WO2022143676A1

WO2022143676A1 - Composite material and preparation method therefor, and quantum dot light-emitting diode

Info

Publication number: WO2022143676A1
Application number: PCT/CN2021/142131
Authority: WO
Inventors: 李俊杰; 张天朔; 郭煜林; 童凯
Original assignee: Tcl科技集团股份有限公司
Priority date: 2020-12-30
Filing date: 2021-12-28
Publication date: 2022-07-07
Also published as: CN114695810A

Abstract

Disclosed are a composite material and a preparation method therefor, and a quantum dot light-emitting diode. The composite material comprises zinc oxide nanoparticles and polypyrrole coated on the surface of the zinc oxide nanoparticles. In the composite material of the present disclosure, the polypyrrole coating can effectively increase the spacing between the zinc oxide nanoparticles, passivate the surface of the zinc oxide nanoparticles and reduce the generation of oxygen vacancies, and the polypyrrole coating can also protect the zinc oxide nanoparticles from agglomeration. N and C atoms are present on the surface of pyrrole, and can effectively provide an electronic transport path and improve the electronic transport capability. The polypyrrole coating can also effectively isolate the erosion of the zinc oxide nanoparticles by water and oxygen, and the compactness of polypyrrole is higher than that of a common ligand.

Description

Composite material and preparation method thereof, and quantum dot light-emitting diode

priority

This disclosure claims the priority of the Chinese patent application with the application date of December 30, 2020, the application number is "202011609538.4", and the application name is "a composite material and its preparation method, quantum dot light-emitting diode" , the entire contents of which are incorporated by reference in this disclosure.

technical field

The present disclosure relates to the field of quantum dot light-emitting diodes, and in particular, to a composite material and a preparation method thereof, and a quantum dot light-emitting diode.

Background technique

A quantum dot light-emitting diode (QLED) is a structure composed of a cathode, a hole transport layer, a quantum dot light-emitting layer, an electron transport layer and an anode. When a voltage is applied, electrons and holes are injected from their respective electrodes, and the two emit light together. QLEDs have attracted more and more attention due to their excellent properties such as wide absorption and narrow emission, high color purity and luminous intensity due to their continuously tunable spectrum in the visible region.

ZnO is a common Ⅱ-Ⅵ semiconductor compound, the forbidden band width of its material can reach 3.34eV, has the coordination of optoelectronic properties, and is an ideal electron transport layer material. Electron transport layer material-ZnO-based nanocrystals have been widely studied as carrier transport materials for QLED devices.

In the application process of zinc oxide, inorganic nano-zinc oxide particles need to be dispersed into the organic matrix, but the agglomeration of inorganic nanoparticles is often caused by the following reasons: (1) particle aggregation caused by intermolecular forces, hydrogen bonds, electrostatic interactions, etc.; ( 2) Due to the quantum tunneling effect between particles, charge transfer and the mutual coupling of interface atoms, the particles are very easy to agglomerate through the interface interaction and solid-phase reaction; After contact with a medium, it is easy to adsorb gas, medium or interact with it and lose its original surface properties, resulting in adhesion and agglomeration; (4) Its surface energy is extremely high, the contact interface is large, and it is in a non-thermodynamically stable state, which makes the crystal grains in a non-thermodynamic stable state. The rate of growth is accelerated, so it is difficult for the particle size to remain constant. The agglomeration of inorganic nano-ZnO particles directly leads to a decrease in the conductivity of ZnO and unbalanced carrier transport, which ultimately leads to lower device efficiency and easy quenching.

Therefore, the existing technology still needs to be improved and developed.

SUMMARY OF THE INVENTION

In view of the above-mentioned deficiencies of the prior art, the purpose of the present disclosure is to provide a composite material and a preparation method thereof, and a quantum dot light-emitting diode, aiming to solve the problem that the existing nano-zinc oxide particles are easy to agglomerate, resulting in a decrease in electrical conductivity and poor carrier transport. balance issue.

The technical solutions of the present disclosure are as follows:

A composite material comprising zinc oxide nanoparticles and polypyrrole coated on the surface of the zinc oxide nanoparticles.

A preparation method of composite material, wherein, comprising the steps:

Mixing the pyrrole with the cationic surfactant to obtain a first mixed solution;

Disperse the basic compound in an organic alcohol solvent to obtain lye;

The lye solution is added to the zinc salt solution and mixed, then the first mixed solution is added to mix, and finally an oxidant is added to mix, and the composite material is prepared by reaction.

A quantum dot light-emitting diode, comprising an electron transport layer, the material of the electron transport layer is the composite material described in the present disclosure or the composite material prepared by the preparation method described in the present disclosure.

Beneficial effects: The composite material provided by the present disclosure includes zinc oxide nanoparticles and polypyrrole coated on the surface of the zinc oxide nanoparticles. The coating of the polypyrrole can effectively increase the interval between the zinc oxide nanoparticles, passivate the surface of the zinc oxide nanoparticles, reduce the generation of oxygen vacancies, and reduce the surface energy of the zinc oxide nanoparticles, thereby protecting the zinc oxide nanoparticles No agglomeration occurs; the surface of the pyrrole has N, C atoms, which can effectively provide an electron transport path and improve the electron transport capacity; the coating of the polypyrrole can also effectively isolate the corrosion of the zinc oxide nanoparticles by water and oxygen, compared with ordinary The ligands of polypyrrole are more dense.

Description of drawings

FIG. 1 is a flow chart of a preferred embodiment of a method for preparing a composite material provided by the present disclosure.

FIG. 2 is a schematic structural diagram of a quantum dot light emitting diode with an upright structure provided by the present disclosure.

FIG. 3 is a flowchart of a preferred embodiment of a method for manufacturing a quantum dot light-emitting diode with an upright structure provided by the present disclosure.

FIG. 4 is a flow chart of a preferred embodiment of a method for manufacturing a quantum dot light emitting diode with an inverted structure provided by the present disclosure.

FIG. 5 is an FT-IR image of the composite material prepared in Example 1. FIG.

6 is a U-I comparison diagram of Comparative Example 1 and Example 1-Example 3.

Detailed ways

The present disclosure provides a composite material, a preparation method thereof, and a quantum dot light-emitting diode. In order to make the purposes, technical solutions and effects of the present disclosure clearer and clearer, the present disclosure will be further described below in detail. It should be understood that the specific embodiments described herein are only used to explain the present disclosure, but not to limit the present disclosure.

Due to the defects on the surface of ZnO nanoparticles, part of Zn does not combine with O to form dangling bonds, which makes ZnO NPs have a large specific surface area and extremely high surface energy, resulting in mutual agglomeration between ZnO nanoparticles, which directly leads to ZnO The nanoparticle conductivity decreases and the carrier transport is unbalanced, ultimately resulting in lower device efficiency and easy quenching.

Based on this, the present disclosure provides a composite material comprising zinc oxide nanoparticles and polypyrrole coated on the surface of the zinc oxide nanoparticles.

In this embodiment, N in the polypyrrole is covalently bonded to zinc containing oxygen defects on the surface of the zinc oxide nanoparticles, thereby forming a composite material. The coating of the polypyrrole can effectively increase the interval between the zinc oxide nanoparticles, passivate the surface of the zinc oxide nanoparticles, reduce the generation of oxygen vacancies, and reduce the surface energy of the zinc oxide nanoparticles, thereby protecting the zinc oxide nanoparticles No agglomeration occurs; the surface of the pyrrole has N, C atoms, which can effectively provide an electron transport path and improve the electron transport capacity; the coating of the polypyrrole can also effectively isolate the corrosion of the zinc oxide nanoparticles by water and oxygen, compared with ordinary The ligands of polypyrrole are more dense.

In this embodiment, the polypyrrole has a conjugated structure in which carbon-carbon single bonds and carbon-carbon double bonds are alternately arranged, the double bonds are composed of σ electrons and π electrons, and the σ electrons are fixed and cannot move freely. , forming covalent bonds between carbon atoms. The 2 pi electrons in the conjugated double bond are not fixed on a certain carbon atom, they can be translocated from one carbon atom to another carbon atom, that is, they have a tendency to extend throughout the molecular chain. That is, the overlapping of the π electron clouds in the molecule produces an energy band common to the whole molecule, and the π electrons are similar to the free electrons in the metal conductor, which achieves the purpose of transporting electrons.

In this embodiment, the conductivity of pyrrole can be adjusted according to different proportions of pyrrole and the selection of alkali source, so as to achieve the purpose of matching the conductivity of the quantum dots, thereby obtaining zinc oxide with stronger adaptability.

In some embodiments, a preparation method of a composite material is also provided, as shown in Figure 1, which comprises the steps:

S10, mixing pyrrole with a cationic surfactant to obtain a first mixed solution;

S20, the basic compound is dispersed in the organic alcohol solvent, obtains lye;

S30, adding the alkali solution to the zinc salt solution and mixing, then adding the first mixed solution and mixing, and finally adding an oxidant to mix, and reacting to prepare the composite material.

In this embodiment, the zinc salt solution and the lye solution can generate zinc oxide nanoparticles after being stirred for a period of time, and as the first mixed solution is added, the pyrrole and the zinc oxide nanoparticles are coordinated and combined, and then the first mixed solution The cationic surfactant in the solution is used to strengthen the surface activity of the zinc oxide nanoparticles, so that the pyrrole can achieve a better coating effect; finally, an oxidant is added for the polymerization of the pyrrole, and the finally formed polypyrrole will be coated on the zinc oxide. A coating film is formed on the surface of the nanoparticles, thereby preparing the composite material.

In the composite material prepared in this example, N in the polypyrrole is coordinately bonded to zinc containing oxygen defects on the surface of the zinc oxide nanoparticles. The coating of the polypyrrole can effectively increase the interval between the zinc oxide nanoparticles, passivate the surface of the zinc oxide nanoparticles, reduce the generation of oxygen vacancies, and reduce the surface energy of the zinc oxide nanoparticles, thereby protecting the zinc oxide nanoparticles No agglomeration occurs; the surface of the pyrrole has N, C atoms, which can effectively provide an electron transport path and improve the electron transport capacity; the coating of the polypyrrole can also effectively isolate the corrosion of the zinc oxide nanoparticles by water and oxygen, compared with ordinary The ligands of polypyrrole are more dense.

In some embodiments, in the step of mixing the pyrrole with the cationic surfactant to obtain the first mixed solution, the molar ratio of the cationic surfactant and the pyrrole is 1:0.5-8.

Specifically, if the amount of the cationic surfactant is too small, the surface activity of the zinc oxide nanoparticles will be reduced, the coating degree will be reduced, and the coating degree will be poor; if the amount of the cationic surfactant is too large, a large amount of cationic surface active The surface activity of the zinc oxide nanoparticles will be too large, and the zinc oxide nanoparticles will react too vigorously, resulting in the agglomeration of the zinc oxide nanoparticles. By adjusting the different ratios of pyrrole and cationic surfactant, the coating degree of polypyrrole can be adjusted, thereby adjusting the electrical conductivity of the composite material, so as to achieve the purpose of matching the electrical conductivity with the quantum dots, so as to obtain a more suitable composite material.

In some embodiments, the cationic surfactant is stearyltrimethylammonium chloride, cetyltrimethylammonium tosylate, octyltrimethylammonium chloride, dodecenyl Di(hydroxyethyl)methylammonium chloride, dodecenyltrimethylammonium chloride, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, tetradecane trimethylammonium chloride, tetradecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, decyltrimethylammonium chloride and One or more of decyltrimethylammonium bromide, but not limited thereto.

In some embodiments, the oxidizing agent is ammonium persulfate or sodium persulfate, and the oxidizing agent is used for the polymerization of pyrrole, so that the finally formed polypyrrole is coated on the surface of the zinc oxide nanoparticles to form a coating film, so as to obtain the the composite material.

In some embodiments, the zinc salt solution includes an organic alcohol and a zinc salt dispersed in the organic alcohol, the zinc salt is one of zinc acetate, zinc nitrate, zinc chloride, zinc sulfate and zinc acetate dihydrate or more, but not limited to.

In some embodiments, the organic alcohol is one or more of isopropanol, ethanol, propanol, butanol, amyl alcohol and hexanol, but is not limited thereto.

In some embodiments, in the step of adding the lye solution to the zinc salt solution, the molar ratio of the zinc ions in the zinc salt to the hydroxide ions in the lye solution is 1:1 -2.

In this embodiment, the basic compound is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide and tetramethylammonium hydroxide pentahydrate, but is not limited thereto.

In some embodiments, a quantum dot light-emitting diode is also provided, which includes an electron transport layer, and the electron transport layer material is the composite material described in the present disclosure or the composite material prepared by the preparation method described in the present disclosure.

In this embodiment, the composite material includes zinc oxide nanoparticles and polypyrrole coated on the surface of the zinc oxide nanoparticles. The coating of the polypyrrole can effectively increase the space between the zinc oxide nanoparticles, passivate the surface of the zinc oxide nanoparticles, and reduce the generation of oxygen vacancies; the coating of the polypyrrole can also protect the zinc oxide nanoparticles from Agglomeration occurs; the surface of the pyrrole has N and C atoms, which can effectively provide an electron transport path, improve the electron transport ability, and adjust the carrier balance; the coating of the polypyrrole can also effectively isolate the water and oxygen from the zinc oxide nanoparticles. Erosion, the density of polypyrrole is higher than that of common ligands. The composite material provided in this embodiment can improve the electron transport performance while reducing the agglomeration phenomenon, and enhance the luminous efficiency and display performance of the device.

In some embodiments, a quantum dot light-emitting diode is also provided, which further comprises an anode, a cathode, a quantum dot light-emitting layer disposed between the anode and the cathode, and a quantum dot light-emitting layer disposed between the anode and the quantum dot light-emitting layer. A hole functional layer, the electron transport layer is disposed between the cathode and the quantum dot light-emitting layer.

In some specific embodiments, a quantum dot light-emitting diode with an upright structure is provided, as shown in FIG. 2 , which includes a substrate 10 , an anode 20 , a hole functional layer 30 , and quantum dots that are sequentially stacked from bottom to top The light-emitting layer 40, the electron transport layer 50 and the cathode 60, the electron transport layer material is the composite material described in this disclosure.

In this embodiment, since the composite material can improve the electron transport performance while reducing the agglomeration phenomenon, the luminous efficiency and display performance of the device can be enhanced.

In some embodiments, a quantum dot light-emitting diode with an inverted structure is also provided, which includes a substrate, a cathode, an electron transport layer, a quantum dot light-emitting layer, a hole function layer and an anode that are sequentially stacked from bottom to top, the The electron transport layer material is the composite material described in this disclosure.

In this embodiment, the hole functional layer may be one or more of an electron blocking layer, a hole injection layer and a hole transport layer, but is not limited thereto.

In some embodiments, the electron transport layer has a thickness of 70-90 nm.

In some embodiments, the anode material is selected from indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped One or more of hetero-zinc oxide (GZO), indium-doped zinc oxide (IZO), magnesium-doped zinc oxide (MZO), and aluminum-doped magnesium oxide (AMO), but not limited thereto.

In some embodiments, the material of the hole transport layer is selected from organic materials with good hole transport ability, such as but not limited to poly(9,9-dioctylfluorene-CO-N-(4- Butylphenyl)diphenylamine)(TFB), polyvinylcarbazole (PVK), poly(N,N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine)( Poly-TPD), poly(9,9-dioctylfluorene-co-bis-N,N-phenyl-1,4-phenylenediamine) (PFB), 4,4',4"-tris(carbohydrate) oxazol-9-yl)triphenylamine (TCTA), 4,4'-bis(9-carbazole)biphenyl (CBP), N,N'-diphenyl-N,N'-bis(3-methyl) Phenyl)-1,1'-biphenyl-4,4'-diamine (TPD), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl One or more of benzene-4,4'-diamine (NPB), doped graphene, undoped graphene, and C60.

In some embodiments, the material of the quantum dot light-emitting layer is selected from one or more of red quantum dots, green quantum dots, and blue quantum dots, and can also be selected from yellow light quantum dots. Specifically, the material of the quantum dot light-emitting layer is selected from CdS, CdSe, CdTe, ZnO, ZnS, ZnSe, ZnTe, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs, InP, InSb, AlAs, AlP, CuInS , CuInSe, and one or more of various core-shell structure quantum dots or alloy structure quantum dots. The quantum dots described in the present disclosure may be selected from cadmium-containing or cadmium-free quantum dots. The quantum dot light-emitting layer of the material has the characteristics of wide excitation spectrum and continuous distribution, and high stability of emission spectrum.

In some specific embodiments, the quantum dot light-emitting layer has a thickness of 20-60 nm.

In some embodiments, the material of the cathode is selected from one or more of conductive carbon materials, conductive metal oxide materials and metal materials; wherein the conductive carbon materials include but are not limited to doped or undoped carbon nanotubes One or more of , doped or undoped graphene, doped or undoped graphene oxide, C60, graphite, carbon fiber and porous carbon; conductive metal oxide materials include but are not limited to ITO, FTO, ATO and one or more of AZO; metal materials include but are not limited to Al, Ag, Cu, Mo, Au, or their alloys; wherein in the metal materials, their forms include but are not limited to dense thin films, nanowires, One or more of nanospheres, nanorods, nanocones, and nanohollow spheres.

In some specific embodiments, the thickness of the cathode is 15-30 nm.

In some embodiments, a method for preparing a quantum dot light-emitting diode with an upright structure is also provided, as shown in FIG. 3 , including the steps:

S100, providing a substrate, on which an anode is provided;

S200, preparing a hole transport layer on the anode;

S300, preparing a quantum dot light-emitting layer on the hole transport layer;

S400, preparing an electron transport layer on the quantum dot light-emitting layer, the electron transport layer material is a composite material, and the composite material includes zinc oxide nanoparticles and polypyrrole coated on the surface of the zinc oxide nanoparticles;

S500, preparing a cathode on the electron transport layer to prepare the quantum dot light-emitting diode.

In this embodiment, the preparation method of each layer may be a chemical method or a physical method, wherein the chemical method includes but is not limited to chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodic oxidation method, electrolytic deposition method, and co-precipitation method. One or more; physical methods include but are not limited to solution methods (such as spin coating, printing, blade coating, dip-pulling, immersion, spraying, roll coating, casting, slot coating method or strip coating method, etc.), evaporation method (such as thermal evaporation method, electron beam evaporation method, magnetron sputtering method or multi-arc ion coating method, etc.), deposition method (such as physical vapor deposition method, atomic One or more of layer deposition method, pulsed laser deposition method, etc.).

In some specific embodiments, the step of preparing the electron transport layer on the quantum dot light-emitting layer specifically includes: placing the substrate on which the quantum dot light-emitting layer has been prepared on a spin coater, and spin-coating the composite material solution onto the substrate , and annealed at 100 °C to prepare an electron transport layer.

In some specific embodiments, the step of preparing the cathode on the electron transport layer specifically includes: placing the substrate on which each functional layer has been deposited into an evaporation chamber and thermally vapor-depositing a layer of 15-30 nm metallic silver through a mask. Alternatively, aluminum or the like can be used as the cathode, or nano-Ag wires or Cu wires can be used. The above-mentioned materials have relatively low resistance so that carriers can be injected smoothly.

In some embodiments, a method for preparing a quantum dot light-emitting diode with an inverted structure is also provided, as shown in FIG. 4 , which includes the steps:

S01, providing a substrate, and the substrate is provided with a cathode;

S02, preparing an electron transport layer on the cathode, the electron transport layer material is a composite material, and the composite material includes zinc oxide nanoparticles and polypyrrole coated on the surface of the zinc oxide nanoparticles;

S03, preparing a quantum dot light-emitting layer on the electron transport layer;

S04, preparing a hole transport layer on the quantum dot light-emitting layer;

S05, preparing an anode on the hole transport layer to prepare the quantum dot light-emitting diode.

In some embodiments, the obtained quantum dot light-emitting diode is subjected to a packaging process, and the packaging process can be packaged by a common machine or by manual packaging. Specifically, in the packaging process environment, the oxygen content and the water content are both lower than 0.1 ppm, so as to ensure the stability of the QLED device.

A composite material, a preparation method thereof, and a quantum dot light-emitting diode of the present disclosure will be further explained below through specific examples:

The present disclosure provides a pair of examples, in Comparative Example 1:

1. The preparation steps of zinc oxide nanoparticle solution are as follows:

01. First, add an appropriate amount of zinc acetate into 50ml of ethanol solution to prepare a 1M zinc acetate ethanol solution, and stir and dissolve at 70°C to prepare precursor solution 1.

02. Weigh potassium hydroxide according to the mole ratio of Zn to OH- being 1:1.1, add sodium hydroxide to 50ml of ethanol solution to prepare 1.1M potassium hydroxide solution, stir and dissolve to obtain precursor solution 2.

02. Inject the precursor solution 1 into the precursor solution 2 at an injection rate of 10 mL/min, wash the prepared solution, and obtain an ethanol solution of zinc oxide nanoparticles.

2. The preparation steps of a QLED device with an upright structure are as follows:

01. Provide a substrate on which an ITO anode is provided;

03. Spin coating the TFB solution on the anode to obtain a hole transport layer;

04. Spin coating a layer of CdSe solution on the hole transport layer to obtain a quantum dot light-emitting layer;

05. Spin-coat the ethanol solution of the zinc oxide nanoparticles on the quantum dot layer to obtain an electron transport layer;

06. Evaporating a layer of Ag on the electron transport layer as a cathode to prepare the upright QLED device.

The present disclosure provides an embodiment, in Embodiment 1:

1. The preparation steps of the composite material are as follows:

01. First, add an appropriate amount of cetyltrimethylammonium bromide to 100ml of aqueous solution to prepare a 0.8M aqueous solution of cetyltrimethylammonium bromide, and then stir 3.2M at 0 °C. 3h, mixed solution 2 was obtained.

02. Weigh an appropriate amount of zinc acetate into 30ml methanol solution to prepare 1M zinc acetate methanol solution.

03. Weigh an appropriate amount of potassium hydroxide into 30ml methanol solution to prepare a 1.05M potassium hydroxide methanol solution.

04. Mix the potassium hydroxide solution and the zinc acetate solution, and stir for 0.5h, then add the mixed solution 2, stir at 60 ° C for 0.25h, and finally wash to obtain the zinc oxide solution;

05. Add the zinc oxide solution to ethanol for cleaning, and then centrifugal sedimentation to obtain the composite material precipitate;

06. Dissolve the composite material precipitate in chlorobenzene to obtain a composite material solution.

2. The preparation steps of the QLED device with the upright structure are as follows:

07. Provide a substrate, which is provided with an ITO anode;

08. Spin-coat TFB solution on ITO to obtain a hole transport layer;

09. Spin coating a layer of CdSe solution on the hole transport layer to obtain a quantum dot light-emitting layer;

10. Spin-coating the composite material solution on the quantum dot layer to obtain an electron transport layer;

11. Evaporating a layer of Ag on the electron transport layer as a cathode to prepare the upright QLED device.

The composite material obtained in Example 1 and the pure polypyrrole were tested by Fourier transform infrared spectroscopy. The results are shown in Figure 5. It can be seen from Figure 5 that the apparent peak intensity of the infrared spectrum of pure polypyrrole is weaker than the described The infrared spectrum of the composite material has obvious peak intensity, which proves that some of the C-N and N-H bonds in the composite material have been combined with zinc oxide, so the intensity becomes weak; The migration phenomenon proves that polypyrrole and zinc oxide have a strong connection relationship, indicating that the surface of zinc oxide nanoparticles in the composite material is coated with polypyrrole.

The present disclosure provides another embodiment, in Embodiment 2:

1. The preparation steps of the composite material are as follows:

01. First, add an appropriate amount of cetyltrimethylammonium chloride to 100ml of aqueous solution to prepare a 0.5M aqueous solution of cetyltrimethylammonium bromide, then stir 2M at 0°C for 5h to obtain mixed solution 2.

02. Weigh an appropriate amount of zinc chloride into 30ml ethanol solution to prepare 1M zinc acetate ethanol solution.

03. Weigh an appropriate amount of potassium hydroxide into 30ml ethanol solution to prepare a 1.1M potassium hydroxide ethanol solution.

04. Mix the potassium hydroxide solution and the zinc acetate solution, and stir for 1 hour, then add the mixed solution 2, stir at 60 ° C for 1 hour, and finally wash to obtain a zinc oxide solution.

06. Dissolve the precipitate in chlorobenzene to obtain a composite material solution;

2. The preparation steps of the upright QLED device are as follows:

07. Provide a substrate, which is provided with an ITO anode;

08. Spin-coat a layer of TFB solution on ITO to obtain a hole transport layer;

The present disclosure provides yet another embodiment, in Embodiment 3:

1. The preparation steps of the composite material are as follows:

01. First add an appropriate amount of cetyltrimethylammonium bromide to 100ml of aqueous solution to prepare a 1M aqueous solution of cetyltrimethylammonium bromide, then stir 4M at 0°C for 1h, A mixed solution 2 was obtained.

02. Weigh an appropriate amount of zinc acetate into 30ml ethanol solution to prepare 1M zinc acetate ethanol solution.

03. Weigh an appropriate amount of potassium hydroxide into 30ml ethanol solution to prepare a 1.3M potassium hydroxide ethanol solution.

04. Mix the potassium hydroxide solution and the zinc acetate solution, and stir for 0.5h, then add the mixed solution 2, stir at 60°C for 0.5h, and finally wash to obtain a zinc oxide solution.

2. The fabrication steps of the inverted QLED device are as follows:

07. Provide a substrate on which a cathode is provided;

08. Spin-coating the composite material solution on the cathode to obtain an electron transport layer;

09. Spin coating a layer of CdSe solution on the electron transport layer to obtain a quantum dot light-emitting layer;

10. Spin-coating the TFB solution on the quantum dot light-emitting layer to obtain a hole transport layer;

11. Evaporating a layer of ITO on the hole transport layer as an anode to prepare the inverted QLED device.

The performance test of the light-emitting diodes prepared in Examples 1-3 and Comparative Example 1 is carried out, and the test results are shown in Table 1 below:

Table 1

It can be seen from Table 1 that the external quantum efficiencies of the light-emitting diodes of Examples 1-3 are significantly higher than those of Comparative Example 1, indicating that the light-emitting diodes prepared in the embodiments of the present disclosure have better luminous efficiency.

Further, the conductive properties of the composite materials prepared in Examples 1-3 and the zinc oxide nanoparticles prepared in Comparative Example 1 were tested. The results are shown in FIG. 6 . It can be seen from FIG. The electrical conductivity of the composite material is significantly higher than that of the zinc oxide nanoparticles in Comparative Example 1, indicating that coating the polypyrrole on the surface of the zinc oxide nanoparticles can enhance its electrical conductivity.

To sum up, the composite material provided by the present disclosure includes zinc oxide nanoparticles and polypyrrole coated on the surface of the zinc oxide nanoparticles. The coating of the polypyrrole can effectively increase the space between the zinc oxide nanoparticles, passivate the surface of the zinc oxide nanoparticles, and reduce the generation of oxygen vacancies; the coating of the polypyrrole can also protect the zinc oxide nanoparticles from Agglomeration occurs; the surface of the pyrrole has N, C atoms, which can effectively provide an electron transport path and improve the electron transport capacity; the coating of the polypyrrole can also effectively isolate the corrosion of the zinc oxide nanoparticles by water and oxygen, compared with ordinary Ligand, polypyrrole is more dense.

It should be understood that the application of the present disclosure is not limited to the above-mentioned examples. For those of ordinary skill in the art, improvements or transformations can be made according to the above-mentioned descriptions, and all these improvements and transformations should belong to the protection scope of the appended claims of the present disclosure.

Claims

A method for preparing a composite material, comprising the steps of:

Mixing the pyrrole with the cationic surfactant to obtain a first mixed solution;

Disperse the basic compound in an organic alcohol solvent to obtain lye;

The lye solution is added to the zinc salt solution and mixed, then the first mixed solution is added to mix, and finally an oxidant is added to mix, and the composite material is prepared by reaction.
The preparation method of the composite material according to claim 1, wherein the cationic surfactant is stearyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium toluene sulfonate, octyl trimethyl ammonium chloride Ammonium, Dodecenylbis(hydroxyethyl)methylammonium chloride, Dodecenyltrimethylammonium chloride, Cetyltrimethylammonium chloride, Cetyltrimethylammonium chloride tetradecyl ammonium bromide, tetradecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, decyl One or more of decyltrimethylammonium chloride and decyltrimethylammonium bromide.
The preparation method of the composite material according to claim 1, wherein, in the step of adding pyrrole to the cationic surfactant, the molar ratio of the cationic surfactant to the pyrrole is 1:0.5-8.
The preparation method of the composite material according to claim 1, wherein the oxidant is ammonium persulfate or sodium persulfate.
The method for preparing a composite material according to claim 1, wherein the organic alcohol is one or more of isopropanol, ethanol, propanol, butanol, amyl alcohol and hexanol.
The method for preparing a composite material according to claim 1, wherein the zinc salt solution comprises an organic alcohol and a zinc salt dispersed in the organic alcohol.
The method for preparing a composite material according to claim 6, wherein the zinc salt is one or more of zinc acetate, zinc nitrate, zinc chloride, zinc sulfate and zinc acetate dihydrate.
The preparation method of the composite material according to claim 1, wherein, in the step of adding the alkali solution to the zinc salt solution, the zinc ions in the zinc salt and the hydroxide in the alkali solution The molar ratio of ions is 1:1-2.
The preparation method of the composite material according to claim 1, wherein the alkaline compound in the alkaline solution is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide and tetramethylammonium hydroxide pentahydrate kind.
A composite material comprising zinc oxide nanoparticles and polypyrrole coated on the surface of the zinc oxide nanoparticles.
The composite material of claim 10, wherein N in the polypyrrole is coordinately bound to zinc containing oxygen defects on the surface of the zinc oxide nanoparticles.
The composite material according to claim 10, wherein the polypyrrole has a conjugated structure in which carbon-carbon single bonds and carbon-carbon double bonds are alternately arranged.
A quantum dot light-emitting diode, comprising an electron transport layer, and the material of the electron transport layer is the composite material prepared by any one of the preparation methods of claims 1-9 or the composite material of any one of claims 10-12 Material.
The quantum dot light emitting diode according to claim 13, further comprising an anode, a cathode, a quantum dot light emitting layer disposed between the anode and the cathode, and a hole function disposed between the anode and the quantum dot light emitting layer layer, the electron transport layer is disposed between the cathode and the quantum dot light-emitting layer.
The quantum dot light-emitting diode according to claim 14, wherein the material of the quantum dot light-emitting layer is CdS, CdSe, CdTe, ZnO, ZnS, ZnSe, ZnTe, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs , InP, InSb, AlAs, AlP, CuInS, CuInSe, and one or more of various core-shell structure quantum dots or alloy structure quantum dots.
The quantum dot light-emitting diode according to claim 14, wherein the anode material is indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped tin oxide One or more of doped zinc oxide, magnesium-doped zinc oxide, and aluminum-doped magnesium oxide.
The quantum dot light-emitting diode according to claim 14, wherein the material of the cathode is one or more of a conductive carbon material, a conductive metal oxide material and a metal material.
The quantum dot light-emitting diode of claim 14, wherein the electron transport layer has a thickness of 70-90 nm.
The quantum dot light-emitting diode according to claim 14, wherein the hole functional layer is one or more of an electron blocking layer, a hole injection layer and a hole transport layer.
The quantum dot light-emitting diode according to claim 19, wherein the material of the hole transport layer is poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine), Polyvinylcarbazole, poly(N,N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), poly(9,9-dioctylfluorene-co-bis- N,N-phenyl-1,4-phenylenediamine), 4,4',4"-tris(carbazol-9-yl)triphenylamine, 4,4'-bis(9-carbazole)biphenyl , N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine, N,N'-diphenyl- One or more of N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, doped graphene, undoped graphene, and C60.