semiconductor materials is further reduced, the intermolecular conjugated resonance effect can be enhanced, the intermolecular conductivity is improved, and the hole mobility is improved.
The embodiment of the invention also provides an application of the composite material or the composite material obtained by the preparation method of the composite material as a hole transport material. The HOMO energy level of the composite material provided by the embodiment of the invention is well matched with the quantum dot luminescent layer, so that the resistance is reduced, the hole mobility is improved, the conduction and recombination capacity of holes at interfaces can be improved, and the transmission efficiency of carriers between interfaces is improved.
Finally, the embodiment of the invention also provides a quantum dot light emitting diode, which comprises an anode, a cathode and a quantum dot light emitting layer positioned between the anode and the cathode, wherein a hole transport layer is arranged between the anode and the quantum dot light emitting layer, and the hole transport layer consists of the composite material or the composite material obtained by the preparation method of the composite material.
Electron injection of QLED devices is generally much stronger than hole injection, resulting in poor charge balance of the device, severely affecting device lifetime. In the embodiment of the invention, unbranched linear dicarboxylic acid (organic molecules shown in the formula I) is added in the HTL layer to coordinate with metal ions, so that the organic semiconductor material is connected with the metal ions, the molecular distance of the organic semiconductor material is shortened, the conjugated resonance effect among the organic semiconductor material molecules is enhanced, the conduction capacity of holes among the organic semiconductor material molecules is improved, the hole mobility of the semiconductor material layer is improved, and the hole transmission capacity is enhanced. Therefore, the hole transport layer in the quantum dot light emitting diode provided by the embodiment of the invention is composed of the special composite material of the embodiment of the invention or the special composite material prepared by the preparation method of the embodiment of the invention, the composite material has good electrical property of a crystal structure, hole injection is enhanced, the HOMO energy level of the composite material is well matched with that of the quantum dot light emitting layer, the effective recombination of electrons and holes in the quantum dot light emitting layer can be promoted, the hole and electron injection rate of a device are balanced, the charge accumulation of the interface of the quantum dot light emitting layer and the hole transport layer is reduced, and the light emitting efficiency and the service life of the device are improved.
In an embodiment, in the device, a hole injection layer is further disposed between the hole transport layer and the anode. In another embodiment, an electron functional layer, such as an electron transport layer, or a stack of an electron injection layer and an electron transport layer, is disposed between the quantum dot light emitting layer and the cathode, wherein the electron injection layer is adjacent to the cathode.
The quantum dot light emitting diode provided by the embodiment of the invention comprises a positive structure and an inverted structure.
In one embodiment, a positive-structure quantum dot light emitting diode includes a stacked structure of an anode and a cathode disposed opposite to each other, a quantum dot light emitting layer disposed between the anode and the cathode, a hole transporting layer disposed between the anode and the quantum dot light emitting layer, and the anode disposed on a substrate. Furthermore, a hole injection layer, an electron blocking layer and other hole functional layers can be arranged between the anode and the quantum dot luminescent layer; an electron transport layer, an electron injection layer, a hole blocking layer and other electron functional layers can be arranged between the cathode and the quantum dot luminescent layer. In some embodiments of the forward structure device, the quantum dot light emitting diode includes a substrate, an anode disposed on a surface of the substrate, the hole injection layer disposed on a surface of the anode, a hole transport layer disposed on a surface of the hole injection layer, a quantum dot light emitting layer disposed on a surface of the hole transport layer, an electron transport layer disposed on a surface of the quantum dot light emitting layer, and a cathode disposed on a surface of the electron transport layer.
In one embodiment, an inverted structure quantum dot light emitting diode includes a stacked structure of an anode and a cathode disposed opposite to each other, a quantum dot light emitting layer disposed between the anode and the cathode, a hole transporting layer disposed between the anode and the quantum dot light emitting layer, and the cathode disposed on a substrate. Furthermore, a hole injection layer, an electron blocking layer and other hole functional layers can be arranged between the anode and the quantum dot luminescent layer; an electron transport layer, an electron injection layer, a hole blocking layer and other electron functional layers can be arranged between the cathode and the quantum dot luminescent layer. In some embodiments of the inverted structure device, the quantum dot light emitting diode includes a substrate, a cathode disposed on a surface of the substrate, the electron transport layer disposed on a surface of the cathode, a quantum dot light emitting layer disposed on a surface of the electron transport layer, a hole transport layer disposed on a surface of the quantum dot light emitting layer, a hole injection layer disposed on a surface of the hole transport layer, and an anode disposed on a surface of the hole injection layer.
Correspondingly, the preparation method of the quantum dot light emitting diode comprises the following steps of:
e01: providing a substrate;
e02: and depositing the composite material or the composite material obtained by the preparation method on the substrate to obtain the hole transport layer.
Specifically, the preparation of the QLED device comprises the following steps:
(1) Providing a substrate, and forming an anode on the substrate;
(2) Forming a hole injection layer on the anode;
(3) And forming a hole transport layer on the hole injection layer, wherein the hole transport layer consists of the composite material.
(4) Forming a quantum dot light emitting layer on the hole transport layer;
(5) Depositing an electron transport layer on the quantum dot light emitting diode layer;
(6) A cathode is formed on the electron transport layer.
The substrate comprises a rigid, flexible substrate, specifically comprising glass, silicon wafer, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyethersulfone, or combinations thereof.
The anode comprises a metal or alloy thereof such as nickel, platinum, vanadium, chromium, copper, zinc,Or gold; conductive metal oxides such as zinc oxide, indium oxide, tin oxide, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), or fluorine doped tin oxide; or a combination of metal and oxide such as ZnO and Al or SnO 2 And Sb, but not limited thereto, may be any two or more of the above.
The hole injection layer comprises a conductive compound including polythiophene, polyaniline, polypyrrole, poly (p-phenylene), polyfluorene, poly (3, 4-ethylenedioxythiophene) polysulfstyrene (PEDOT: PSS), moO 3 、WoO 3 、NiO、HATCN、CuO、V 2 O 5 CuS, or a combination thereof.
The hole transport layer can be a composite material film layer prepared and formed through the steps.
The quantum dots of the quantum dot luminous layer are CdS, cdSe, cdTe, znS, znSe, znTe, znO, hgS, hgSe, hgTe, cdSeS, cdSeTe, cdSTe, znSeS, znSeTe, znSTe, hgSeS, hgSeTe, hgSTe, cdZnS, cdZnSe, cdZnTe, cdHgS, cdHgSe, cdHgTe, hgZnS, hgZnSe, hgZnTe, cdZnSeS, cdZnSeTe, cdZnSTe, cdHgSeS, cdHgSeTe, cdHgSTe, hgZnSeS, hgZnSeTe, hgZnSTe of II-VI groups; or group III-V GaN, gaP, gaAs, gaSb, alN, alP, alAs, alSb, inN, inP, inAs, inSb, gaNP, gaNAs, gaNSb, gaPAs, gaPSb, alNP, alNAs, alNSb, alPAs, alPSb, inNP, inNAs, inNSb, inPAs, inPSb, gaAlNP, gaAlNAs, gaAlNSb, gaAlPAs, gaAlPSb, gaInNP, gaInNAs, gaInNSb, gaInPAs, gaInPSb, inAlNP, inAlNAs, inAlNSb, inAlPAs, inAlPSb; or group IV-VI SnS, snSe, snTe, pbS, pbSe, pbTe, snSeS, snSeTe, snSTe, pbSeS, pbSeTe, pbSTe, snPbS, snPbSe, snPbTe, snPbSSe, snPbSeTe, snPbSTe; or a combination of any one or more of the above.
The electron transport layer is ZnO and TiO 2 、Alq 3 、SnO 2 、ZrO、AlZnO、ZnSnO、BCP、TAZ、PBD、TPBI、Bphen、CsCO 3 One or more of the following.
The cathode comprises a metal or alloy thereof such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin,Lead, cesium, or barium; the multi-layer structural material includes a first layer of an alkali metal halide, alkaline earth metal halide, alkali metal oxide, or combination thereof, and a structure of a metal layer, wherein the metal layer includes an alkaline earth metal, a group 13 metal, or combination thereof. For example LiF/Al, liO 2 Al, liF/Ca, liq/Al, and BaF 2 /Ca, but is not limited thereto.
The thickness of the bottom electrode is 20-200 nm; the thickness of the hole injection layer is 20-200 nm; the thickness of the hole transport layer is 30-180 nm; the total thickness of the quantum dot mixed luminescent layer is 30-180 nm. The thickness of the electron transport layer is 10-180 nm; the thickness of the top electrode is 40-190 nm.
The invention has been tested several times in succession, and the invention will now be described in further detail with reference to a few test results, which are described in detail below in connection with specific examples.
Example 1
The present embodiment provides a QLED device having a structure as shown in fig. 2, which includes, from bottom to top, a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a quantum dot light emitting layer 5, an electron transport layer 6, and a cathode 7. Wherein, the material of the substrate 1 is a glass sheet, the material of the anode 2 is an ITO substrate, and the material of the hole injection layer 3 is PEDOT: PSS, a hole transport layer 4, a quantum dot luminescent layer 5 and an electron transport layer 6 are respectively made of a composite material of suberic acid doped TFB, cdZnSe/ZnSe quantum dots, znO and Al, respectively.
The preparation method of the device comprises the following steps:
1. to a TFB solution dissolved in chloroform solvent, a certain amount of monomethyl suberate and zinc acetate in n-octanoic acid solution was added at room temperature. The mass ratio of the doped dicarboxylic acid monoester to the TFB material is 1:30, the molar ratio of the dicarboxylic acid monoester to the zinc acetate is 1:1, and the dicarboxylic acid monoester is heated for 2 hours at 80 ℃ to realize complete hydrolysis of the dicarboxylic acid monoester to form suberic acid, so that a solution 1 is obtained.
2. The prepared solution 1 was deposited on a hole injection layer (PEDOT: PSS) under spin-coating at 3000r/min for 30s, and then heated at 150℃for 2 hours to complete crystallization, thereby obtaining a hole transport layer.
3. And depositing CdZnSe/ZnSe quantum dots on the hole transport layer, and spin-coating for 30s at a certain revolution of 3000 r/min.
4. An electron transport layer, namely a ZnO layer, is deposited, spin-coated for 30s at 3000r/min and then heated at 80 ℃ for 30min.
5. And evaporating an Al electrode, and packaging by adopting electronic glue to obtain the QLED device.
Example 2
The present embodiment provides a QLED device having a structure as shown in fig. 2, which includes, from bottom to top, a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a quantum dot light emitting layer 5, an electron transport layer 6, and a cathode 7. Wherein, the material of the substrate 1 is a glass sheet, the material of the anode 2 is an ITO substrate, and the material of the hole injection layer 3 is PEDOT: PSS, a hole transport layer 4, a quantum dot luminescent layer 5, an electron transport layer 6 and a cathode 7 are respectively made of a composite material of succinic acid doped with TFB, cdZnSe/ZnSe/CdZnS quantum dots, znO and Al.
The preparation method of the device comprises the following steps:
1. a certain amount of monomethyl succinate and zinc acetate n-octanoic acid solution is added into TFB solution dissolved by chloroform solvent at room temperature. The mass ratio of the doped dicarboxylic acid monoester to the TFB material is 1:30, the molar ratio of the dicarboxylic acid monoester to the zinc acetate is 1:2, and the dicarboxylic acid monoester is heated for 3 hours at 80 ℃ to realize complete hydrolysis of the dicarboxylic acid monoester to form succinic acid, so that solution 1 is obtained.
2. The prepared solution 1 was deposited on a hole injection layer (PEDOT: PSS) under spin-coating at 3000r/min for 30s, and then heated at 140℃for 2 hours to complete crystallization, thereby obtaining a hole transport layer.
3. And depositing CdZnSe/ZnSe/CdZnS quantum dots on the hole transmission layer, and spin-coating for 30s at a certain revolution of 2000 r/min.
4. An electron transport layer, namely a ZnO layer, is deposited, spin-coated for 30s at 3000r/min and then heated at 80 ℃ for 30min.
5. And evaporating an Al electrode, and packaging by adopting electronic glue to obtain the QLED device.
Example 3
The present embodiment provides a QLED device having a structure as shown in fig. 2, which includes, from bottom to top, a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a quantum dot light emitting layer 5, an electron transport layer 6, and a cathode 7. Wherein, the material of the substrate 1 is a glass sheet, the material of the anode 2 is an ITO substrate, and the material of the hole injection layer 3 is PEDOT: PSS, a hole transport layer 4, a quantum dot luminescent layer 5, an electron transport layer 6 and a cathode 7 are respectively made of a composite material of glutaric acid doped TFB, cdZnSe/ZnSe/ZnS quantum dots, znO and Al.
The preparation method of the device comprises the following steps:
1. to a TFB solution dissolved in chlorobenzene solvent, a certain amount of monomethyl glutarate and zinc acetate in n-octanoic acid solution was added at room temperature. The mass ratio of the doped dicarboxylic acid monoester to the TFB material is 1:20, the molar ratio of the dicarboxylic acid monoester to the zinc acetate is 1:3, and the dicarboxylic acid monoester is heated for 2 hours at 80 ℃ to realize complete hydrolysis of the dicarboxylic acid monoester to form glutaric acid, so that a solution 1 is obtained.
2. The prepared solution 1 was deposited on PEDOT: spin-coating for 30s at 3000r/min on PSS, and heating at 150deg.C for 40min to complete crystallization to obtain hole transport layer.
3. And depositing CdZnSe/ZnSe/ZnS quantum dots on the hole transmission layer, and spin-coating for 30s at 4000r/min of a certain revolution.
4. And depositing an ETL layer, namely a ZnO layer, spin-coating at 3000r/min for 30s, and heating at 80 ℃ for 30min.
5. And evaporating an Al electrode, and packaging by adopting electronic glue to obtain the QLED device.
Example 4
The present embodiment provides a QLED device having a structure as shown in fig. 2, which includes, from bottom to top, a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a quantum dot light emitting layer 5, an electron transport layer 6, and a cathode 7. Wherein, the material of the substrate 1 is a glass sheet, the material of the anode 2 is an ITO substrate, and the material of the hole injection layer 3 is PEDOT: PSS, a hole transport layer 4, a quantum dot luminescent layer 5, an electron transport layer 6 and a cathode 7 are respectively made of composite materials of adipic acid doped TFB, cdZnSeS/ZnS quantum dots, znO and Al.
The preparation method of the device comprises the following steps:
1. to a TFB solution dissolved in toluene solvent, a certain amount of monomethyl adipate and zinc acetate in n-octanoic acid solution was added at room temperature. The mass ratio of the doped dicarboxylic acid monoester to the TFB material is 1:15, the molar ratio of the dicarboxylic acid monoester to the zinc acetate is 1:3, and the dicarboxylic acid monoester is heated for 2.5 hours at 90 ℃ to realize complete hydrolysis of the dicarboxylic acid monoester to form adipic acid, so that solution 1 is obtained.
2. The prepared solution 1 was deposited on PEDOT: spin-coating for 30s at 3000r/min on PSS, and heating at 150deg.C for 2 hr to complete crystallization to obtain hole transport layer.
3. And depositing CdZnSeS/ZnS quantum dots on the hole transport layer, and spin-coating for 30s at 4000r/min of a certain revolution.
4. And depositing an ETL layer, namely a ZnO layer, spin-coating at 3000r/min for 30s, and heating at 80 ℃ for 30min.
5. And evaporating an Al electrode, and packaging by adopting electronic glue to obtain the QLED device.
Example 5
The present embodiment provides a QLED device having a structure as shown in fig. 2, which includes, from bottom to top, a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a quantum dot light emitting layer 5, an electron transport layer 6, and a cathode 7. Wherein, the material of the substrate 1 is a glass sheet, the material of the anode 2 is an ITO substrate, and the material of the hole injection layer 3 is PEDOT: PSS, a hole transport layer 4 is made of suberic acid doped 4,4' -tris (N-carbazolyl) -triphenylamine composite material, a quantum dot luminescent layer 5 is made of CdZnSe/ZnSe quantum dots, an electron transport layer 6 is made of ZnO, and a cathode 7 is made of Al.
The preparation method of the device comprises the following steps:
1. to a solution of 4,4',4 "-tris (N-carbazolyl) -triphenylamine dissolved in chloroform at room temperature was added a certain amount of monomethyl suberate and indium acetate in N-octanoic acid solution. The mass ratio of the doped dicarboxylic acid monoester to the 4,4' -tris (N-carbazolyl) -triphenylamine material is 1:30, the molar ratio of the dicarboxylic acid monoester to the indium acetate is 1:1, and the dicarboxylic acid monoester is heated at 80 ℃ for 2 hours to realize complete hydrolysis of the dicarboxylic acid monoester to form suberic acid, so that a solution 1 is obtained.
2. The prepared solution 1 was deposited on a hole injection layer (PEDOT: PSS) under spin-coating at 3000r/min for 30s, and then heated at 150℃for 2 hours to complete crystallization, thereby obtaining a hole transport layer.
3. And depositing CdZnSe/ZnSe quantum dots on the hole transport layer, and spin-coating for 30s at a certain revolution of 3000 r/min.
4. An electron transport layer, namely a ZnO layer, is deposited, spin-coated for 30s at 3000r/min and then heated at 80 ℃ for 30min.
5. And evaporating an Al electrode, and packaging by adopting electronic glue to obtain the QLED device.
Example 6
The present embodiment provides a QLED device having a structure as shown in fig. 2, which includes, from bottom to top, a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a quantum dot light emitting layer 5, an electron transport layer 6, and a cathode 7. Wherein, the material of the substrate 1 is a glass sheet, the material of the anode 2 is an ITO substrate, and the material of the hole injection layer 3 is PEDOT: PSS, a hole transmission layer 4 is made of suberic acid doped 4,4' -tris (N-carbazolyl) -triphenylamine composite material, a quantum dot luminescent layer 5 is made of CdZnSe/ZnSe/ZnS quantum dots, an electron transmission layer 6 is made of ZnO, and a cathode 7 is made of Al.
The preparation method of the device comprises the following steps:
1. to a solution of 4,4',4 "-tris (N-carbazolyl) -triphenylamine dissolved in chloroform at room temperature was added a certain amount of monomethyl suberate and titanium acetate in N-octanoic acid. The mass ratio of the doped dicarboxylic acid monoester to the 4,4' -tris (N-carbazolyl) -triphenylamine material is 1:30, the molar ratio of the dicarboxylic acid monoester to the titanium acetate is 1:1, and the dicarboxylic acid monoester is heated at 80 ℃ for 2 hours to realize complete hydrolysis of the dicarboxylic acid monoester to form suberic acid, so that a solution 1 is obtained.
2. The prepared solution 1 was deposited on a hole injection layer (PEDOT: PSS) under spin-coating at 3000r/min for 30s, and then heated at 150℃for 2 hours to complete crystallization, thereby obtaining a hole transport layer.
3. And depositing CdZnSe/ZnSe/ZnS quantum dots on the hole transport layer, and spin-coating for 30s at a certain revolution of 3000 r/min.
4. An electron transport layer, namely a ZnO layer, is deposited, spin-coated for 30s at 3000r/min and then heated at 80 ℃ for 30min.
5. And evaporating an Al electrode, and packaging by adopting electronic glue to obtain the QLED device.
Comparative example 1
This comparative example was prepared in the same manner as in example 1, except that the hole transport layer material was undoped TFB material.
Comparative example 2
This comparative example was prepared in the same manner as in example 2, except that the hole transport layer material was undoped TFB material.
Comparative example 3
This comparative example was prepared in the same manner as in example 3, except that the hole transport layer material was undoped TFB material.
Comparative example 4
This comparative example was prepared in the same manner as in example 4, except that the hole transport layer material was undoped TFB material.
Comparative example 5
This comparative example was prepared in the same manner as in example 5 except that the hole transport layer material was an undoped 4,4',4 "-tris (N-carbazolyl) -triphenylamine material.
Comparative example 6
This comparative example was prepared in the same manner as in example 6 except that the hole transport layer material was undoped 4,4',4 "-tris (N-carbazolyl) -triphenylamine material.
Performance testing
The above comparative examples 1 to 6 and the quantum dot light emitting diodes prepared in examples 1 to 6 were subjected to performance test as follows:
(1) External quantum dot efficiency:
the ratio of electron-hole pairs injected into the quantum dots to the number of outgoing photons is shown in the unit, and is an important parameter for measuring the advantages and disadvantages of the electroluminescent device, and the quantum dots can be obtained by measuring the electron-hole pairs with an EQE optical test instrument. The specific calculation formula is as follows:
in eta e For light out-coupling efficiency, eta r Is the ratio of the number of combined carriers to the number of injected carriers, χ is the ratio of the number of excitons generating photons to the total number of excitons, K R For the rate of the radiation process, K NR Is the non-radiative process rate.
Test conditions: the process is carried out at room temperature, and the air humidity is 30-60%.
(2) QLED device lifetime:
the time required for the device to decrease in brightness to a certain proportion of the maximum brightness under constant current or voltage drive is defined as T95, and the lifetime is the measured lifetime. To shorten the test period, the device lifetime test is usually performed by accelerating the aging of the device under high brightness with reference to the OLED device test, and the lifetime under high brightness is obtained by fitting an extended exponential decay brightness decay fitting formula, for example: lifetime meter at 1000nit T95 1000nit . The specific calculation formula is as follows:
t95 in L T95 is the life at low brightness H For the actual life under high brightness, L H To accelerate the device to the highest brightness, L L For 1000nit, A is an acceleration factor, for OLED, the value is usually 1.6-2, and the experiment obtains the A value to be 1.7 by measuring the service lives of a plurality of groups of green QLED devices under rated brightness.
And (3) carrying out life test on the corresponding device by adopting a life test system, wherein the test conditions are as follows: the process is carried out at room temperature, and the air humidity is 30-60%.
(3) Hole mobility: the average velocity obtained by the carriers under the action of unit electric field reflects the transport capacity of the carriers under the action of the electric field, and the unit is cm 2 /(v·s). The method is obtained by preparing a corresponding pure hole type device and then adopting a space charge limited amperometric (SCLC) measurement. The structure of the pure hole type device is as follows: yang (Yang)A pole/hole transport layer/cathode. The specific calculation formula is as follows:
wherein d is the thickness of the material of the hole transport layer to be determined, the unit is nm, F is the applied electric field, the unit is V/m, L is the thickness of the whole device, and the unit is nm.
Test conditions: the process is carried out at room temperature, and the air humidity is 30-60%.
The test results are shown in table 1:
TABLE 1
As can be seen from table 1 above, the hole transport layer films of the examples of the present invention have significantly higher hole mobility than the hole transport layer films of the respective comparative examples. The external quantum efficiency and the service life of the quantum dot light emitting diode provided by the embodiment of the invention are obviously higher than those of the quantum dot light emitting diode in the corresponding comparative example, which shows that the quantum dot light emitting diode provided by the embodiment of the invention has better light emitting efficiency.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.

Claims (10)

1. A composite material, characterized in that the composite material comprises an organic semiconductor material, an organic molecule and a metal ion, wherein the organic molecule has a structure shown in the following formula I, and a carboxyl group on the organic molecule coordinates with the metal ion and is connected to the organic semiconductor material through the metal ion;
wherein R is 1 Is- (CH) 2 ) n -n is an integer greater than or equal to 1.
2. The composite material of claim 1, wherein R of the organic molecule 1 N=2 to 20; and/or the number of the groups of groups,
the mass ratio of the organic molecules to the organic semiconductor material is (0.1-1): 30; and/or the number of the groups of groups,
the molar ratio of the organic molecule to the metal ion is (1-3): 1.
3. the composite material of claim 1, wherein the organic semiconductor material is selected from one or more of poly (9, 9-dioctyl-fluorene-co-N- (4-butylphenyl) -diphenylamine), polyarylamine, poly (N-vinylcarbazole), polyaniline, polypyrrole, N ' -tetrakis (4-methoxyphenyl) -benzidine, 4-bis [ N- (1-naphthyl) -N-phenyl-amino ] biphenyl, 4',4 "-tris [ phenyl (m-tolyl) amino ] triphenylamine, 4',4" -tris (N-carbazolyl) -triphenylamine, and 1, 1-bis [ (di-4-tolylamino) phenylcyclohexane; and/or the number of the groups of groups,
the organic semiconductor material is selected from organic hole transport materials containing amino groups; and/or the number of the groups of groups,
the metal ion is selected from one or more of zinc ion, titanium ion, aluminum ion, indium ion, tin ion, zirconium ion and gallium ion.
4. A composite material according to any one of claims 1 to 3, wherein the composite material consists of the organic semiconductor material, organic molecules and metal ions.
5. The preparation method of the composite material is characterized by comprising the following steps:
providing an organic semiconductor material, a dicarboxylic acid monoester organic compound shown in the following formula II and a metal ion precursor;
dissolving the organic semiconductor material, the dicarboxylic acid monoester organic matter and the metal ion precursor in a nonpolar solvent, and performing heating treatment to obtain a mixed solution;
carrying out solid-liquid separation on the mixed solution to obtain the composite material;
wherein R is 1 Is- (CH) 2 ) n -，R 2 is-O (CH) 2 ) m CH 3 N is an integer greater than or equal to 1, and m is an integer greater than or equal to 0.
6. The method of preparing a composite material according to claim 5, wherein R is a dicarboxylic acid monoester organic compound 1 N=2 to 20; and/or the number of the groups of groups,
r of said dicarboxylic acid monoester organic matter 2 M=2 to 20.
7. The method for producing a composite material according to claim 5, wherein the mass ratio of the dicarboxylic acid monoester organic substance to the organic semiconductor material is (0.1 to 1): 30; and/or the number of the groups of groups,
the molar ratio of the dicarboxylic acid monoester organic matter to the metal ion precursor is (1-3): 1.
8. the method of preparing a composite material according to claim 5, wherein the conditions of the heat treatment include: the temperature is 60-120 ℃ and the time is 30 min-4 h; and/or the number of the groups of groups,
the solid-liquid separation comprises annealing crystallization at 140-160 ℃.
9. The method of preparing a composite material according to any one of claims 5 to 8, wherein the organic semiconductor material is selected from one or more of poly (9, 9-dioctyl-fluorene-co-N- (4-butylphenyl) -diphenylamine), polyarylamine, poly (N-vinylcarbazole), polyaniline, polypyrrole, N ' -tetrakis (4-methoxyphenyl) -benzidine, 4-bis [ N- (1-naphthyl) -N-phenyl-amino ] biphenyl, 4',4 "-tris [ phenyl (m-tolyl) amino ] triphenylamine, 4',4" -tris (N-carbazolyl) -triphenylamine, and 1, 1-bis [ (di-4-tolylamino) phenylcyclohexane; and/or the number of the groups of groups,
the metal ion precursor is selected from one or more of zinc ion precursor, titanium ion precursor, aluminum ion precursor, indium ion precursor, tin ion precursor, zirconium ion precursor and gallium ion precursor.
10. A quantum dot light emitting diode comprising an anode, a cathode and a quantum dot light emitting layer between the anode and the cathode, a hole transport layer being provided between the anode and the quantum dot light emitting layer, characterized in that the hole transport layer consists of the composite material according to any one of claims 1 to 4 or the composite material obtained by the preparation method according to any one of claims 5 to 9.
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