CN109390493B - Display device and preparation method thereof - Google Patents

Display device and preparation method thereof Download PDF

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Publication number
CN109390493B
CN109390493B CN201710683612.9A CN201710683612A CN109390493B CN 109390493 B CN109390493 B CN 109390493B CN 201710683612 A CN201710683612 A CN 201710683612A CN 109390493 B CN109390493 B CN 109390493B
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graphene oxide
layer
reduced graphene
emitting device
light
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CN109390493A (en
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刘佳
曹蔚然
梁柱荣
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TCL Technology Group Co Ltd
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TCL Technology Group Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • 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
    • H10K50/80—Constructional details
    • H10K50/87—Arrangements for heating or cooling
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • 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

Abstract

The invention belongs to the field of display devices and provides display equipment and a preparation method thereof. According to the display equipment provided by the invention, the reduction graphene oxide layer is introduced between the light-emitting device and the packaging structure, the reduction graphene oxide layer is the oxidized graphene functionalized by the diaminopyridine, under the driving of heat emitted by the device, the reduction graphene oxide layer absorbs heat, electrons are transited to LUMO energy level, and then radiation transition is carried out to generate blue light, so that the blue light compensation is realized while the heat of the device is reduced, the service life stability of the device is favorably improved, and full-color display is formed.

Description

Display device and preparation method thereof
Technical Field
The invention belongs to the field of display devices, and particularly relates to a display device and a preparation method thereof.
Background
Quantum Dots (QDs) have the characteristics of tunable size, narrow width of light-emitting line, high photoluminescence efficiency, thermal stability and the like, so that Quantum dot light-emitting diodes (QLEDs) using the QDs as light-emitting layers are potential next-generation display and solid-state illumination light sources.
Quantum dot light emitting diodes have attracted considerable attention and research in the fields of illumination and display in recent years due to their advantages of high brightness, low power consumption, wide color gamut, and easy processing. Through years of development, the QLED technology has been greatly developed. From the publicly reported literature, the external quantum efficiency of the currently highest red and green QLEDs has exceeded or approached 20%, indicating that the internal quantum efficiency of the red and green QLEDs has actually approached the 100% limit. However, the blue QLED, which is indispensable for high-performance full-color display, is currently much lower than the red-green QLED in both the electro-optical conversion efficiency and the lifetime, thereby limiting the application of the QLED in full-color display. Moreover, from data published by various international research institutes and related companies, it is difficult to achieve good repeatability of the performance of the QLED, which results in many problems to be solved in large-scale practical production of the QLED.
Therefore, the existing light-emitting device has the problems of low blue light-emitting efficiency and short service life, thereby limiting the application of the light-emitting device in full-color display and large-scale practical production.
Disclosure of Invention
The invention aims to provide a display device and a preparation method thereof, and aims to solve the problem that the application of a light-emitting device in full-color display and large-scale practical production are limited due to low blue light emitting efficiency and short service life of the existing light-emitting device.
The present invention provides a display device including:
a substrate;
a light emitting device disposed on the substrate;
a reduced graphene oxide layer covering the light emitting device, the material of the reduced graphene oxide layer comprising diaminopyridine functionalized graphene oxide;
a package structure disposed on the substrate and the light emitting device covered by the reduced graphene oxide layer, the package structure covering the light emitting device covered by the reduced graphene oxide layer.
The invention also provides a preparation method of the display device, which comprises the following steps:
providing a substrate;
forming a light emitting device on the substrate;
depositing a layer of reduced graphene oxide on the light emitting device such that the layer of reduced graphene oxide covers the light emitting device, wherein the material of the layer of reduced graphene oxide comprises diaminopyridine functionalized graphene oxide;
and forming a packaging structure on the substrate and the light-emitting device covered by the reduced graphene oxide layer, so that the packaging structure covers the light-emitting device covered by the reduced graphene oxide layer.
According to the display equipment provided by the invention, the reduction graphene oxide layer is introduced between the light-emitting device and the packaging structure, the reduction graphene oxide layer is the oxidized graphene functionalized by the diaminopyridine, under the driving of heat emitted by the device, the reduction graphene oxide layer absorbs the heat, the electronic transition is carried out to the LUMO energy level, and then the radiation transition is carried out to generate blue light, so that the blue light compensation is realized while the heat of the device is reduced, the service life stability of the device is favorably improved, and the full-color display is formed. The preparation method of the display device provided by the invention has the advantages of simple preparation process and low cost, and can realize large-scale production.
Drawings
Fig. 1 is a schematic structural diagram of a display device provided in an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a light-emitting device provided by an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
Referring to fig. 1, fig. 1 is a schematic structural diagram of a display device according to an embodiment of the present invention. The display device comprises a substrate 1, a light-emitting device 2 arranged on the substrate, a reduced graphene oxide layer 3 formed on the upper surface of the light-emitting device 2, and a packaging structure 4 covering the light-emitting device 2 and the reduced graphene oxide layer 3, wherein the material of the reduced graphene oxide layer 3 comprises diaminopyridine functionalized graphene oxide, and the reduced graphene oxide layer 3 emits light in a blue light range after absorbing heat.
In the embodiment of the present invention, the substrate 1 is not limited to be used, and a rigid substrate or a flexible substrate may be used. Wherein the rigid substrate includes, but is not limited to, one or more of glass, metal foil; the flexible substrate includes, but is not limited to, one or more of polyethylene terephthalate (PET), polyethylene terephthalate (PEN), Polyetheretherketone (PEEK), Polystyrene (PS), Polyethersulfone (PES), Polycarbonate (PC), Polyarylate (PAT), Polyarylate (PAR), Polyimide (PI), polyvinyl chloride (PV), Polyethylene (PE), polyvinylpyrrolidone (PVP), textile fibers.
In the embodiment of the present invention, the light emitting device 2 has a conventional structure (see fig. 2), and includes a bottom electrode 201 disposed on the substrate 1, and a first functional layer 202, a light emitting layer 203, a second functional layer 204, and a top electrode 205 sequentially disposed on the bottom electrode 201. The light emitting device 2 is not limited to the device structure, and may be a device having a positive type structure or a device having an inverted type structure. When the structure of the light emitting device 2 is a positive structure, the bottom electrode 201 is an anode, the first functional layer 202 is a hole functional layer, the second functional layer 204 is an electron functional layer, and the top electrode 205 is a cathode; when the structure of the light emitting device 2 is an inversion structure, the bottom electrode 201 is a cathode, the first functional layer 202 is an electron functional layer, the second functional layer 204 is a hole functional layer, and the top electrode 205 is an anode.
In one embodiment, the structure of the light-emitting device 2 is used as a positive structure to explain the device, and it should be noted that the description of the anode, the hole function layer, the electron function layer, and the cathode in this embodiment is not limited to the description of the positive structure, and the description of the anode, the hole function layer, the electron function layer, and the cathode in the inversion structure is also applicable.
Further, the bottom electrode 201 is an anode deposited on the substrate 1, the material of the bottom electrode 201 is not limited, and may be selected from doped metal oxides, including but not limited to, one or more of indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), magnesium-doped zinc oxide (MZO), and aluminum-doped magnesium oxide (AMO), or may be selected from a composite electrode sandwiching metal between doped or undoped transparent metal oxides, including but not limited to, AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO/Al/ZnO, and doped or undoped transparent metal oxides2/Ag/TiO2、TiO2/Al/TiO2、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO2/Ag/TiO2、TiO2/Al/TiO2One or more of (a).
Further, the first functional layer 202 is a hole functional layer for injecting and transporting holes, including but not limited to at least one hole transport layer disposed on the bottom electrode. In this embodiment, the thickness of the hole transport layer has a large influence on the conductivity of the film layer and the injection efficiency of holes, and if the thickness is too thin, the conductivity is weak, and the hole and the electron are not balanced, and the light emitting region may be in the electron transport layer but not in the light emitting layer; too thick is not conducive to implantation. In order to make the film layer have a strong conductivity and a high hole injection efficiency, the hole transport layer preferably has a thickness of 0nm to 100nm, more preferably 40nm to 50 nm. Specifically, the hole transport layer may be selected from an organic material having a hole transport ability and/or an inorganic material having a hole transport ability. Among them, organic materials having a hole transport ability include, but are 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 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), 4' -bis (9-Carbazole) Biphenyl (CBP), N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1 ' -biphenyl-4, one or more of 4' -diamine (TPD), N ' -diphenyl-N, N ' - (1-naphthyl) -1,1 ' -biphenyl-4, 4' -diamine (NPB); inorganic materials with hole transport capability include, but are not limited to, doped graphene, undoped graphene, C60, doped or undoped MoO3、VO2、WO3、CrO3、CuO、MoS2、MoSe2、WS2、WSe2And CuS.
Further, the light emitting layer 203 is disposed on the first functional layer 202, and preferably, the film thickness of the light emitting layer 203 is 10nm to 100 nm. Specifically, the material of the light-emitting layer 203 includes at least one of an inorganic semiconductor nanocrystal, an inorganic perovskite type semiconductor, an organic-inorganic hybrid perovskite nanocrystal, and an organic light-emitting material. Wherein the inorganic semiconductor nanocrystal comprises a doped or undoped II-V group compound semiconductor, a III-V group compound semiconductorOne or more of a compound semiconductor, a group IV-VI compound semiconductor and a core-shell structure semiconductor thereof. The inorganic perovskite type semiconductor may be doped or undoped, and specifically, the structural formula of the inorganic perovskite type semiconductor is AMX3Wherein A is Cs+Ion, M is a divalent metal cation, including but not limited to Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+X is a halide anion, including but not limited to Cl-、Br-、I-. The structural general formula of the organic-inorganic hybrid perovskite type nanocrystalline is BMX3Wherein B is an organic amine cation including but not limited to CH3(CH2)n-2NH3 +(n.gtoreq.2) or NH3(CH2)nNH3 2+(n is not less than 2), when n is 2, the inorganic metal halide octahedron MX6 4-The metal cations M are positioned in the center of a halogen octahedron through connection in a roof sharing mode, and the organic amine cations B are filled in gaps among the octahedrons to form an infinitely extending three-dimensional structure; inorganic metal halide octahedra MX linked in a coterminous manner when n > 26 4-The organic amine cation bilayer (protonated monoamine) or the organic amine cation monolayer (protonated diamine) is inserted between the layers, and the organic layer and the inorganic layer are overlapped with each other to form a stable two-dimensional layered structure; m is a divalent metal cation including, but not limited to, Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+(ii) a X is a halide anion, including but not limited to Cl-、Br-、I-. The organic light emitting material is an organic light emitting material that is conventional in the art, and includes, but is not limited to, Alq, Balq, DPVBi, and the like. Depending on the choice of the material of the light-emitting layer 203, the light-emitting form of the light-emitting layer 203 may be mainly organic material light-emitting, corresponding to an organic light-emitting (OLED) device(ii) a The quantum dot material can also be used for emitting light, and the quantum dot material corresponds to a quantum dot light emitting (QLED) device.
Further, the second functional layer 204 is an electron functional layer for transporting electrons, including but not limited to an electron transport layer and an electron injection layer disposed on the light emitting layer. Wherein the electron transport layer preferably has a thickness of 30nm-60nm, and the electron transport layer is not limited to be made of oxide electron transport material, such as n-type ZnO and TiO2、SnO、Ta2O3、AlZnO、ZnSnO、InSnO、Alq3、Ca、Ba、CsF、LiF、CsCO3Preferably n-type zinc oxide having high electron transport properties; the material of the electron transport layer can also be a sulfide electron transport material or an organic electron transport material. The material of the electron injection layer can be selected from Ca, Ba and other metals with low work function, and can also be selected from CsF, LiF and CsCO3The compound can also be other electrolyte type electron transport layer materials.
Further, the top electrode 205 is a cathode, the thickness of which is preferably 50nm to 150nm, and the material of the top electrode is one or more of various conductive carbon materials, conductive metal oxide materials and metal materials; wherein the conductive carbon material includes, but is not limited to, doped or undoped carbon nanotubes, doped or undoped graphene oxide, C60, graphite, carbon fibers, porous carbon, or mixtures thereof; conductive metal oxide materials include, but are not limited to, ITO, FTO, ATO, AZO, or mixtures thereof; metallic materials include, but are not limited to, Al, Ag, Cu, Mo, Au, or alloys thereof; wherein the metal material has a form including, but not limited to, a dense thin film, a nanowire, a nanosphere, a nanorod, a nanocone, a hollow nanosphere, or a mixture thereof; preferably, the cathode is Ag or Al.
In the embodiment of the present invention, the reduced graphene oxide layer 3 is formed on the upper surface of the light emitting device 2, wherein the bottom surface of the light emitting device 2 is connected to the substrate 1, and the side opposite to the bottom surface is the upper surface of the light emitting device 2. The material of the reduced graphene oxide layer 3 comprises diaminopyridine functionalized reduced graphene oxide (r-GO), and the reduced graphene oxide layer 3 emits light in the blue light range after absorbing heat. Generally, the temperature of the device during the light emitting and heat dissipating process is approximately in the range of 20 ℃ to 70 ℃, and in this range, the reduced graphene oxide layer 3 will absorb heat and emit light in the blue light range. Specifically, in the process of functionalizing graphene oxide with diaminopyridine, the energy level of the graphene oxide is hybridized to generate a hybrid orbit, and when electrons transit from the LUMO energy level to the hybrid orbit, blue light is emitted. Therefore, the reduced graphene oxide layer 3 absorbs heat under the driving of heat emitted by the device, the electron is transited to the LUMO energy level, and then the radiation transition is generated to generate blue light, so that the blue light compensation is realized while the heat of the device is reduced, the service life stability of the device is improved, and full-color display is formed.
In the traditional packaging process, the light emitted from the device chip is easy to generate total reflection phenomenon at the interface of the packaging structure, so that part of light is totally reflected back to the inside of the device due to the fact that the light enters the optical dense medium from the optical sparse medium, and the light emitting rate of the device is influenced. In the embodiment of the present invention, since the reduced graphene oxide layer 3 is disposed between the light emitting device 2 and the package structure 4, and the refractive index of the reduced graphene oxide layer 3 is preferably greater than 2, a total reflection phenomenon can be effectively avoided, the light extraction rate of the interface between the device and the package structure 4 is increased, and the reduced graphene oxide layer 3 can improve the light emitting efficiency of the light emitting device 2. Specifically, the encapsulation structure 4 generally includes an encapsulation adhesive and an encapsulation layer, and since the refractive index of the encapsulation adhesive is generally about 1.45-1.7, when the refractive index of the reduced graphene oxide layer 3 is greater than 2, the refractive index of the reduced graphene oxide layer 3 is greater than the refractive index of the encapsulation adhesive, and is greater than the refractive index of the encapsulation layer, and the refractive index is gradually decreased from the reduced graphene oxide layer 3, the encapsulation adhesive and the encapsulation layer, and the refractive index is matched, which is beneficial to light transmission.
In the embodiment of the present invention, the thickness of the reduced graphene oxide layer 3 has a large influence on the light emitting efficiency of the device, and preferably, the reduced graphene oxide layer 3 is a thin film layer with a thickness of 50nm to 300 nm. When the thickness is less than 5nm, the LED chip cannot be completely covered by the packaging structure 4, so that the packaging structure 4 is in contact with the chip and is totally reflected, and on the other hand, when the thickness is more than 30nm, the thickness of the whole device is increased, the probability that the packaging structure 4 cannot be completely covered is increased, so that the water vapor barrier property is reduced, and the service life is influenced.
In the embodiment of the present invention, the package structure 4 generally includes an encapsulant and an encapsulant layer, where the encapsulant is made of a conventional encapsulant material and has a refractive index of generally 1.45-1.7. The encapsulation layer is used as a functional layer for blocking water and oxygen, and can be made of an encapsulation material with good sealing performance, and further, in order to ensure the performance of the light-emitting device 2, the encapsulation material cannot react with the materials of the layers of the light-emitting device 2 in the embodiment of the present invention. Preferably, the encapsulation layer may be an encapsulation cover glass with a refractive index of 1.45.
According to the display equipment provided by the embodiment of the invention, the reduced graphene oxide layer 3 is introduced between the light-emitting device 2 and the packaging structure 4, and under the drive of heat emitted by the device, the reduced graphene oxide layer 3 absorbs heat, electronic transition is carried out to LUMO energy level, and then radiation transition is carried out to generate blue light, so that blue light compensation is realized while the heat of the device is reduced, the service life stability of the device is favorably improved, and full-color display is formed.
The display device provided by the embodiment of the invention can be prepared by the preparation method of the display device provided by the following embodiment.
The embodiment of the invention provides a preparation method of display equipment, which comprises the following steps:
step S101: a substrate is provided.
Step S102: a light emitting device is formed on a substrate.
Step S103: depositing a reduced graphene oxide layer on the light emitting device such that the reduced graphene oxide layer covers the light emitting device, wherein a material of the reduced graphene oxide layer includes diaminopyridine functionalized graphene oxide.
Step S104: and forming a packaging structure on the substrate and the light-emitting device covered by the reduced graphene oxide layer, so that the light-emitting device covered by the reduced graphene oxide layer is covered by the packaging structure.
In the embodiment of the present invention, the description of the substrate, the light emitting device, the reduced graphene oxide layer, and the package structure related to steps S101, S102, S103, and S104 is the same as the description of the substrate 1, the light emitting device 2, the reduced graphene oxide layer 3, and the package structure 4 related to the foregoing embodiments, and will not be described here.
In the embodiment of the present invention, the deposition method involved in the above steps may be a chemical method or a physical method, wherein the chemical method includes, but is not limited to, one or more of a chemical vapor deposition method, a continuous ion layer adsorption and reaction method, an anodic oxidation method, an electrolytic deposition method, a coprecipitation method; physical methods include, but are not limited to, physical coating methods or solution methods, wherein solution methods include, but are not limited to, spin coating, transfer printing, blade coating, dip-draw, dipping, spray coating, roll coating, casting, slit coating, bar coating; physical coating methods include, but are not limited to, one or more of thermal evaporation coating, electron beam evaporation coating, magnetron sputtering, multi-arc ion coating, physical vapor deposition, atomic layer deposition, pulsed laser deposition.
Further, taking a light emitting device with a positive structure, in which the first functional layer includes a hole transport layer disposed on the anode, and the second functional layer includes an electron transport layer disposed on the light emitting layer as an example, the step S102 specifically includes:
step S1011: depositing an anode on the substrate, carrying out ultrasonic cleaning for 10-20 min, and drying.
As a preferred embodiment, step S1011 may specifically be: and (3) placing the substrate deposited with the anode in acetone, washing liquor, deionized water and isopropanol in sequence for ultrasonic cleaning, wherein the ultrasonic cleaning of each step lasts for 10-20 min to remove impurities on the substrate, and after the ultrasonic cleaning is finished, placing the substrate deposited with the anode in a clean oven for drying.
Step S1021: depositing a hole transport layer on the anode and annealing at 100-200 deg.C for 10-30 min.
Step S1031: a light emitting layer is deposited over the hole transport layer.
Step S1041: depositing an electron transport layer on the luminescent layer, and heating at 60-100 ℃ for 20-40 min.
As a preferred embodiment, the heating process may be performed on a heating stage, and the solvent remaining on the light emitting layer may be effectively removed by heating at a temperature of 60 ℃ to 100 ℃ for 20min to 40 min.
Step S1051: a cathode is deposited on the electron transport layer.
As a preferred embodiment, step S1051 may specifically be: and (3) putting the sheet on which the functional layers are deposited into an evaporation bin, and thermally evaporating a layer of 50-150 nm metal silver or aluminum as a cathode through a mask plate.
Further, taking a light emitting device with an inversion structure, for example, the first functional layer includes an electron transport layer disposed on the cathode, and the second functional layer includes a hole transport layer disposed on the light emitting layer, then the step S101 specifically includes:
step S1012: and depositing a cathode on the substrate, carrying out ultrasonic cleaning for 10-20 min, and drying.
Step S1022: depositing an electron transport layer on the cathode, and heating at 60-100 deg.C for 20-40 min.
Step S1032: depositing the light emitting layer on the electron transport layer.
Step S1042: depositing a hole transport layer on the luminescent layer and annealing at 100-200 ℃ for 10-30 min.
Step S1052: an anode is deposited on the hole transport layer.
Further, as a preferred embodiment, the step of depositing a reduced graphene oxide layer on the light emitting device in step S103 includes: providing a mixed solution containing diaminopyridine and reduced graphene oxide, wherein the mass ratio of the diaminopyridine to the reduced graphene oxide in the mixed solution is 1-5: 10-25; and depositing the mixed solution on the light-emitting device by a solution method, and heating to prepare the reduced graphene oxide layer material.
Specifically, the mixed solution containing diaminopyridine and reduced graphene oxide is prepared by the following method: and adding the diaminopyridine and the reduced graphene oxide into a polar organic solvent according to an acid solution with the mass ratio of the diaminopyridine to the graphene oxide of 1-5:10-25 and the pH of 2-5, wherein the volume ratio of the acid solution to the polar organic solvent is 1:10-1:60, and preparing to obtain a mixed solution containing the diaminopyridine and the reduced graphene oxide.
In a specific embodiment, 1mg to 5mg of diaminopyridine and 10mg to 25m of reduced graphene oxide are added into 30ml to 60ml of polar organic solvent, 1ml to 3ml of acid solution with the pH value of 2 to 5 is added, and the mixture is heated at 80 ℃ to 120 ℃ for 4h to 8h to react to generate the reduced graphene oxide layer material. An acid solution with pH of 2-5 is used as a catalyst in the reaction process, and preferably, the acid solution can be a dilute hydrochloric acid solution; the polar organic solvent may preferably be an ethanol solution.
Further, as a preferred embodiment, after step S103, annealing the reduced graphene oxide layer deposited on the top electrode is further included. Specifically, the temperature of the annealing treatment is 50-100 ℃, and the time of the annealing treatment is 20-30 min.
Further, as a preferred embodiment, after step S104, a heating process is further included for the package structure. Specifically, the package structure may be subjected to ozone-ultraviolet baking for 3 min.
The preparation is illustrated by way of example below:
(1) and (3) putting the ITO substrate into acetone, washing liquor, deionized water and isopropanol in sequence for ultrasonic cleaning, wherein the ultrasonic cleaning lasts for 15min in each step. And after the ultrasonic treatment is finished, the substrate is placed in a clean oven to be dried for later use.
(2) After the ITO substrate is dried, a hole transport layer TFB is deposited on the ITO substrate, the thickness of the hole transport layer TFB is 80nm, and the ITO substrate is placed on a heating table at 150 ℃ to be heated for 15 min.
(3) And (3) after the step (2) is cooled, depositing quantum dots on the hole transport layer TFB, wherein the thickness of the layer is 40nm, and heating is not needed.
(4) After that, an electron transport layer ZnO with a thickness of 40nm was deposited. The sheet on which the electron transport layer ZnO was deposited was placed on a heating stage at 80 ℃ and heated for 30 minutes to remove the residual solvent.
(5) And finally, placing the sheets on which the functional layers are deposited in an evaporation bin, and thermally evaporating a layer of 100nm metal silver through a mask plate, thereby completing the preparation of the device.
(6) And depositing the reduced graphene oxide layer on the surface of the cathode by a solution film forming method, and annealing for 30 minutes at 80 ℃.
(7) And (3) dripping packaging glue on the device on which the reduced graphene oxide layer is deposited, covering a glass packaging cover plate, and baking for 3min by ozone-ultraviolet. And finishing the packaging of the device.
The preparation method of the display device provided by the embodiment of the invention can prepare the display device with uniform and stable light emission, high heat dissipation efficiency, long service life and high light emission efficiency, has low process difficulty, is easy to operate, has low cost and can realize large-scale production.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. A display device, comprising:
a substrate;
a light emitting device disposed on the substrate;
a reduced graphene oxide layer covering the light emitting device, the material of the reduced graphene oxide layer comprising diaminopyridine-functionalized reduced graphene oxide;
an encapsulation structure disposed on the substrate and the light emitting device covered by the reduced graphene oxide layer, the encapsulation structure covering the light emitting device covered by the reduced graphene oxide layer;
the refractive index of the reduced graphene oxide layer is greater than that of the packaging structure.
2. The display device of claim 1, wherein the reduced graphene oxide layer has a refractive index greater than 2.
3. The display device of claim 1, wherein the layer of reduced graphene oxide has a thickness of 5nm to 30 nm.
4. A display device according to any one of claims 1 to 3, wherein the light-emitting device is a positive-structure light-emitting device or an inverted-structure light-emitting device.
5. The display device according to claim 4, wherein the light-emitting device includes a light-emitting layer having a thickness of 10nm to 100 nm; and/or the material of the luminescent layer is at least one of inorganic semiconductor nanocrystalline, IV group simple substance semiconductor luminescent material, perovskite nanocrystalline and organic luminescent material.
6. A method for manufacturing a display device, the method comprising:
providing a substrate;
forming a light emitting device on the substrate;
depositing a layer of reduced graphene oxide on the light emitting device such that the layer of reduced graphene oxide covers the light emitting device, wherein the material of the layer of reduced graphene oxide comprises diaminopyridine functionalized graphene oxide;
forming a packaging structure on the substrate and the light-emitting device covered by the reduced graphene oxide layer, so that the packaging structure covers the light-emitting device covered by the reduced graphene oxide layer;
the refractive index of the reduced graphene oxide layer is greater than that of the packaging structure.
7. The method of claim 6, wherein the step of depositing the layer of reduced graphene oxide on the light emitting device comprises:
providing a mixed solution containing diaminopyridine and reduced graphene oxide, wherein the mass ratio of the diaminopyridine to the reduced graphene oxide in the mixed solution is (1-5) to (10-25);
and depositing the mixed solution on the light-emitting device by a solution method, and heating to prepare the reduced graphene oxide layer material layer.
8. The method of claim 6 or 7, further comprising, after depositing the layer of reduced graphene oxide on the outer surface of the light emitting device:
and annealing the reduced graphene oxide layer.
9. The method according to claim 8, wherein the temperature of the annealing treatment is 50 ℃ to 100 ℃, and the time of the annealing treatment is 20min to 30 min.
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