WO2018192334A1 - Acrylate copolymer modified metal oxide, preparation method and quantum dot light emitting diode - Google Patents

Acrylate copolymer modified metal oxide, preparation method and quantum dot light emitting diode Download PDF

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WO2018192334A1
WO2018192334A1 PCT/CN2018/079801 CN2018079801W WO2018192334A1 WO 2018192334 A1 WO2018192334 A1 WO 2018192334A1 CN 2018079801 W CN2018079801 W CN 2018079801W WO 2018192334 A1 WO2018192334 A1 WO 2018192334A1
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metal oxide
acrylate copolymer
quantum dot
light emitting
dot light
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PCT/CN2018/079801
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French (fr)
Chinese (zh)
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杨成玉
杨一行
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Tcl集团股份有限公司
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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]
    • H10K50/11—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
    • 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
    • H10K50/16—Electron transporting layers
    • 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
    • H10K50/16—Electron transporting layers
    • H10K50/165—Electron transporting layers comprising dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour

Definitions

  • the invention relates to the technical field of light-emitting diodes, in particular to an acrylate copolymer modified metal oxide, a preparation method thereof and a quantum dot light-emitting diode.
  • Quantum dots are nanocrystals with three dimensions in the order of nanometers. Due to their unique optical characteristics, such as adjustable luminescence spectrum, narrow half-width of luminescence, and high luminous efficiency, quantum dot materials are used.
  • QLED Quantum Dot Light Emitting Diode
  • OLED Organic Light-Emitting Diode
  • the basic structure of a quantum dot light emitting diode is an anode/light emitting layer/cathode.
  • the carrier injection and transfer capability of the device is an important criterion for measuring its performance.
  • an electron transport layer is usually disposed between the cathode of the quantum dot light emitting diode and the quantum dot light emitting layer.
  • the introduction of a suitable electron transport layer is an effective way to improve the ability of electron injection and transmission.
  • Commonly used electron transport and injection materials are lithium quinolate, 8-hydroxyquinoline aluminum, phenanthroline derivatives, oxadiazole derivatives, cesium carbonate, lithium fluoride, magnesium fluoride, calcium acetylacetonate, oxidation.
  • nano-zinc oxide as an electron transport material commonly used in quantum dot light-emitting diodes, has a conduction band level that facilitates electron injection from a cathode to a quantum dot, and its deep valence band energy level can also block air. The role of the hole.
  • These materials are usually formed into a film by vacuum evaporation or sputtering, which is time consuming and energy consuming, and is not conducive to achieving high volume roll-to-roll production.
  • electron transport materials particularly metal oxides, such as nano zinc oxide, are generally prepared by a low temperature sol-gel method, and the resulting nano metal oxide has a low crystallinity.
  • the present invention aims to provide an acrylate copolymer modified metal oxide, a preparation method thereof and a quantum dot light emitting diode, which aims to solve the structural defects of the existing electron transport materials and lead to electron transport.
  • the problem of low transportability and light transmission of the layer is a problem of low transportability and light transmission of the layer.
  • a method for preparing an acrylate copolymer modified metal oxide comprising:
  • the mixture was purified by adding a solvent, and centrifuged to obtain an acrylate copolymer-modified metal oxide.
  • the method for preparing an acrylate copolymer-modified metal oxide wherein the metal oxide solution has a concentration of 10 to 100 mg/ml.
  • the method for producing an acrylate copolymer-modified metal oxide wherein 2-20 ml of an acrylate copolymer solution is added to a prepared 2-20 ml of a metal oxide solution.
  • the method for preparing an acrylate copolymer-modified metal oxide wherein the atmosphere is one of an inert atmosphere, a vacuum atmosphere, and an air atmosphere.
  • An acrylate copolymer-modified metal oxide prepared by the method for preparing a metal oxide modified by the acrylate copolymer of the present invention.
  • the acrylate copolymer-modified metal oxide wherein the acrylate copolymer-modified metal oxide has a particle diameter ranging from 3 to 50 nm.
  • the acrylate copolymer modified metal oxide wherein the metal oxide is zinc oxide or titanium oxide.
  • a quantum dot light emitting diode wherein the quantum dot light emitting diode comprises an electron transport layer, and the material of the electron transport layer is an acrylate copolymer modified metal oxide according to the invention.
  • the quantum dot light emitting diode wherein the quantum dot light emitting diode further comprises a substrate including a bottom electrode and a top electrode, and a quantum dot light emitting layer is disposed between the substrate and the top electrode, and the electron transport The layer is disposed between the quantum dot emitting layer and the top electrode, and an interface modifying layer is disposed between the quantum dot emitting layer and the electron transporting layer.
  • the quantum dot light emitting diode wherein the electron transport layer has a thickness ranging from 3 to 100 nm.
  • the quantum dot light emitting diode wherein the interface modification layer has a thickness ranging from 0.5 to 20 nm.
  • the quantum dot light emitting diode wherein the interface modification layer is made of a material having a relatively high polarity which is easily dissolved in an alcohol solvent but insoluble in an alkane.
  • the quantum dot light emitting diode wherein the material is one of epoxy resin, polyacrylic acid, polyethyleneimine, polyvinylpyrrolidone, polyethoxyethyleneimine, polyethylene glycol, polyethylene oxide Or a variety.
  • the quantum dot light emitting diode wherein the alcohol solvent is an alcohol having a total of 1-14 carbon atoms.
  • the present invention utilizes an acrylate copolymer to modify a metal oxide, on the one hand, it can passivate surface defects of metal oxides, reduce surface defects, quenching of excitons and recombination of carriers, and on the other hand, can improve metal The oxide surface potential, thereby improving the electron injection level and electron transporting ability, and the acrylate copolymer can improve the dispersibility of the metal oxide nanoparticles, facilitate the formation of a smooth film layer, and improve the light transmittance of the film.
  • Figure 1 is a molecular structural formula of an acrylate copolymer of the present invention.
  • FIG. 2 is a schematic structural view of a preferred embodiment of a quantum dot light emitting diode according to the present invention.
  • FIG. 3 is a flow chart of a preferred embodiment of a method of fabricating a quantum dot light emitting diode of the present invention.
  • the present invention provides an acrylate copolymer-modified metal oxide, a preparation method thereof, and a quantum dot light-emitting diode.
  • the present invention will be further described in detail below in order to clarify and clarify the objects, technical solutions and effects of the present invention. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
  • Step (1) adding an acrylate copolymer solution to a prepared metal oxide solution under a certain atmosphere to cause a metal coordination reaction to obtain an acrylate copolymer-modified metal oxide mixed solution;
  • an acrylate copolymer is prepared, and then the acrylate copolymer is formulated into an acrylate copolymer solution.
  • the present invention also prepares a metal oxide which is then formulated into a metal oxide solution.
  • the molecular structure formula of the acrylate copolymer of the present invention is shown in FIG. 1.
  • the preparation method of the acrylate copolymer is described in detail below by way of specific examples, but the preparation method is not limited thereto.
  • the present invention dissolves the prepared acrylate copolymer in a xylene solvent to prepare an acrylate copolymer solution having a concentration of 10 to 100 mg/ml.
  • the present invention uses a sol-gel method to prepare a metal oxide.
  • the sol-gel method for preparing a metal oxide is known in the art and will not be described herein.
  • the prepared metal oxide is then formulated into a metal oxide solution having a concentration of 10-100 mg/ml.
  • step (1) 2-20 ml of the acrylate copolymer solution is added to a prepared 2-20 ml of a metal oxide solution under a certain atmosphere, and then at 60-80 ° C (for example, 70 ° C). Stir at a temperature of 0.5-8 h (for example, 1 h) to obtain a mixed solution.
  • the atmosphere of the present invention may be one of an inert atmosphere, a vacuum atmosphere, and an air atmosphere, and the preferred atmosphere is an air atmosphere.
  • the metal coordination reaction means that the N element in the acrylate copolymer is coordinated with the metal element in the metal oxide to obtain an acrylate copolymer-modified metal oxide.
  • Step (2) adding a solvent to purify the mixture, and centrifuging to obtain an acrylate copolymer-modified metal oxide.
  • the mixture was purified by adding a solvent such as methanol, and centrifuged at 8000 rpm for 5 minutes, and then filtered to remove the filtrate to obtain a white precipitate which is an acrylate copolymer-modified metal oxide.
  • a solvent such as methanol
  • the acrylate copolymer modified metal oxide prepared by the invention is soluble in an alkane solution, and the obtained acrylate copolymer modified metal oxide dispersion has the following characteristics: stable nanoparticle property, small particle size and uniformity Well, the dispersant is an alkane, and the concentration of the solution after the dispersion of the nanoparticles is controllable; the transparency of the film is good.
  • the invention utilizes an acrylate copolymer to modify the metal oxide, on the one hand, it can passivate the surface defects of the metal oxide, reduce the quenching of the exciton and the recombination of the carrier by the surface defect, and can improve the surface of the metal oxide on the other hand.
  • the electric potential, thereby improving the electron injection level and the electron transporting ability, and the acrylate copolymer can improve the dispersibility of the metal oxide nanoparticles, thereby facilitating the formation of a smooth film layer and improving the light transmittance of the film.
  • the present invention provides an acrylate copolymer-modified metal oxide prepared by a method for producing a metal oxide modified by an acrylate copolymer as described above.
  • the acrylate copolymer modified metal oxide has a particle size ranging from 3 to 50 nm.
  • the surface of the metal oxide prepared by the existing low-temperature sol-gel method has many defects, resulting in low transportability and light transmittance of the electron transport layer made of metal oxide.
  • the present invention utilizes an acrylate copolymer to modify a metal oxide, on the one hand, it can passivate the surface defects of the metal oxide, reduce the quenching of excitons and the recombination of carriers by surface defects, and the like.
  • the aspect can improve the surface potential of the metal oxide, thereby improving the electron injection level and the electron transporting ability.
  • the acrylate copolymer can improve the dispersibility of the metal oxide nanoparticles, and is favorable for forming a smooth film layer and improving the light transmittance of the film. .
  • a quantum dot light emitting diode according to the present invention wherein the quantum dot light emitting diode comprises an electron transport layer, and the material of the electron transport layer is an acrylate copolymer modified metal oxide according to the present invention.
  • the quantum dot light emitting diode further includes a substrate including a bottom electrode and a top electrode, and a quantum dot light emitting layer is disposed between the substrate and the top electrode, and the electron transport layer is disposed on the quantum Between the point light-emitting layer and the top electrode, an interface modification layer is disposed between the quantum dot light-emitting layer and the electron transport layer.
  • the quantum dot light emitting diode comprises a substrate 1 including a bottom electrode 2 and a hole injection layer 3 provided in a stack.
  • a hole transport layer 4 a quantum dot light-emitting layer 5, an interface modification layer 6, an electron transport layer 7, and a top electrode 8;
  • the material of the electron transport layer 7 is an acrylate copolymer-modified metal oxide as described above Things.
  • the invention utilizes the metal oxide modified by the acrylate copolymer as the material of the electron transport layer in the quantum dot light emitting diode, on the one hand, the surface defect of the metal oxide can be reduced, and the exciton quenching and carrier recombination can be reduced.
  • the electron injection level and electron transport ability can be improved, and the acrylate copolymer can improve the dispersibility of the metal oxide nanoparticles, facilitate the formation of a smooth film layer, and improve the light transmittance of the film.
  • a flow chart of a preferred embodiment of a method for fabricating a quantum dot light-emitting diode of the present invention includes:
  • Step S100 preparing a hole injection layer on a substrate containing a bottom electrode, and preparing a hole transport layer on the hole injection layer;
  • the material of the substrate containing the bottom electrode may be a transparent conductive material in the visible light region, and the transparent conductive material in the visible light region may be, but not limited to, indium tin oxide (ITO), indium zinc oxide (IZO), or the like.
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • the preferred visible light region transparent conductive material is ITO.
  • the method further comprises: first cleaning the substrate containing the bottom electrode, and then treating the surface of the substrate with ultraviolet ozone or oxygen plasma.
  • the specific cleaning process includes: using a dust-free cloth to extract the detergent, gently wiping the surface of the substrate (such as ITO) containing the bottom electrode several times, rinsing with deionized water, and then ultrasonically using ultrapure water, acetone, and ethanol. After washing for 15 minutes, after the completion of the ultrasonication, the substrate containing the bottom electrode was placed in a clean oven for drying, and the dried substrate containing the bottom electrode was irradiated for 5 minutes in an ozone ultraviolet cleaner (UVO).
  • UVO ozone ultraviolet cleaner
  • the material of the hole injection layer may be one or more of PEDOT:PSS, MoO 3 , Nb 2 O 5 , NiO, etc.; the thickness of the film layer ranges from 20 to 80 nm.
  • the material of the hole transport layer may be an organic compound or metal oxide having electron donating ability, and the organic compound having electron donating ability may be NPB, TPD, TAPC, TFB, OTPD, QTPD, Poly- One or more of TPD, PVK, etc.; the metal oxide may be one or more of molybdenum oxide, vanadium oxide, nickel oxide, copper oxide, tungsten oxide, and the like. This film thickness can range from 10 to 100 nm.
  • the method of depositing the hole injecting layer and the hole transporting layer of the present invention is not limited and may be deposited by a conventional solution processing method in the art, such as ink jet printing, spin coating, spray coating, or the like.
  • Step S200 preparing a quantum dot light-emitting layer on the hole transport layer, preparing an interface modification layer on the quantum dot light-emitting layer, and then preparing an electron transport layer on the interface modification layer;
  • the material of the electron transport layer is as described above Acrylate copolymer modified metal oxide;
  • the material of the quantum dot luminescent layer may be at least one of a common red light quantum dot, a green light quantum dot, a blue light quantum dot and a yellow light quantum dot, and an infrared light quantum dot and an ultraviolet light quantum dot.
  • the method of depositing the quantum dot luminescent layer of the present invention is not limited and may be deposited by conventional solution processing methods in the art, such as ink jet printing, spin coating, spray coating, and the like.
  • the interfacial modification layer is made of a highly polar material which is soluble in an alcohol solvent but insoluble in an alkane, such as epoxy resin, polyacrylic acid, polyethyleneimine (PEI), polyvinylpyrrolidone (PVP). ), one or more of PEIE (polyethoxyethyleneimine), PEG (polyethylene glycol), PEO (polyethylene oxide), etc.; the film is formed by using a total of 1-14 carbon atoms.
  • the solvent is formed into a film by spin coating, spray coating or ink jet printing, and the film thickness ranges from 0.5 to 20 nm.
  • the dispersion solvent of the commonly used quantum dots is an alkane
  • the metal oxide dispersion solvent modified by the acrylate copolymer is also an alkane
  • the acrylate copolymer-modified metal oxide thin film layer is directly deposited on the quantum dot light-emitting layer by a solution film formation method. It will cause damage to adjacent layers. Therefore, the present invention deposits the interface modification layer on the quantum dot luminescent layer, which can effectively prevent the destruction of the adjacent film layer by depositing the acrylate copolymer modified metal oxide film layer directly on the quantum dot luminescent layer by the solution method.
  • the performance of each film layer is kept intact, and the interface modification layer can also function to block holes and the like.
  • the metal oxide may be, but not limited to, zinc oxide, titanium oxide, or the like.
  • the metal oxide is nano zinc oxide.
  • the acrylate copolymer-modified nano zinc oxide has a particle size ranging from 3 to 50 nm.
  • the acrylate copolymer modified metal oxide is soluble in an alkane but insoluble in an alcohol; in the film formation, the acrylate copolymer modified metal oxide is dispersed in an alkane molecule, and the solution concentration ranges from 0.1 to 300 mg.
  • the layer thickness is 3-100 nm.
  • Step S300 preparing a top electrode on the electron transport layer, and then performing packaging to obtain a quantum dot light emitting diode.
  • a top electrode having a thickness of 10-500 nm is prepared by vapor deposition on the electron transport layer, and after the evaporation is completed, the top electrode is packaged to obtain a quantum dot light emitting diode.
  • the invention can be used with conventional machine packages or simple manual packages.
  • the top electrode may be one or more of aluminum, silver, gold, platinum, copper, magnesium, calcium, barium, titanium, and the like.
  • the film layers in order to prepare the film layers by using the solution method, in order to adjust the morphology of the film layers, the film layers may be annealed separately, the annealing temperature ranges from 100 ° C to 300 ° C, and the annealing time is 1- 120 minutes.
  • the invention utilizes an acrylate copolymer modified metal oxide, in particular nano zinc oxide, as an electron transport layer of a quantum dot light emitting diode.
  • the acrylate copolymer inactivates metal oxide surface defects, thereby reducing surface defects on excitons. Quenching and carrier recombination enhances its electron transport capability; on the other hand, modification of nanometal oxide by acrylate copolymer can increase the surface potential of metal oxide, thereby improving the level of electron injection; in addition, the improvement of acrylate copolymer
  • the dispersing ability of the metal oxide is favorable for forming a smooth film layer and improving the light transmittance of the film.
  • the invention can realize the preparation of an electron transport layer by a solution method, wherein the metal oxide modified by the acrylate copolymer is easily soluble in an alkane, and an interface modification layer is added between the quantum oxide layer modified by the quantum dot light-emitting layer and the acrylate copolymer.
  • the interface modification layer material is soluble in the alcohol solution and is insoluble in the alkane, so that the electron transport layer can be prepared by the solution method.
  • the solution method can improve the utilization rate of the material, simplify the process, and reduce the production cost. Achieve large-scale production.
  • the preparation steps of the acrylate copolymer modified zinc oxide nanoparticle dispersion are as follows:
  • the white precipitate was redispersed with a n-octane solution to obtain an acrylate copolymer-modified zinc oxide nanoparticle dispersion having a concentration of about 5 mg/ml.
  • the acrylate copolymer-modified zinc oxide nanoparticle dispersion has the following characteristics: the nanoparticle has stable properties, small particle size and good uniformity, the dispersant is an alkane, and the concentration of the solution after the dispersion of the nanoparticles is controllable; .
  • the preparation steps of the quantum dot light emitting diode are as follows:
  • the ITO substrate is cleaned, and then the surface of the ITO substrate is treated with ultraviolet ozone.
  • the specific cleaning process includes: gently rubbing the detergent on the surface of the ITO substrate with a dust-free cloth, rinsing with deionized water, and then ultrasonically cleaning with ultrapure water, acetone, and ethanol for 15 minutes, after the ultrasonication is completed.
  • the ITO substrate was placed in a clean oven for drying, and after drying, the ITO substrate was placed in an ultraviolet ozone cleaner (UVO) for 5 minutes.
  • UVO ultraviolet ozone cleaner
  • a PEDOT:PSS hole injection layer was deposited on the ITO substrate by spin coating, and then the solvent in the PEDOT:PSS hole injection layer was removed by heating at 120 ° C for 20 min. By this method, the solvent in the PEDOT:PSS hole injection layer can be effectively removed, and at the same time, a dense PEDOT:PSS film can be formed.
  • the aluminum electrode is thermally evaporated onto the substrate.
  • the thickness of the aluminum layer is controlled to be around 100 nm.
  • the acrylate copolymer-modified zinc oxide nanoparticle precipitate was prepared in the same manner as in Example 1, and then the acrylate copolymer-modified zinc oxide nanoparticles were redispersed with an octadecane solution to obtain a final concentration of about 3 mg/ml. Acrylate copolymer modified zinc oxide nanoparticle dispersion.
  • a quantum dot light-emitting diode was prepared according to the method of Example 1, except that the hole transport layer was vacuum-deposited and the quantum dot light-emitting layer was vacuum-evaporated: the triphenylamine compound 4,4'-di-(N-naphthyl group was selected.
  • -N-Phenylamino)biphenyl (NPB) As a hole transporting layer, the NPB film layer was vacuum-vapor-deposited at a vacuum of 3 ⁇ 10 -4 Pa using a vacuum coater to have a thickness of 30 nm.
  • the quantum dot light-emitting layer was deposited on the hole transport layer under a vacuum of 3 ⁇ 10 -4 Pa by a vacuum coater.
  • the present invention provides an acrylate copolymer modified metal oxide and a preparation method thereof and a quantum dot light emitting diode.
  • the invention utilizes an acrylate copolymer to modify the metal oxide, on the one hand, it can passivate the surface defects of the metal oxide, reduce the quenching of the exciton and the recombination of the carrier by the surface defect, and can improve the surface of the metal oxide on the other hand.
  • the electric potential, thereby improving the electron injection level and the electron transporting ability, and the acrylate copolymer can improve the dispersibility of the metal oxide nanoparticles, thereby facilitating the formation of a smooth film layer and improving the light transmittance of the film.

Abstract

An acrylate copolymer modified metal oxide and a preparation method thereof are provided. The method comprises following steps: adding an acrylate copolymer solution to a metal oxide solution prepared in advance under a certain atmosphere and performing a metal coordination reaction to obtain an acrylate copolymer modified metal oxide mixture solution; and adding a solvent to the mixture solution and performing refining and purification, and separating by centrifugal force to obtain the acrylate copolymer modified metal oxide. A quantum dot light emitting diode is further provided, the quantum dot light emitting diode comprising an electron transport layer, wherein a material of the electron transport layer is the acrylate copolymer modified metal oxide. By utilizing an acrylate copolymer to modify a metal oxide, surface defects of the metal oxide can be passivated, reducing the quenching of excitons and the recombination of carriers by the surface defects, and the surface potential of the metal oxide can be increased, thereby improving the electron injection level and electron transport ability. Moreover, the acrylate copolymer can improve the dispersibility of nanoparticles of the metal oxide, facilitating the formation of a smooth film layer and increasing the light transmittance of a film.

Description

丙烯酸酯共聚物修饰的金属氧化物及制备方法与量子点发光二极管Acrylate copolymer modified metal oxide and preparation method thereof and quantum dot light emitting diode 技术领域Technical field
本发明涉及发光二极管技术领域，尤其涉及一种丙烯酸酯共聚物修饰的金属氧化物及制备方法与量子点发光二极管。The invention relates to the technical field of light-emitting diodes, in particular to an acrylate copolymer modified metal oxide, a preparation method thereof and a quantum dot light-emitting diode.
背景技术Background technique
量子点(quantum dot)是三个维度尺寸均在纳米数量级的纳米晶，由于其具有独特的光学特点，如发光光谱可调、发光半峰宽极窄、发光效率高等特点，将量子点材料制成量子点发光二极管(Quantum Dot Light Emitting Diode，简称QLED)，可以实现比有机电致发光二极管(Organic Light-Emitting Diode，简称OLED)显示器件更好的色域，其有望成为下一代平板技术的选择。Quantum dots are nanocrystals with three dimensions in the order of nanometers. Due to their unique optical characteristics, such as adjustable luminescence spectrum, narrow half-width of luminescence, and high luminous efficiency, quantum dot materials are used. A Quantum Dot Light Emitting Diode (QLED) can achieve a better color gamut than an Organic Light-Emitting Diode (OLED) display device, which is expected to become the next generation of flat panel technology. select.
量子点发光二极管的基本结构为阳极/发光层/阴极。器件的载流子的注入和传输能力是衡量其性能优劣的一个重要标准。为了提高电子的注入效率，通常在量子点发光二极管的阴极和量子点发光层之间设置电子传输层。引入合适的电子传输层来成为提高电子注入和传输能力的有效途径。常用的电子传输和注入材料有8-羟基喹啉锂，8-羟基喹啉铝，菲啰啉衍生物，噁二唑衍生物，碳酸铯，氟化锂，氟化镁，乙酰丙酮钙，氧化锌等。特别是纳米氧化锌，作为量子点发光二极管中普遍采用的电子传输材料，其导带能级有利于电子从阴极到量子点的注入，且其较深的价带能级又可起到阻挡空穴的作用。这些材料通常是依靠真空蒸镀或溅射的方法制备成膜，耗时耗能，且不利于实现大批量的卷对卷生产。目前，溶液加工制备电子传输层时，电子传输材料特别是金属氧化物，如纳米氧化锌的制备一般采用低温的溶胶-凝胶方法，由此得到的纳米金属氧化物，其结晶度较低，存在大量的结构缺陷如空位、位错等，这些结构缺陷成为激子的无辐射复合中心，从而降低器件的传输性和透光性，影响量子点发光二极管的发光效率。此外，现有的电子传输材料如纳米氧化锌的导带能级还不够低，其注入效率特别是在蓝光器件中的注入效率不是非常有效。The basic structure of a quantum dot light emitting diode is an anode/light emitting layer/cathode. The carrier injection and transfer capability of the device is an important criterion for measuring its performance. In order to improve the injection efficiency of electrons, an electron transport layer is usually disposed between the cathode of the quantum dot light emitting diode and the quantum dot light emitting layer. The introduction of a suitable electron transport layer is an effective way to improve the ability of electron injection and transmission. Commonly used electron transport and injection materials are lithium quinolate, 8-hydroxyquinoline aluminum, phenanthroline derivatives, oxadiazole derivatives, cesium carbonate, lithium fluoride, magnesium fluoride, calcium acetylacetonate, oxidation. Zinc and so on. In particular, nano-zinc oxide, as an electron transport material commonly used in quantum dot light-emitting diodes, has a conduction band level that facilitates electron injection from a cathode to a quantum dot, and its deep valence band energy level can also block air. The role of the hole. These materials are usually formed into a film by vacuum evaporation or sputtering, which is time consuming and energy consuming, and is not conducive to achieving high volume roll-to-roll production. At present, when solution processing is used to prepare an electron transport layer, electron transport materials, particularly metal oxides, such as nano zinc oxide, are generally prepared by a low temperature sol-gel method, and the resulting nano metal oxide has a low crystallinity. There are a large number of structural defects such as vacancies, dislocations, etc. These structural defects become the non-radiative recombination centers of excitons, thereby reducing the transmission and light transmission of the device and affecting the luminous efficiency of the quantum dot light emitting diode. In addition, the conduction band energy levels of existing electron transport materials such as nano zinc oxide are not sufficiently low, and the injection efficiency, particularly the implantation efficiency in blue light devices, is not very effective.
因此，迫切需要找到合适的材料修饰电子传输层的金属氧化物特别是ZnO，以减少其表面缺陷，提高电子传输性能和透光性，提高器件整体性能。Therefore, it is urgent to find a suitable material to modify the metal oxide of the electron transport layer, especially ZnO, to reduce surface defects, improve electron transport performance and light transmittance, and improve overall device performance.
发明内容Summary of the invention
鉴于上述现有技术的不足，本发明的目的在于提供一种丙烯酸酯共聚物修饰的金属氧化物及制备方法与量子点发光二极管，旨在解决现有电子传输材料结构缺陷较多，导致电子传输层的传输性和透光性较低的问题。In view of the above deficiencies of the prior art, the present invention aims to provide an acrylate copolymer modified metal oxide, a preparation method thereof and a quantum dot light emitting diode, which aims to solve the structural defects of the existing electron transport materials and lead to electron transport. The problem of low transportability and light transmission of the layer.
本发明的技术方案如下：The technical solution of the present invention is as follows:
一种丙烯酸酯共聚物修饰的金属氧化物的制备方法，其中，包括：A method for preparing an acrylate copolymer modified metal oxide, comprising:
在一定气氛下，将丙烯酸酯共聚物溶液添加至预先备好的金属氧化物溶液中，发生金属配位反应，得到丙烯酸酯共聚物修饰的金属氧化物混合液；Adding an acrylate copolymer solution to a prepared metal oxide solution under a certain atmosphere to cause a metal coordination reaction to obtain an acrylate copolymer-modified metal oxide mixture;
加入溶剂对所述混合液进行提纯，并离心分离，获取丙烯酸酯共聚物修饰的金属氧化物。The mixture was purified by adding a solvent, and centrifuged to obtain an acrylate copolymer-modified metal oxide.
所述的丙烯酸酯共聚物修饰的金属氧化物的制备方法，其中，所述丙烯酸酯共聚物溶液的浓度为10-100mg/ml。The method for preparing an acrylate copolymer-modified metal oxide, wherein the acrylate copolymer solution has a concentration of 10 to 100 mg/ml.
所述的丙烯酸酯共聚物修饰的金属氧化物的制备方法，其中，所述金属氧化物溶液的浓度为10-100mg/ml。The method for preparing an acrylate copolymer-modified metal oxide, wherein the metal oxide solution has a concentration of 10 to 100 mg/ml.
所述的丙烯酸酯共聚物修饰的金属氧化物的制备方法，其中，将2-20ml丙烯酸酯共聚物溶液添加至预先备好的2-20ml金属氧化物溶液中。The method for producing an acrylate copolymer-modified metal oxide, wherein 2-20 ml of an acrylate copolymer solution is added to a prepared 2-20 ml of a metal oxide solution.
所述的丙烯酸酯共聚物修饰的金属氧化物的制备方法，其中，所述气氛为惰性氛围、真空氛围、空气氛围中的一种。The method for preparing an acrylate copolymer-modified metal oxide, wherein the atmosphere is one of an inert atmosphere, a vacuum atmosphere, and an air atmosphere.
所述的丙烯酸酯共聚物修饰的金属氧化物的制备方法，其中，所述溶剂为甲醇。The method for preparing an acrylate copolymer-modified metal oxide, wherein the solvent is methanol.
所述的丙烯酸酯共聚物修饰的金属氧化物的制备方法，其中，所述金属配位反应的温度为60-80℃。The method for preparing an acrylate copolymer-modified metal oxide, wherein the metal coordination reaction has a temperature of 60-80 ° C.
所述的丙烯酸酯共聚物修饰的金属氧化物的制备方法，其中，所述金属配位反应的时间为0.5-8h。The method for preparing an acrylate copolymer-modified metal oxide, wherein the metal coordination reaction has a time of 0.5-8 h.
一种丙烯酸酯共聚物修饰的金属氧化物，其中，采用本发明所述的丙烯酸酯共聚物修饰的金属氧化物的制备方法制备而成。An acrylate copolymer-modified metal oxide prepared by the method for preparing a metal oxide modified by the acrylate copolymer of the present invention.
所述的丙烯酸酯共聚物修饰的金属氧化物，其中，所述丙烯酸酯共聚物修饰的金属氧化物的粒径范围为3-50nm。The acrylate copolymer-modified metal oxide, wherein the acrylate copolymer-modified metal oxide has a particle diameter ranging from 3 to 50 nm.
所述的丙烯酸酯共聚物修饰的金属氧化物，其中，所述金属氧化物为氧化锌 或氧化钛。The acrylate copolymer modified metal oxide, wherein the metal oxide is zinc oxide or titanium oxide.
一种量子点发光二极管，其中，所述量子点发光二极管包括电子传输层，所述电子传输层的材料为本发明所述的丙烯酸酯共聚物修饰的金属氧化物。A quantum dot light emitting diode, wherein the quantum dot light emitting diode comprises an electron transport layer, and the material of the electron transport layer is an acrylate copolymer modified metal oxide according to the invention.
所述的量子点发光二极管，其中，所述量子点发光二极管还包括含有底电极的衬底和顶电极，所述衬底和所述顶电极之间设置有量子点发光层，所述电子传输层设置于所述量子点发光层和所述顶电极之间，所述量子点发光层和所述电子传输层之间设置有界面修饰层。The quantum dot light emitting diode, wherein the quantum dot light emitting diode further comprises a substrate including a bottom electrode and a top electrode, and a quantum dot light emitting layer is disposed between the substrate and the top electrode, and the electron transport The layer is disposed between the quantum dot emitting layer and the top electrode, and an interface modifying layer is disposed between the quantum dot emitting layer and the electron transporting layer.
所述的量子点发光二极管，其中，所述电子传输层的厚度范围为3-100nm。The quantum dot light emitting diode, wherein the electron transport layer has a thickness ranging from 3 to 100 nm.
所述的量子点发光二极管，其中，所述界面修饰层的厚度范围为0.5-20nm。The quantum dot light emitting diode, wherein the interface modification layer has a thickness ranging from 0.5 to 20 nm.
所述的量子点发光二极管，其中，所述界面修饰层由易溶解于醇类溶剂但不溶于烷烃的极性较大的材料制成。The quantum dot light emitting diode, wherein the interface modification layer is made of a material having a relatively high polarity which is easily dissolved in an alcohol solvent but insoluble in an alkane.
所述的量子点发光二极管，其中，所述材料为环氧树脂、聚丙烯酸、聚乙烯亚胺、聚乙烯吡咯烷酮、聚乙氧基乙烯亚胺、聚乙二醇、聚氧化乙烯中的一种或多种。The quantum dot light emitting diode, wherein the material is one of epoxy resin, polyacrylic acid, polyethyleneimine, polyvinylpyrrolidone, polyethoxyethyleneimine, polyethylene glycol, polyethylene oxide Or a variety.
所述的量子点发光二极管，其中，所述醇类溶剂为碳原子总数为1-14的醇。The quantum dot light emitting diode, wherein the alcohol solvent is an alcohol having a total of 1-14 carbon atoms.
有益效果：本发明利用丙烯酸酯共聚物修饰金属氧化物，一方面可以起到钝化金属氧化物表面缺陷，减少表面缺陷对激子的淬灭和载流子的复合，另一方面可以提高金属氧化物表面电势，从而改善电子的注入水平和电子传输能力，此外丙烯酸酯共聚物可改善金属氧化物纳米粒子的分散性，有利于形成光滑的薄膜层，提高了膜的透光性。Advantageous Effects: The present invention utilizes an acrylate copolymer to modify a metal oxide, on the one hand, it can passivate surface defects of metal oxides, reduce surface defects, quenching of excitons and recombination of carriers, and on the other hand, can improve metal The oxide surface potential, thereby improving the electron injection level and electron transporting ability, and the acrylate copolymer can improve the dispersibility of the metal oxide nanoparticles, facilitate the formation of a smooth film layer, and improve the light transmittance of the film.
附图说明DRAWINGS
图1为本发明丙烯酸酯共聚物的分子结构式。Figure 1 is a molecular structural formula of an acrylate copolymer of the present invention.
图2为本发明一种量子点发光二极管较佳实施例的结构示意图。2 is a schematic structural view of a preferred embodiment of a quantum dot light emitting diode according to the present invention.
图3为本发明一种量子点发光二极管的制备方法较佳实施例的流程图。3 is a flow chart of a preferred embodiment of a method of fabricating a quantum dot light emitting diode of the present invention.
具体实施方式detailed description
本发明提供一种丙烯酸酯共聚物修饰的金属氧化物及制备方法与量子点发光二极管，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。The present invention provides an acrylate copolymer-modified metal oxide, a preparation method thereof, and a quantum dot light-emitting diode. The present invention will be further described in detail below in order to clarify and clarify the objects, technical solutions and effects of the present invention. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
本发明的一种丙烯酸酯共聚物修饰的金属氧化物的制备方法较佳实施例，其包括：A preferred embodiment of a method for preparing an acrylate copolymer-modified metal oxide of the present invention comprises:
步骤(1)、在一定气氛下，将丙烯酸酯共聚物溶液添加至预先备好的金属氧化物溶液中，发生金属配位反应，得到丙烯酸酯共聚物修饰的金属氧化物混合液；Step (1), adding an acrylate copolymer solution to a prepared metal oxide solution under a certain atmosphere to cause a metal coordination reaction to obtain an acrylate copolymer-modified metal oxide mixed solution;
本发明上述步骤(1)之前，先制备丙烯酸酯共聚物，然后将丙烯酸酯共聚物配制成丙烯酸酯共聚物溶液。同时，本发明还制备金属氧化物，然后将金属氧化物配制成金属氧化物溶液。Prior to the above step (1) of the present invention, an acrylate copolymer is prepared, and then the acrylate copolymer is formulated into an acrylate copolymer solution. At the same time, the present invention also prepares a metal oxide which is then formulated into a metal oxide solution.
具体地，本发明所述丙烯酸酯共聚物的分子结构式如图1所示，下面通过具体实施例对所述丙烯酸酯共聚物的制备方法进行详细说明，但制备方法不限于此。Specifically, the molecular structure formula of the acrylate copolymer of the present invention is shown in FIG. 1. The preparation method of the acrylate copolymer is described in detail below by way of specific examples, but the preparation method is not limited thereto.
先将甲基丙烯酸甲酯6.2g、丙烯酸丁酯3.3g、N,N-二甲基丙烯酸乙酯0.5g和偶氮二异丁腈0.2g溶解于15mL甲苯中，然后在80℃下于氮气气氛中聚合反应8小时。反应完毕后降温，接着用甲醇沉淀，得到约9.8g丙烯酸酯共聚物。将所得的丙烯酸酯共聚物于40℃下真空干燥，备用。First, 6.2 g of methyl methacrylate, 3.3 g of butyl acrylate, 0.5 g of N,N-dimethacrylate, and 0.2 g of azobisisobutyronitrile were dissolved in 15 mL of toluene, followed by nitrogen at 80 ° C. The polymerization was carried out for 8 hours in the atmosphere. After completion of the reaction, the temperature was lowered, followed by precipitation with methanol to obtain about 9.8 g of an acrylate copolymer. The obtained acrylate copolymer was vacuum dried at 40 ° C until use.
具体地，本发明将制备好的丙烯酸酯共聚物溶于二甲苯溶剂中，配制成浓度为10-100mg/ml的丙烯酸酯共聚物溶液。Specifically, the present invention dissolves the prepared acrylate copolymer in a xylene solvent to prepare an acrylate copolymer solution having a concentration of 10 to 100 mg/ml.
具体地，本发明采用溶胶凝胶法制备金属氧化物，所述溶胶凝胶法制备金属氧化物为现有技术，在此不再赘述。然后将制备好的金属氧化物配制成浓度为10-100mg/ml的金属氧化物溶液。Specifically, the present invention uses a sol-gel method to prepare a metal oxide. The sol-gel method for preparing a metal oxide is known in the art and will not be described herein. The prepared metal oxide is then formulated into a metal oxide solution having a concentration of 10-100 mg/ml.
具体地，上述步骤(1)中，在一定气氛下，将2-20ml丙烯酸酯共聚物溶液添加至预先备好的2-20ml金属氧化物溶液中，然后在60-80℃(如70℃)温度下，搅拌0.5-8h(如1h)，得到混合液。本发明所述气氛可以为惰性氛围、真空氛围、空气氛围中的一种，优选的气氛为空气氛围。Specifically, in the above step (1), 2-20 ml of the acrylate copolymer solution is added to a prepared 2-20 ml of a metal oxide solution under a certain atmosphere, and then at 60-80 ° C (for example, 70 ° C). Stir at a temperature of 0.5-8 h (for example, 1 h) to obtain a mixed solution. The atmosphere of the present invention may be one of an inert atmosphere, a vacuum atmosphere, and an air atmosphere, and the preferred atmosphere is an air atmosphere.
本发明步骤(1)中，所述金属配位反应指的是，丙烯酸酯共聚物中的N元素与金属氧化物中的金属元素配位，得到丙烯酸酯共聚物修饰的金属氧化物。In the step (1) of the present invention, the metal coordination reaction means that the N element in the acrylate copolymer is coordinated with the metal element in the metal oxide to obtain an acrylate copolymer-modified metal oxide.
步骤(2)、加入溶剂对混合液进行提纯，并离心分离，获取丙烯酸酯共聚物修饰的金属氧化物。Step (2), adding a solvent to purify the mixture, and centrifuging to obtain an acrylate copolymer-modified metal oxide.
具体地，加入甲醇等溶剂对混合液进行提纯，并在8000rpm下离心5min，然后过滤，去除滤液，获取白色沉淀，所述白色沉淀即为丙烯酸酯共聚物修饰的金属氧化物。Specifically, the mixture was purified by adding a solvent such as methanol, and centrifuged at 8000 rpm for 5 minutes, and then filtered to remove the filtrate to obtain a white precipitate which is an acrylate copolymer-modified metal oxide.
本发明制备的所述丙烯酸酯共聚物修饰的金属氧化物可溶于烷烃溶液中，获得的丙烯酸酯共聚物修饰的金属氧化物分散液具有以下特征：纳米粒子性质稳定、粒径小且均一性好，分散剂为烷烃，纳米粒子分散后溶液浓度可控；制成薄膜透明性好。The acrylate copolymer modified metal oxide prepared by the invention is soluble in an alkane solution, and the obtained acrylate copolymer modified metal oxide dispersion has the following characteristics: stable nanoparticle property, small particle size and uniformity Well, the dispersant is an alkane, and the concentration of the solution after the dispersion of the nanoparticles is controllable; the transparency of the film is good.
本发明利用丙烯酸酯共聚物修饰金属氧化物，一方面可以起到钝化金属氧化物表面缺陷，减少表面缺陷对激子的淬灭和载流子的复合，另一方面可以提高金属氧化物表面电势，从而改善电子的注入水平和电子传输能力，此外丙烯酸酯共聚物可改善金属氧化物纳米粒子的分散性，有利于形成光滑的膜层，提高膜的透光性。The invention utilizes an acrylate copolymer to modify the metal oxide, on the one hand, it can passivate the surface defects of the metal oxide, reduce the quenching of the exciton and the recombination of the carrier by the surface defect, and can improve the surface of the metal oxide on the other hand. The electric potential, thereby improving the electron injection level and the electron transporting ability, and the acrylate copolymer can improve the dispersibility of the metal oxide nanoparticles, thereby facilitating the formation of a smooth film layer and improving the light transmittance of the film.
本发明提供一种丙烯酸酯共聚物修饰的金属氧化物，其中，采用如上任一所述的丙烯酸酯共聚物修饰的金属氧化物的制备方法制备而成。优选地，所述丙烯酸酯共聚物修饰的金属氧化物的粒径范围为3-50nm。The present invention provides an acrylate copolymer-modified metal oxide prepared by a method for producing a metal oxide modified by an acrylate copolymer as described above. Preferably, the acrylate copolymer modified metal oxide has a particle size ranging from 3 to 50 nm.
现有低温溶胶凝胶方法制备的金属氧化物表面存在较多的缺陷，导致以金属氧化物制成的电子传输层的传输性和透光性较低。与现有技术相比，本发明利用丙烯酸酯共聚物修饰金属氧化物，一方面可以起到钝化金属氧化物表面缺陷，减少表面缺陷对激子的淬灭和载流子的复合，另一方面可以提高金属氧化物表面电势，从而改善电子的注入水平和电子传输能力，此外丙烯酸酯共聚物可改善金属氧化物纳米粒子的分散性，有利于形成光滑的膜层，提高膜的透光性。The surface of the metal oxide prepared by the existing low-temperature sol-gel method has many defects, resulting in low transportability and light transmittance of the electron transport layer made of metal oxide. Compared with the prior art, the present invention utilizes an acrylate copolymer to modify a metal oxide, on the one hand, it can passivate the surface defects of the metal oxide, reduce the quenching of excitons and the recombination of carriers by surface defects, and the like. The aspect can improve the surface potential of the metal oxide, thereby improving the electron injection level and the electron transporting ability. In addition, the acrylate copolymer can improve the dispersibility of the metal oxide nanoparticles, and is favorable for forming a smooth film layer and improving the light transmittance of the film. .
本发明的一种量子点发光二极管，其中，所述量子点发光二极管包括电子传输层，所述电子传输层的材料为本发明所述的丙烯酸酯共聚物修饰的金属氧化物。A quantum dot light emitting diode according to the present invention, wherein the quantum dot light emitting diode comprises an electron transport layer, and the material of the electron transport layer is an acrylate copolymer modified metal oxide according to the present invention.
本发明中，所述量子点发光二极管还包括含有底电极的衬底和顶电极，所述衬底和所述顶电极之间设置有量子点发光层，所述电子传输层设置于所述量子点发光层和所述顶电极之间，所述量子点发光层和所述电子传输层之间设置有界面修饰层。In the present invention, the quantum dot light emitting diode further includes a substrate including a bottom electrode and a top electrode, and a quantum dot light emitting layer is disposed between the substrate and the top electrode, and the electron transport layer is disposed on the quantum Between the point light-emitting layer and the top electrode, an interface modification layer is disposed between the quantum dot light-emitting layer and the electron transport layer.
结合图2所示，本发明的一种量子点发光二极管较佳实施例的结构示意图，其中，所述量子点发光二极管包括叠层设置的含有底电极2的衬底1、空穴注入层3、空穴传输层4、量子点发光层5、界面修饰层6、电子传输层7和顶电极8；所述电子传输层7的材料为如上任一所述的丙烯酸酯共聚物修饰的金属氧化物。本发明利用经丙烯酸酯共聚物修饰的金属氧化物作为量子点发光二极管中电子传输 层的材料，一方面可以减少金属氧化物表面缺陷对激子的淬灭和载流子的复合，另一方面可以改善电子的注入水平和电子传输能力，此外丙烯酸酯共聚物可改善金属氧化物纳米粒子的分散性，有利于形成光滑的膜层，提高膜的透光性。2 is a schematic structural diagram of a preferred embodiment of a quantum dot light emitting diode according to the present invention, wherein the quantum dot light emitting diode comprises a substrate 1 including a bottom electrode 2 and a hole injection layer 3 provided in a stack. a hole transport layer 4, a quantum dot light-emitting layer 5, an interface modification layer 6, an electron transport layer 7, and a top electrode 8; the material of the electron transport layer 7 is an acrylate copolymer-modified metal oxide as described above Things. The invention utilizes the metal oxide modified by the acrylate copolymer as the material of the electron transport layer in the quantum dot light emitting diode, on the one hand, the surface defect of the metal oxide can be reduced, and the exciton quenching and carrier recombination can be reduced. The electron injection level and electron transport ability can be improved, and the acrylate copolymer can improve the dispersibility of the metal oxide nanoparticles, facilitate the formation of a smooth film layer, and improve the light transmittance of the film.
结合图3所示，本发明的一种量子点发光二极管的制备方法较佳实施例的流程图，如图所示，其包括：As shown in FIG. 3, a flow chart of a preferred embodiment of a method for fabricating a quantum dot light-emitting diode of the present invention, as shown in the figure, includes:
步骤S100、在含有底电极的衬底上制备空穴注入层，在空穴注入层上制备空穴传输层；Step S100, preparing a hole injection layer on a substrate containing a bottom electrode, and preparing a hole transport layer on the hole injection layer;
所述步骤S100中，所述含有底电极的衬底的材料可以为可见光区透明导电材料，所述可见光区透明导电材料可以为但不限于氧化锡铟(ITO)、氧化铟锌(IZO)等，优选的可见光区透明导电材料为ITO。In the step S100, the material of the substrate containing the bottom electrode may be a transparent conductive material in the visible light region, and the transparent conductive material in the visible light region may be, but not limited to, indium tin oxide (ITO), indium zinc oxide (IZO), or the like. The preferred visible light region transparent conductive material is ITO.
所述步骤S100之前还包括：先对含有底电极的衬底进行清洗，然后采用紫外臭氧或氧气等离子体处理衬底表面。具体清洗过程包括：用无尘布蘸取洗涤剂在含有底电极的衬底(如ITO)表面轻轻擦拭数次，用去离子水冲洗干净后，再依次用超纯水、丙酮、乙醇超声清洗15分钟，待超声完成后，将含有底电极的衬底放置于洁净烘箱内烘干，烘干后的含有底电极的衬底放在臭氧紫外清洗机(UVO)中照射5分钟。Before the step S100, the method further comprises: first cleaning the substrate containing the bottom electrode, and then treating the surface of the substrate with ultraviolet ozone or oxygen plasma. The specific cleaning process includes: using a dust-free cloth to extract the detergent, gently wiping the surface of the substrate (such as ITO) containing the bottom electrode several times, rinsing with deionized water, and then ultrasonically using ultrapure water, acetone, and ethanol. After washing for 15 minutes, after the completion of the ultrasonication, the substrate containing the bottom electrode was placed in a clean oven for drying, and the dried substrate containing the bottom electrode was irradiated for 5 minutes in an ozone ultraviolet cleaner (UVO).
优选地，所述空穴注入层的材料可以为PEDOT:PSS、MoO 3、Nb 2O 5、NiO等中的一种或多种；此膜层厚度范围为20-80nm。 Preferably, the material of the hole injection layer may be one or more of PEDOT:PSS, MoO 3 , Nb 2 O 5 , NiO, etc.; the thickness of the film layer ranges from 20 to 80 nm.
优选地，所述空穴传输层的材料可以为具有给电子能力的有机化合物或金属氧化物，所述具有给电子能力的有机化合物可以为NPB、TPD、TAPC、TFB、OTPD、QTPD、Poly-TPD、PVK等中的一种或多种；所述金属氧化物可以为氧化钼、氧化钒、氧化镍、氧化铜、氧化钨等中的一种或多种。此膜层厚度范围可以为10-100nm。本发明所述空穴注入层和空穴传输层的沉积方法不受限制，可采用本领域常规溶液加工方法沉积，如喷墨打印、旋涂、喷涂等。Preferably, the material of the hole transport layer may be an organic compound or metal oxide having electron donating ability, and the organic compound having electron donating ability may be NPB, TPD, TAPC, TFB, OTPD, QTPD, Poly- One or more of TPD, PVK, etc.; the metal oxide may be one or more of molybdenum oxide, vanadium oxide, nickel oxide, copper oxide, tungsten oxide, and the like. This film thickness can range from 10 to 100 nm. The method of depositing the hole injecting layer and the hole transporting layer of the present invention is not limited and may be deposited by a conventional solution processing method in the art, such as ink jet printing, spin coating, spray coating, or the like.
步骤S200、在空穴传输层上制备量子点发光层，在量子点发光层上制备界面修饰层，然后在界面修饰层上制备电子传输层；所述电子传输层的材料为如上任一所述的丙烯酸酯共聚物修饰的金属氧化物；Step S200, preparing a quantum dot light-emitting layer on the hole transport layer, preparing an interface modification layer on the quantum dot light-emitting layer, and then preparing an electron transport layer on the interface modification layer; the material of the electron transport layer is as described above Acrylate copolymer modified metal oxide;
优选地，所述量子点发光层的材料可以为常见的红光量子点、绿光量子点、蓝光量子点和黄光量子点以及红外光量子点和紫外光量子点中的至少一种。本发 明所述量子点发光层的沉积方法不受限制，可采用本领域常规溶液加工方法沉积，如喷墨打印、旋涂、喷涂等。Preferably, the material of the quantum dot luminescent layer may be at least one of a common red light quantum dot, a green light quantum dot, a blue light quantum dot and a yellow light quantum dot, and an infrared light quantum dot and an ultraviolet light quantum dot. The method of depositing the quantum dot luminescent layer of the present invention is not limited and may be deposited by conventional solution processing methods in the art, such as ink jet printing, spin coating, spray coating, and the like.
优选地，所述界面修饰层由易溶解于醇类溶剂但不溶于烷烃的极性较大的材料制成，如环氧树脂、聚丙烯酸、聚乙烯亚胺(PEI)、聚乙烯吡咯烷酮(PVP)、PEIE(聚乙氧基乙烯亚胺)、PEG(聚乙二醇)、PEO(聚氧化乙烯)等中的一种或多种；成膜时选用碳原子总数为1-14的醇做溶剂，采用旋涂、喷涂或喷墨打印成膜，膜层厚度范围为0.5-20nm。由于常用量子点的分散溶剂为烷烃，而丙烯酸酯共聚物修饰的金属氧化物分散溶剂也为烷烃，利用溶液成膜法直接在量子点发光层上沉积丙烯酸酯共聚物修饰的金属氧化物薄膜层会对相邻膜层造成破坏。因此本发明在量子点发光层上沉积所述界面修饰层，可有效阻止利用溶液法直接在量子点发光层上沉积丙烯酸酯共聚物修饰的金属氧化物膜层对相邻膜层造成的破坏，保持各膜层性能完好，此外所述界面修饰层还可以起到阻止空穴等作用。Preferably, the interfacial modification layer is made of a highly polar material which is soluble in an alcohol solvent but insoluble in an alkane, such as epoxy resin, polyacrylic acid, polyethyleneimine (PEI), polyvinylpyrrolidone (PVP). ), one or more of PEIE (polyethoxyethyleneimine), PEG (polyethylene glycol), PEO (polyethylene oxide), etc.; the film is formed by using a total of 1-14 carbon atoms. The solvent is formed into a film by spin coating, spray coating or ink jet printing, and the film thickness ranges from 0.5 to 20 nm. Since the dispersion solvent of the commonly used quantum dots is an alkane, and the metal oxide dispersion solvent modified by the acrylate copolymer is also an alkane, the acrylate copolymer-modified metal oxide thin film layer is directly deposited on the quantum dot light-emitting layer by a solution film formation method. It will cause damage to adjacent layers. Therefore, the present invention deposits the interface modification layer on the quantum dot luminescent layer, which can effectively prevent the destruction of the adjacent film layer by depositing the acrylate copolymer modified metal oxide film layer directly on the quantum dot luminescent layer by the solution method. The performance of each film layer is kept intact, and the interface modification layer can also function to block holes and the like.
优选地，所述金属氧化物可以为但不限于氧化锌、氧化钛等，优选地，所述金属氧化物为纳米氧化锌。更优选地，所述丙烯酸酯共聚物修饰的纳米氧化锌的粒径范围为3-50nm。优选地，所述丙烯酸酯共聚物修饰的金属氧化物可以溶于烷烃但不溶于醇类；成膜时将丙烯酸酯共聚物修饰的金属氧化物分散于烷烃分子中，溶液浓度范围为0.1-300mg/mL，由于在该层与量子点发光层中***了可溶于醇而不溶于烷烃的界面修饰层，因而可采用旋涂、印刷、喷涂、滴涂或喷墨打印的方法成膜，膜层厚度3-100nm。Preferably, the metal oxide may be, but not limited to, zinc oxide, titanium oxide, or the like. Preferably, the metal oxide is nano zinc oxide. More preferably, the acrylate copolymer-modified nano zinc oxide has a particle size ranging from 3 to 50 nm. Preferably, the acrylate copolymer modified metal oxide is soluble in an alkane but insoluble in an alcohol; in the film formation, the acrylate copolymer modified metal oxide is dispersed in an alkane molecule, and the solution concentration ranges from 0.1 to 300 mg. /mL, since an interfacial modification layer soluble in alcohol and insoluble in an alkane is inserted into the layer and the quantum dot emitting layer, film formation by a spin coating, printing, spraying, dispensing or ink jet printing may be employed. The layer thickness is 3-100 nm.
步骤S300、在电子传输层上制备顶电极，然后进行封装，得到量子点发光二极管。Step S300, preparing a top electrode on the electron transport layer, and then performing packaging to obtain a quantum dot light emitting diode.
所述步骤S300中，在电子传输层上通过蒸镀的方式制备一层厚度为10-500nm的顶电极，待蒸镀完成后，对其进行封装，得到量子点发光二极管。本发明可以使用常用的机器封装也可以使用简单的手动封装。其中，所述顶电极可以为铝、银、金、铂、铜、镁、钙、钡、钛等中的一种或多种。In the step S300, a top electrode having a thickness of 10-500 nm is prepared by vapor deposition on the electron transport layer, and after the evaporation is completed, the top electrode is packaged to obtain a quantum dot light emitting diode. The invention can be used with conventional machine packages or simple manual packages. The top electrode may be one or more of aluminum, silver, gold, platinum, copper, magnesium, calcium, barium, titanium, and the like.
本发明上述步骤S100-S300中，在使用溶液法制备各膜层时，为调整膜层的形貌，可分别对膜层做退火处理，退火温度范围100℃至300℃，退火时间为1-120分钟。In the above steps S100-S300 of the present invention, in order to prepare the film layers by using the solution method, in order to adjust the morphology of the film layers, the film layers may be annealed separately, the annealing temperature ranges from 100 ° C to 300 ° C, and the annealing time is 1- 120 minutes.
本发明利用丙烯酸酯共聚物修饰的金属氧化物特别是纳米氧化锌作为量子 点发光二极管的电子传输层，一方面丙烯酸酯共聚物钝化了金属氧化物表面缺陷，从而减少表面缺陷对激子的淬灭和载流子的复合，提高了其电子传输能力；另一方面通过丙烯酸酯共聚物修饰纳米金属氧化物可以提高金属氧化物表面电势，从而改善电子的注入水平；此外丙烯酸酯共聚物改善了金属氧化物的分散能力，有利于形成光滑的薄膜层，提高了膜的透光性。The invention utilizes an acrylate copolymer modified metal oxide, in particular nano zinc oxide, as an electron transport layer of a quantum dot light emitting diode. On the one hand, the acrylate copolymer inactivates metal oxide surface defects, thereby reducing surface defects on excitons. Quenching and carrier recombination enhances its electron transport capability; on the other hand, modification of nanometal oxide by acrylate copolymer can increase the surface potential of metal oxide, thereby improving the level of electron injection; in addition, the improvement of acrylate copolymer The dispersing ability of the metal oxide is favorable for forming a smooth film layer and improving the light transmittance of the film.
本发明可实现溶液法制备电子传输层，经丙烯酸酯共聚物修饰过的金属氧化物易溶于烷烃，通过在量子点发光层与丙烯酸酯共聚物修饰的金属氧化物膜层间增加界面修饰层，该界面修饰层材料可溶于醇溶液而不溶于烷烃，从而可实现溶液法制备电子传输层，相比真空蒸镀法，溶液法能够提高材料的利用率，简化工艺，降低生产成本，可实现大面积生产。The invention can realize the preparation of an electron transport layer by a solution method, wherein the metal oxide modified by the acrylate copolymer is easily soluble in an alkane, and an interface modification layer is added between the quantum oxide layer modified by the quantum dot light-emitting layer and the acrylate copolymer. The interface modification layer material is soluble in the alcohol solution and is insoluble in the alkane, so that the electron transport layer can be prepared by the solution method. Compared with the vacuum evaporation method, the solution method can improve the utilization rate of the material, simplify the process, and reduce the production cost. Achieve large-scale production.
下面通过实施例对本发明进行详细说明。The invention will now be described in detail by way of examples.
实施例1Example 1
丙烯酸酯共聚物修饰的氧化锌纳米粒子分散液的制备步骤如下：The preparation steps of the acrylate copolymer modified zinc oxide nanoparticle dispersion are as follows:
(1)、用乙二醇单甲醚作溶剂分别配制30mg/ml的乙酸锌溶液10ml和200mg/ml的四甲基氢氧化铵溶液2ml。用二甲苯作为溶剂配制50mg/ml的丙烯酸酯共聚物溶液；(1) 10 ml of a 30 mg/ml zinc acetate solution and 2 ml of a 200 mg/ml tetramethylammonium hydroxide solution were separately prepared using ethylene glycol monomethyl ether as a solvent. Preparing a 50 mg/ml acrylate copolymer solution using xylene as a solvent;
(2)、把(1)所述乙酸锌溶液加热到80℃、用磁子在1500rpm的转速下对其进行搅拌，使其充分溶解，然后把配好的四甲基氢氧化铵溶液匀速注入到乙酸锌溶液中，持续搅拌几分钟，加入(1)所述的丙烯酸酯共聚物溶液10mL，保持温度60℃，搅拌1h，得到混合液；(2) heating the zinc acetate solution of (1) to 80 ° C, stirring it with a magnet at 1,500 rpm to dissolve it sufficiently, and then uniformly injecting the prepared tetramethylammonium hydroxide solution. To the zinc acetate solution, stirring for a few minutes, adding 10 mL of the acrylate copolymer solution (1), maintaining the temperature at 60 ° C, stirring for 1 h, to obtain a mixed solution;
(3)、向混合液中加入甲醇溶液提纯丙烯酸酯共聚物修饰的氧化锌纳米粒子，取混合液离心(8000rpm，5min)后，去除滤液，得到白色沉淀；(3) adding MeOH solution to the mixed solution to purify the acrylate copolymer-modified zinc oxide nanoparticles, and centrifuging the mixture (8000 rpm, 5 min), and then removing the filtrate to obtain a white precipitate;
(4)、用正辛烷溶液对白色沉淀进行再分散，得到浓度约为5mg/ml的丙烯酸酯共聚物修饰的氧化锌纳米粒子分散液。此丙烯酸酯共聚物修饰的氧化锌纳米粒子分散液具有以下特征：纳米粒子性质稳定、粒径小且均一性好，分散剂为烷烃，纳米粒分散后溶液浓度可控；制成薄膜透明性好。(4) The white precipitate was redispersed with a n-octane solution to obtain an acrylate copolymer-modified zinc oxide nanoparticle dispersion having a concentration of about 5 mg/ml. The acrylate copolymer-modified zinc oxide nanoparticle dispersion has the following characteristics: the nanoparticle has stable properties, small particle size and good uniformity, the dispersant is an alkane, and the concentration of the solution after the dispersion of the nanoparticles is controllable; .
量子点发光二极管的制备步骤如下：The preparation steps of the quantum dot light emitting diode are as follows:
(a)、先对理ITO基板进行清洗，然后采用紫外臭氧处理ITO基板表面。具体清洗过程包括：用无尘布蘸取洗涤剂在ITO基板表面轻轻擦拭数次，用去离 子水冲洗干净后，再依次用超纯水、丙酮、乙醇超声清洗15分钟，待超声完成后，将ITO基板放置于洁净烘箱内烘干，烘干后将ITO基板放在紫外臭氧清洗机(UVO)中照射5分钟。(a) First, the ITO substrate is cleaned, and then the surface of the ITO substrate is treated with ultraviolet ozone. The specific cleaning process includes: gently rubbing the detergent on the surface of the ITO substrate with a dust-free cloth, rinsing with deionized water, and then ultrasonically cleaning with ultrapure water, acetone, and ethanol for 15 minutes, after the ultrasonication is completed. The ITO substrate was placed in a clean oven for drying, and after drying, the ITO substrate was placed in an ultraviolet ozone cleaner (UVO) for 5 minutes.
采用旋涂法在ITO基板上沉积PEDOT:PSS空穴注入层，然后将所述PEDOT:PSS空穴注入层中的溶剂去除，所述去除溶剂的方法为：在120℃条件下加热20min。通过该方法，可有效去除所述PEDOT:PSS空穴注入层中的溶剂，同时可形成致密性好的PEDOT:PSS薄膜。A PEDOT:PSS hole injection layer was deposited on the ITO substrate by spin coating, and then the solvent in the PEDOT:PSS hole injection layer was removed by heating at 120 ° C for 20 min. By this method, the solvent in the PEDOT:PSS hole injection layer can be effectively removed, and at the same time, a dense PEDOT:PSS film can be formed.
(b)、采用旋涂法在空穴注入层上沉积Poly-TPD空穴传输层；此膜层厚度为50nm。在沉积完Poly-TPD空穴传输层后，将基板置于150℃的加热台上加热10分钟。(b) depositing a Poly-TPD hole transport layer on the hole injection layer by spin coating; the film layer has a thickness of 50 nm. After depositing the Poly-TPD hole transport layer, the substrate was placed on a heating table at 150 ° C for 10 minutes.
(c)、采用旋涂法在空穴传输层上沉积量子点发光层；沉积完薄膜后，将薄膜置于120℃下退火处理10min。量子点发光层的厚度为50nm。(c) depositing a quantum dot luminescent layer on the hole transport layer by spin coating; after depositing the film, the film was annealed at 120 ° C for 10 min. The quantum dot light-emitting layer has a thickness of 50 nm.
(d)、将环氧树脂分散于甲醇溶液中，向量子点发光层上滴加数滴所述环氧树脂溶液，用匀胶机在8000rpm的转速下旋涂40s制成界面修饰层。随后，将薄膜置于120℃下退火处理10min。界面修饰层的厚度为5nm。(d) Dispersing the epoxy resin in the methanol solution, adding a few drops of the epoxy resin solution onto the vector sub-dot light-emitting layer, and spin-coating the adhesive layer at 8000 rpm for 40 s to prepare an interface-modifying layer. Subsequently, the film was annealed at 120 ° C for 10 min. The thickness of the interface modification layer was 5 nm.
(e)、将丙烯酸酯共聚物修饰的氧化锌纳米粒子的正辛烷分散液用0.22μm的滤头过滤后，用匀胶机在8000rpm的转速下旋涂40s成膜，其厚度为45nm。随后，将薄膜置于150℃下退火处理10min。(e) The n-octane dispersion of the acrylate copolymer-modified zinc oxide nanoparticles was filtered through a 0.22 μm filter, and then spin-coated at a speed of 8000 rpm for 40 s to form a film having a thickness of 45 nm. Subsequently, the film was annealed at 150 ° C for 10 min.
(f)、当样品室真空度达到6.0×10 -4Pa时，向基片上热蒸镀铝电极。铝层厚度控制在100nm左右。 (f) When the vacuum degree of the sample chamber reaches 6.0 × 10 -4 Pa, the aluminum electrode is thermally evaporated onto the substrate. The thickness of the aluminum layer is controlled to be around 100 nm.
实施例2Example 2
首先按照实施例1同样方法制备丙烯酸酯共聚物修饰的氧化锌纳米粒子沉淀，然后用十八烷溶液对丙烯酸酯共聚物修饰的氧化锌纳米粒子进行再分散，得到最终浓度约为3mg/ml的丙烯酸酯共聚物修饰的氧化锌纳米粒子分散液。First, the acrylate copolymer-modified zinc oxide nanoparticle precipitate was prepared in the same manner as in Example 1, and then the acrylate copolymer-modified zinc oxide nanoparticles were redispersed with an octadecane solution to obtain a final concentration of about 3 mg/ml. Acrylate copolymer modified zinc oxide nanoparticle dispersion.
按实施例1的方法制备量子点发光二极管，所不同的是采用真空蒸镀空穴传输层和真空蒸镀量子点发光层：选用三苯胺类化合物4,4'-二-(N-萘基-N-苯基氨基)联苯(NPB)作为空穴传输层，利用真空镀膜机在3×10 -4Pa的真空度下真空热蒸镀NPB膜层，厚度为30nm。利用真空镀膜机在3×10 -4Pa的真空度下向空穴传输层蒸镀量子点发光层。 A quantum dot light-emitting diode was prepared according to the method of Example 1, except that the hole transport layer was vacuum-deposited and the quantum dot light-emitting layer was vacuum-evaporated: the triphenylamine compound 4,4'-di-(N-naphthyl group was selected. -N-Phenylamino)biphenyl (NPB) As a hole transporting layer, the NPB film layer was vacuum-vapor-deposited at a vacuum of 3 × 10 -4 Pa using a vacuum coater to have a thickness of 30 nm. The quantum dot light-emitting layer was deposited on the hole transport layer under a vacuum of 3 × 10 -4 Pa by a vacuum coater.
综上所述，本发明提供的一种丙烯酸酯共聚物修饰的金属氧化物及制备方法与量子点发光二极管。本发明利用丙烯酸酯共聚物修饰金属氧化物，一方面可以起到钝化金属氧化物表面缺陷，减少表面缺陷对激子的淬灭和载流子的复合，另一方面可以提高金属氧化物表面电势，从而改善电子的注入水平和电子传输能力，此外丙烯酸酯共聚物可改善金属氧化物纳米粒子的分散性，有利于形成光滑的膜层，提高膜的透光性。In summary, the present invention provides an acrylate copolymer modified metal oxide and a preparation method thereof and a quantum dot light emitting diode. The invention utilizes an acrylate copolymer to modify the metal oxide, on the one hand, it can passivate the surface defects of the metal oxide, reduce the quenching of the exciton and the recombination of the carrier by the surface defect, and can improve the surface of the metal oxide on the other hand. The electric potential, thereby improving the electron injection level and the electron transporting ability, and the acrylate copolymer can improve the dispersibility of the metal oxide nanoparticles, thereby facilitating the formation of a smooth film layer and improving the light transmittance of the film.
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。It is to be understood that the application of the present invention is not limited to the above-described examples, and those skilled in the art can make modifications and changes in accordance with the above description, all of which are within the scope of the appended claims.

Claims (18)

  1. 一种丙烯酸酯共聚物修饰的金属氧化物的制备方法，其特征在于，包括：A method for preparing an acrylate copolymer modified metal oxide, comprising:
    在一定气氛下，将丙烯酸酯共聚物溶液添加至预先备好的金属氧化物溶液中，发生金属配位反应，得到丙烯酸酯共聚物修饰的金属氧化物混合液；Adding an acrylate copolymer solution to a prepared metal oxide solution under a certain atmosphere to cause a metal coordination reaction to obtain an acrylate copolymer-modified metal oxide mixture;
    加入溶剂对所述混合液进行提纯，并离心分离，获取丙烯酸酯共聚物修饰的金属氧化物。The mixture was purified by adding a solvent, and centrifuged to obtain an acrylate copolymer-modified metal oxide.
  2. 根据权利要求1所述的丙烯酸酯共聚物修饰的金属氧化物的制备方法，其特征在于，所述丙烯酸酯共聚物溶液的浓度为10-100mg/ml。The method for producing an acrylate copolymer-modified metal oxide according to claim 1, wherein the acrylate copolymer solution has a concentration of 10 to 100 mg/ml.
  3. 根据权利要求1所述的丙烯酸酯共聚物修饰的金属氧化物的制备方法，其特征在于，所述金属氧化物溶液的浓度为10-100mg/ml。The method for producing an acrylate copolymer-modified metal oxide according to claim 1, wherein the metal oxide solution has a concentration of 10 to 100 mg/ml.
  4. 根据权利要求1所述的丙烯酸酯共聚物修饰的金属氧化物的制备方法，其特征在于，将2-20ml丙烯酸酯共聚物溶液添加至预先备好的2-20ml金属氧化物溶液中。The method for producing an acrylate copolymer-modified metal oxide according to claim 1, wherein 2 to 20 ml of the acrylate copolymer solution is added to a prepared 2-20 ml of a metal oxide solution.
  5. 根据权利要求1所述的丙烯酸酯共聚物修饰的金属氧化物的制备方法，其特征在于，所述气氛为惰性氛围、真空氛围、空气氛围中的一种。The method for producing an acrylate copolymer-modified metal oxide according to claim 1, wherein the atmosphere is one of an inert atmosphere, a vacuum atmosphere, and an air atmosphere.
  6. 根据权利要求1所述的丙烯酸酯共聚物修饰的金属氧化物的制备方法，其特征在于，所述溶剂为甲醇。The method for producing an acrylate copolymer-modified metal oxide according to claim 1, wherein the solvent is methanol.
  7. 根据权利要求1所述的丙烯酸酯共聚物修饰的金属氧化物的制备方法，其特征在于，所述金属配位反应的温度为60-80℃。The method for producing an acrylate copolymer-modified metal oxide according to claim 1, wherein the metal coordination reaction has a temperature of from 60 to 80 °C.
  8. 根据权利要求1所述的丙烯酸酯共聚物修饰的金属氧化物的制备方法，其特征在于，所述金属配位反应的时间为0.5-8h。The method for preparing an acrylate copolymer-modified metal oxide according to claim 1, wherein the metal coordination reaction has a time of from 0.5 to 8 hours.
  9. 一种丙烯酸酯共聚物修饰的金属氧化物，其特征在于，采用如权利要求1所述的丙烯酸酯共聚物修饰的金属氧化物的制备方法制备而成。An acrylate copolymer-modified metal oxide prepared by the method for producing a metal oxide modified with an acrylate copolymer according to claim 1.
  10. 根据权利要求9所述的丙烯酸酯共聚物修饰的金属氧化物，其特征在于，所述丙烯酸酯共聚物修饰的金属氧化物的粒径范围为3-50nm。The acrylate copolymer-modified metal oxide according to claim 9, wherein the acrylate copolymer-modified metal oxide has a particle diameter ranging from 3 to 50 nm.
  11. 根据权利要求9所述的丙烯酸酯共聚物修饰的金属氧化物，其特征在于，所述金属氧化物为氧化锌或氧化钛。The acrylate copolymer-modified metal oxide according to claim 9, wherein the metal oxide is zinc oxide or titanium oxide.
  12. 一种量子点发光二极管，其特征在于，所述量子点发光二极管包括电子传输层，所述电子传输层的材料为权利要求9所述的丙烯酸酯共聚物修饰的金属氧化物。A quantum dot light emitting diode, characterized in that the quantum dot light emitting diode comprises an electron transport layer, and the material of the electron transport layer is the acrylate copolymer modified metal oxide according to claim 9.
  13. 根据权利要求12所述的量子点发光二极管，其特征在于，所述量子点发光二极管还包括含有底电极的衬底和顶电极，所述衬底和所述顶电极之间设置有量子点发光层，所述电子传输层设置于所述量子点发光层和所述顶电极之间，所述量子点发光层和所述电子传输层之间设置有界面修饰层。The quantum dot light emitting diode according to claim 12, wherein the quantum dot light emitting diode further comprises a substrate including a bottom electrode and a top electrode, and quantum dot illumination is disposed between the substrate and the top electrode a layer, the electron transport layer is disposed between the quantum dot light emitting layer and the top electrode, and an interface modification layer is disposed between the quantum dot light emitting layer and the electron transport layer.
  14. 根据权利要求12所述的量子点发光二极管，其特征在于，所述电子传输层的厚度范围为3-100nm。The quantum dot light emitting diode according to claim 12, wherein the electron transport layer has a thickness ranging from 3 to 100 nm.
  15. 根据权利要求13所述的量子点发光二极管，其特征在于，所述界面修饰层的厚度范围为0.5-20nm。The quantum dot light emitting diode according to claim 13, wherein the interface modification layer has a thickness ranging from 0.5 to 20 nm.
  16. 根据权利要求13所述的量子点发光二极管，其特征在于，所述界面修饰层由易溶解于醇类溶剂但不溶于烷烃的极性较大的材料制成。The quantum dot light emitting diode according to claim 13, wherein the interface modification layer is made of a highly polar material which is easily soluble in an alcohol solvent but insoluble in an alkane.
  17. 根据权利要求16所述的量子点发光二极管，其特征在于，所述材料为环氧树脂、聚丙烯酸、聚乙烯亚胺、聚乙烯吡咯烷酮、聚乙氧基乙烯亚胺、聚乙二醇、聚氧化乙烯中的一种或多种。The quantum dot light emitting diode according to claim 16, wherein the material is epoxy resin, polyacrylic acid, polyethyleneimine, polyvinylpyrrolidone, polyethoxyethyleneimine, polyethylene glycol, poly One or more of ethylene oxide.
  18. 根据权利要求16所述的量子点发光二极管，其特征在于，所述醇类溶剂为碳原子总数为1-14的醇。The quantum dot light emitting diode according to claim 16, wherein the alcohol solvent is an alcohol having a total of 1 to 14 carbon atoms.
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