CN111384298A - Composite material, thin film and preparation method thereof, and quantum dot light-emitting diode - Google Patents
Composite material, thin film and preparation method thereof, and quantum dot light-emitting diode Download PDFInfo
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- 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
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
- H10K50/165—Electron transporting layers comprising dopants
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
Abstract
The invention provides a composite material which is composed of nano zinc oxide and graphene, wherein the graphene accounts for 0.1-10 wt% of the total weight of the composite material as 100%. When the composite material of the nano zinc oxide and a proper amount of graphene is used as an electron transport layer material of a quantum dot light-emitting device, electrons can be prevented from being further transported to a valence band of the quantum dot, exciton quenching probability is reduced, and light-emitting efficiency of the device is improved.
Description
Technical Field
The invention belongs to the technical field of display, and particularly relates to a composite material, a thin film and a preparation method thereof, and a quantum dot light-emitting diode.
Background
A quantum dot light emitting diode (QLED) is a device that applies a dc voltage to an anode and a cathode to drive a quantum dot material to emit light, has the advantages of color saturation, high purity, good monochromaticity, color adjustability, and solution preparation, and is considered as an advantageous technology of the next-generation flat panel display.
Currently, a well-studied QLED generally adopts a multilayer structure, and a device includes an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode. Acceptable carrier transport layers generally require suitable optoelectronic properties (including band structure, conductivity, work function), good stability and solution processability. ZnO has the characteristics of wide band gap, high optical transparency, good chemical and thermal stability, high carrier concentration, high electron transmission rate and the like, and is an ideal electron transmission layer material. However, as the ZnO has more surface defect states generated by oxygen vacancies, electrons injected from the electrode can be captured and further transmitted to the valence band of the quantum dot, so that excitons are quenched, and the luminous efficiency of the device is reduced. Meanwhile, in the currently mainstream QLED devices (ZnO is used as an electron transport layer, and organic is used as a hole transport layer), the electron transport efficiency of the electron transport layer is much higher than the hole transport efficiency of the hole transport layer, so in order to achieve charge balance, researchers have reduced the injection of electrons by adding a blocking layer between ZnO and quantum dot light emitting layers (QDs), and improved the light emitting efficiency of the device.
Disclosure of Invention
The invention aims to provide a composite material, and aims to solve the problems that in the prior art, when nano zinc oxide is used as an electron transport layer, the surface defect state is more, excitons are quenched, and the charge balance is not easy to realize.
The invention provides a film containing the composite material and a preparation method thereof.
Another object of the present invention is to provide a quantum dot light emitting diode comprising the composite material or the thin film.
In order to achieve the purpose, the invention adopts the following technical scheme:
the composite material is nano zinc oxide and graphene, and the weight percentage of the graphene is 0.1% -10% based on 100% of the total weight of the composite material.
The film comprises a composite material which is nano zinc oxide and graphene, wherein the graphene accounts for 0.1-10 wt% of the total weight of the composite material as 100%.
A method of making a film comprising the steps of:
dispersing the nano zinc oxide and the graphene in an organic solvent according to the proportion that the graphene accounts for 0.1-10% of the total weight of the graphene and the nano zinc oxide, and carrying out ultrasonic treatment after mixing to obtain a mixed solution;
and depositing the mixed solution on the surface of a substrate, and drying to form a film.
A quantum dot light-emitting diode comprises an anode and a cathode which are oppositely arranged, a quantum dot light-emitting layer arranged between the anode and the cathode, and an electron transport layer arranged between the cathode and the quantum dot light-emitting layer, wherein the electron transport layer is made of the composite material or the thin film.
Correspondingly, the preparation method of the quantum dot light-emitting diode comprises the following steps:
dispersing the nano zinc oxide and the graphene in an organic solvent according to the proportion that the graphene accounts for 0.1-10% of the total weight of the graphene and the nano zinc oxide, and carrying out ultrasonic treatment after mixing to obtain a mixed solution;
and providing a first substrate, depositing the mixed solution on the surface of the first substrate, drying to form a film, and preparing the electron transport layer.
The composite material provided by the invention takes nano zinc oxide as a material main body and is compounded with a graphene material. In the composite material, as the graphene is a good electron acceptor, the work function (-4.42eV) is lower than the conduction band (-4.05eV) of the nano zinc oxide. After a proper amount of graphene is doped into the nano zinc oxide, electrons captured by the surface defect state of the nano zinc oxide are easy to migrate into the graphene. Therefore, when the composite material of the nano zinc oxide and a proper amount of graphene is used as an electron transport layer material of the quantum dot light-emitting device, electrons can be prevented from being further transported to a valence band of the quantum dot, exciton quenching probability is reduced, and light-emitting efficiency of the device is improved. In the present invention, the more graphene is added to the composite material, the better the graphene is. Specifically, the weight percentage of the graphene is 0.1% -10% based on 100% of the total weight of the composite material, and when the obtained composite material is used as an electron transmission material of a light emitting diode, electrons can be effectively prevented from being further transmitted to a valence band of a quantum dot, the exciton quenching probability is reduced, and the light emitting efficiency of a device is improved. When the content of the graphene is excessive, the excessive graphene doped into the nano zinc oxide can obviously reduce the Fermi level of the nano zinc oxide, promote the transmission of electrons at an interface from the nano zinc oxide to the quantum dot light emitting layer, destroy the charge balance in the quantum dot light emitting diode and reduce the light emitting efficiency of the device.
The film material of the film provided by the invention is the composite material of the nano zinc oxide and the graphene. Therefore, when the film is used as an electron transport layer of the light-emitting diode, electrons can be effectively prevented from being further transported to the valence band of the quantum dot, the exciton quenching probability is reduced, and the light-emitting efficiency of the device is improved.
The preparation method of the film provided by the invention comprises the steps of dispersing graphene and nano zinc oxide in an organic solvent according to the dosage ratio, mixing, performing ultrasonic dispersion, depositing the obtained mixed solution on the surface of a target substrate of the film to be deposited, and drying to obtain the film. The method is simple and easy to operate, and when the obtained film is used as an electron transmission layer of the light-emitting diode, electrons can be effectively prevented from being further transmitted to a valence band of a quantum dot, the exciton quenching probability is reduced, and the luminous efficiency of the device is improved.
The quantum dot light-emitting diode provided by the invention comprises an electron transport layer, wherein the electron transport layer is made of a composite material of the nano zinc oxide and the graphene. The quantum dot light-emitting diode obtained by the method can effectively prevent electrons from being further transmitted to the valence band of the quantum dot, reduce the exciton quenching probability and improve the light-emitting efficiency of the device. The preparation method of the quantum dot light-emitting diode provided by the invention comprises the steps of dispersing graphene and nano zinc oxide in an organic solvent according to the dosage ratio, mixing, performing ultrasonic dispersion, depositing the obtained mixed solution on the surface of a first substrate of a film to be deposited, and drying to obtain the electron transport layer. The method is simple and easy to operate, and the obtained electron transfer layer can effectively prevent electrons from being further transferred to the valence band of the quantum dot, reduce the exciton quenching probability and improve the luminous efficiency of the device.
Drawings
Fig. 1 is a schematic structural diagram of a quantum dot light-emitting diode provided in an embodiment of the present invention;
fig. 2 is a schematic flow chart of a method for preparing a thin film according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In 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.
The embodiment of the invention provides a composite material which is composed of nano zinc oxide and graphene, wherein the graphene accounts for 0.1-10 wt% of the total weight of the composite material as 100%.
The composite material provided by the embodiment of the invention takes nano zinc oxide as a material main body and is compounded with a graphene material. In the composite material, as the graphene is a good electron acceptor, the work function (-4.42eV) is lower than the conduction band (-4.05eV) of the nano zinc oxide. After a proper amount of graphene is doped into the nano zinc oxide, electrons captured by the surface defect state of the nano zinc oxide are easy to migrate into the graphene. Therefore, when the composite material of the nano zinc oxide and a proper amount of graphene is used as an electron transport layer material of the quantum dot light-emitting device, electrons can be prevented from being further transported to a valence band of the quantum dot, exciton quenching probability is reduced, and light-emitting efficiency of the device is improved. In the embodiment of the invention, the addition amount of the graphene in the composite material is not as large as possible. Specifically, the weight percentage of the graphene is 0.1% -10% based on 100% of the total weight of the composite material, and when the obtained composite material is used as an electron transmission material of a light emitting diode, electrons can be effectively prevented from being further transmitted to a valence band of a quantum dot, the exciton quenching probability is reduced, and the light emitting efficiency of a device is improved. When the content of the graphene is excessive, the excessive graphene doped into the nano zinc oxide can obviously reduce the Fermi level of the nano zinc oxide, promote the transmission of electrons at an interface from the nano zinc oxide to the quantum dot light emitting layer, destroy the charge balance in the quantum dot light emitting diode and reduce the light emitting efficiency of the device.
In the embodiment of the present invention, the nano zinc oxide and the graphene are both conventional nano zinc oxide and graphene, and the present invention is not strictly limited. Preferably, the graphene accounts for 3-10 wt% of the total weight of the composite material as 100%. In this case, the doping amount of the graphene in the nano zinc oxide is more appropriate, and electrons captured by the surface defect state of the nano zinc oxide can be better transferred to the graphene. Furthermore, when the composite material of the nano zinc oxide and a proper amount of graphene is used as an electron transport layer material of the quantum dot light-emitting device, electrons can be better prevented from being further transported to a valence band of the quantum dot, exciton quenching probability is reduced, and light-emitting efficiency of the device is improved.
The embodiment of the invention provides a film, wherein the material of the film comprises a composite material, the composite material comprises nano zinc oxide and graphene, and the weight percentage of the graphene is 0.1-10% based on 100% of the total weight of the composite material.
According to the film provided by the embodiment of the invention, the film material is a composite material of the nano zinc oxide and the graphene. Therefore, when the film is used as an electron transport layer of the light-emitting diode, electrons can be effectively prevented from being further transported to the valence band of the quantum dot, the exciton quenching probability is reduced, and the light-emitting efficiency of the device is improved.
In a preferred embodiment, the graphene accounts for 3 to 10 weight percent of the total weight of the composite material, so that when the thin film is used as an electron transport layer, electrons can be better prevented from being further transported to a valence band of a quantum dot, exciton quenching probability is reduced, and luminous efficiency of a device is improved.
On the basis of the above embodiment, preferably, in the thin film, the weight percentage of the graphene is distributed in a gradient manner along a direction perpendicular to the thin film. Specifically, when the film is used as an electron transport layer of a light emitting device, particularly a quantum dot light emitting diode, the graphene concentration in the film gradually increases along the direction from a light emitting layer such as a quantum dot light emitting layer to a cathode, so that a graphene/ZnO composite electron transport layer with graphene gradient distribution is formed. At the moment, the ZnO concentration at one end close to the quantum dot light-emitting layer is higher, correspondingly, the graphene concentration is low, the graphene in the thin film is not easy to be excessive, the Fermi level of ZnO is not obviously reduced, the transmission of electrons at the interface from ZnO to the quantum dot light-emitting layer is promoted, the charge balance in the QLED device is damaged, and the light-emitting efficiency of the device is reduced. The formed film can effectively utilize graphene to passivate ZnO, reduce quenching of ZnO surface defect states to excitons, avoid the phenomenon of unbalanced device charges caused by excessively reducing the Fermi level of ZnO, and finally effectively improve the luminous efficiency of the device.
The film provided by the embodiment of the invention can be prepared by the following method.
Correspondingly, referring to a schematic flow chart of a method for preparing a thin film in an embodiment of the present invention shown in fig. 2, an embodiment of the present invention provides a method for preparing a thin film, including the following steps:
s01, dispersing nano zinc oxide and graphene in an organic solvent according to the proportion that the graphene accounts for 0.1% -10% of the total weight of the graphene and the nano zinc oxide, and carrying out ultrasonic treatment after mixing to obtain a mixed solution;
s02, depositing the mixed solution on the surface of a substrate, and drying to form a film.
The preparation method of the film provided by the embodiment of the invention comprises the steps of dispersing graphene and nano zinc oxide in an organic solvent according to the dosage ratio, mixing, performing ultrasonic dispersion, depositing the obtained mixed solution on the surface of a target substrate of the film to be deposited, and drying to obtain the film. The method is simple and easy to operate, and when the obtained film is used as an electron transmission layer of the light-emitting diode, electrons can be effectively prevented from being further transmitted to a valence band of a quantum dot, the exciton quenching probability is reduced, and the luminous efficiency of the device is improved.
Specifically, in step S01, in the embodiment of the present invention, both the nano zinc oxide and the graphene may be prepared by referring to an existing method.
As an example, the preparation method of the zinc oxide is as follows: dissolving zinc acetate in dimethyl sulfoxide, dissolving tetramethyl ammonium hydroxide in ethanol, mixing, and stirring at room temperature for reaction; after the reaction is finished, adding ethyl acetate, and removing supernatant liquor after centrifugal treatment; and adding ethanolamine and ethanol into the collected precipitate to stabilize the nano particles, washing with ethyl acetate, centrifuging to remove supernatant, and drying to obtain the ZnO nano particles. As a specific preferred embodiment, zinc acetate and dimethyl sulfoxide are dissolved in the mass volume ratio of 1g to 60ml, and tetramethylammonium hydroxide and ethanol are dissolved in the mass volume ratio of 1.0 g:10ml, dissolving tetramethyl ammonium hydroxide in ethanol, mixing, and stirring for 24 hours at room temperature; adding ethyl acetate after the reaction is finished, centrifuging for 10min at the rotating speed of 8000rpm, removing supernatant, adding ethanolamine and ethanol to the precipitate according to the mass-volume ratio of 1g to 1ml of zinc acetate to ethanolamine and the mass-volume ratio of 1g to 10ml of zinc acetate to ethanol to stabilize nanoparticles, cleaning with ethyl acetate, centrifuging for 10min at the rotating speed of 8000rpm, removing supernatant, drying to obtain ZnO nanoparticles, and finally dissolving in an appropriate amount of ethanol.
As an embodiment, the preparation method of the graphene comprises the following steps: graphene oxide is prepared by a hummer method, and then the graphene oxide is reduced by hydrazine hydrate to obtain graphene.
The nano zinc oxide and the graphene are dispersed in the organic solvent according to the proportion that the graphene accounts for 0.1-10% of the total weight of the graphene and the nano zinc oxide, and the method can be realized by various methods.
In some embodiments, the organic solution of graphene and the organic solution of nano zinc oxide are provided separately, and the organic solution of graphene and the organic solution of nano zinc oxide are mixed in a ratio of 0.1% to 10% of graphene based on the total weight of graphene and nano zinc oxide. The solvent in the organic solution of graphene can be an organic solvent capable of effectively dispersing graphene, and is preferably an organic alcohol; the solvent in the organic solution of the nano zinc oxide is an organic solvent capable of effectively dispersing the nano zinc oxide and the graphene, and is preferably organic alcohol. In a particularly preferred embodiment, the solvent in the organic solution of graphene and the solvent in the organic solution of nano zinc oxide are both ethanol.
In some embodiments, the graphene and the nano zinc oxide are separately provided, dispersed in an organic solvent, and subjected to a mixing process. The organic solvent is an organic solvent capable of effectively dispersing the nano zinc oxide and the graphene at the same time, and is preferably an organic alcohol, and particularly preferably ethanol.
And dispersing the nano zinc oxide and the graphene in an organic solvent, and mixing. In order to disperse both uniformly, the obtained dispersion system was subjected to ultrasonic treatment. Preferably, the ultrasonic treatment is carried out for 4 to 6 hours in a natural state to obtain a mixed solution.
In step S02, the mixed solution is deposited on the surface of the substrate by conventional solution processing methods, such as inkjet printing, spin coating, etc. Further, the film is formed by drying treatment. The substrate is any substrate on which the mixed solution needs to be deposited, and particularly, when the composite material of nano zinc oxide and graphene is used as an electron transport layer material of a quantum dot light emitting diode, the substrate may be a stack in which an anode/a quantum dot light emitting layer, a stack in which an anode/a hole functional layer/a quantum dot light emitting layer, a cathode, and a stack in which a cathode/an electron injection layer are stacked.
Preferably, the mixed solution is deposited on the surface of a substrate to prepare a film with graphene gradient distribution along the direction vertical to the film layer.
In some embodiments, the mixed solution is deposited on the surface of a substrate, and the film is dried to form a film by the following method:
s021, depositing the mixed solution on the surface of a substrate, and placing the substrate deposited with the mixed solution into a heatable device, wherein the heatable device comprises a bottom plate and a top plate which are oppositely and parallelly arranged, and the substrate deposited with the mixed solution is placed in the closable device in parallel to the bottom plate;
s022, heating the closable device.
According to the method, the mixed solution is deposited on the surface of a substrate, the substrate deposited with the mixed solution is placed in a heatable device with a specific structure, and gradient distribution of graphene in a film layer is achieved by regulating and controlling heating conditions. Specifically, the heatable device comprises a bottom plate and a top plate which are oppositely and parallelly arranged, and the substrate deposited with the mixed solution is placed in the closable device in parallel with the bottom plate.
Preferably, in the step of heating the closable device, the temperature of the bottom plate is 60 to 80 ℃, the temperature of the top plate is 80 to 120 ℃, and the temperature difference between the bottom plate and the top plate is not less than 20 ℃. Under the heating condition, a temperature gradient is formed, under the driving of the temperature gradient, zinc oxide nanoparticles loaded on graphene by physical adsorption move from the top (the side close to the top plate) to the bottom (the side close to the top plate), and finally, a composite graphene/ZnO thin film with low top nano-zinc oxide concentration and high bottom nano-zinc oxide concentration is formed after drying. Since the solution itself is easy to form a state with lower surface energy, graphene is more prone to be exposed on the surface, and in the presence of a temperature gradient, the movement of zinc oxide nanoparticles is accelerated, which is more beneficial to forming a thin film with a concentration gradient.
Preferably, the substrate deposited with the mixed solution is not in direct contact with the bottom plate and the top plate of the heatable device, thereby facilitating the formation of a significant temperature gradient in the thin film layer. More preferably, the height between the bottom plate and the top plate is h, the substrate deposited with the mixed solution is placed between h/3-2 h/3, so that a relatively uniform and gentle temperature gradient is favorably formed, the smooth change of the concentration of the graphene in the obtained film layer is favorably realized, the graphene passivation ZnO is favorably and effectively utilized, the quenching of ZnO surface defect states to excitons is reduced, meanwhile, the phenomenon of unbalanced device charges caused by excessively reducing the Fermi level of ZnO is avoided, and the luminous efficiency of the device is effectively improved.
In some embodiments, the mixed solution is deposited on the surface of a substrate, and the film is dried to form a film by the following method:
and depositing the mixed solution on the surface of a substrate, placing the substrate deposited with the mixed solution on a hot plate, and carrying out heating treatment under the condition that the hot plate is externally connected with a positive voltage to prepare the film.
Preferably, in the method, the step of performing the heat treatment under the condition that the hot plate is externally connected with a positive voltage is performed at a temperature of 80 to 120 ℃. Because the surfaces of the nano zinc oxide particles in the mixed solution usually have hydroxyl groups and show negative electricity, the nano zinc oxide particles loaded on the graphene can move from the top to the bottom under the driving of electrostatic adsorption, and finally, a composite graphene/ZnO film with low top nano zinc oxide concentration and high bottom nano zinc oxide concentration is formed after drying.
As shown in fig. 1, an embodiment of the present invention further provides a quantum dot light emitting diode, which includes an anode 1 and a cathode 6 that are oppositely disposed, a quantum dot light emitting layer 4 disposed between the anode 1 and the cathode 6, and an electron transport layer 5 disposed between the cathode 6 and the quantum dot light emitting layer 4, where the material of the electron transport layer 5 is the composite material according to the embodiment of the present invention, or the electron transport layer 5 is the thin film according to the embodiment of the present invention.
The quantum dot light-emitting diode provided by the embodiment of the invention comprises an electron transport layer, wherein the electron transport layer is made of a composite material of the nano zinc oxide and the graphene. The quantum dot light-emitting diode obtained by the method can effectively prevent electrons from being further transmitted to the valence band of the quantum dot, reduce the exciton quenching probability and improve the light-emitting efficiency of the device.
Preferably, the content of graphene in the electron transport layer 5 increases gradually from the quantum dot light emitting layer 4 to the cathode 6. At the moment, the concentration of ZnO at one end close to the quantum dot light-emitting layer 4 is higher, correspondingly, the concentration of graphene is low, so that the formed film can effectively utilize the graphene to passivate ZnO, the quenching of ZnO surface defect states to excitons is reduced, meanwhile, the phenomenon of unbalanced device charge caused by excessively reducing the Fermi level of ZnO is avoided, and the light-emitting efficiency of the device is finally and effectively improved.
Specifically, the quantum dot light-emitting diode further comprises a substrate 0, wherein the substrate 0 can be arranged at one end of the anode 1 to form an upright quantum dot light-emitting diode; the substrate 0 may be disposed at one end of the cathode 6 to form an inverted quantum dot light emitting diode.
In some embodiments, the quantum dot light emitting diode further comprises at least one of a hole function layer and a hole injection layer disposed between the anode 1 and the quantum dot light emitting layer 4. In a preferred embodiment, the quantum dot light emitting diode includes a hole function layer 2 disposed between an anode 1 and a quantum dot light emitting layer 4, and a hole injection layer 3 disposed between the hole transport layer 2 and the quantum dot light emitting layer 4.
In some embodiments, the qd-led further comprises an electron injection layer (not shown) disposed between the cathode 6 and the electron transport layer 5.
Correspondingly, the embodiment of the invention provides a preparation method of a quantum dot light-emitting diode, which comprises the following steps:
dispersing the nano zinc oxide and the graphene in an organic solvent according to the proportion that the graphene accounts for 0.1-10% of the total weight of the graphene and the nano zinc oxide, and carrying out ultrasonic treatment after mixing to obtain a mixed solution;
and providing a first substrate, depositing the mixed solution on the surface of the first substrate, drying to form a film, and preparing the electron transport layer.
According to the preparation method of the quantum dot light-emitting diode provided by the embodiment of the invention, graphene and nano zinc oxide are dispersed in an organic solvent according to the dosage ratio, ultrasonic dispersion is carried out after mixing, the obtained mixed solution is deposited on the surface of a first substrate of a film to be deposited, and an electron transmission layer can be obtained after drying treatment. The method is simple and easy to operate, and the obtained electron transfer layer can effectively prevent electrons from being further transferred to the valence band of the quantum dot, reduce the exciton quenching probability and improve the luminous efficiency of the device.
In the embodiments of the present invention, the step of preparing the electron transport layer on the surface of the first substrate and the preferred embodiments thereof are not repeated herein for saving space, as described above.
In one embodiment, the first substrate includes an anode, and a quantum dot light emitting layer disposed on the anode. Preferably, the first substrate further includes a hole function layer disposed between the anode and the quantum dot light emitting layer. Wherein the hole function layer includes but is not limited to at least one of a hole injection layer, a hole transport layer, and an electron blocking layer. In some embodiments, the anode is an anode disposed on a substrate.
Further, after the electron transport layer is prepared, a cathode is prepared on the surface of the electron transport layer, which is far away from the quantum dot light emitting layer. Preferably, before preparing the cathode, preparing an electron injection layer on the surface of the electron transport layer, which faces away from the quantum dot light emitting layer.
As another implementation, the first substrate is a cathode. In some embodiments, the cathode is a cathode disposed on the substrate. Preferably, before preparing the electron transport layer, an electron injection layer is prepared on the cathode.
Furthermore, after the electron transport layer is prepared, a quantum dot light-emitting layer is prepared on the surface of the electron transport layer, which is far away from the cathode, and an anode is prepared on the surface of the quantum dot light-emitting layer, which is far away from the cathode. Preferably, before preparing the anode, the method further comprises preparing a hole function layer on the surface of the quantum dot light-emitting layer, which faces away from the cathode. Wherein the hole function layer includes but is not limited to at least one of a hole injection layer, a hole transport layer, and an electron blocking layer.
The following description will be given with reference to specific examples.
Example 1
A quantum dot light emitting diode comprises a substrate, an anode and a cathode arranged on the substrate, and a laminated structure arranged between the anode and the cathode, wherein the laminated structure comprises a hole injection layer, a hole transport layer, a quantum dot light emitting layer and an electron transport layer which are combined in a laminated mode, the hole injection layer is arranged adjacent to the anode, and the electron transport layer is arranged adjacent to the cathode.
The preparation method of the quantum dot light-emitting diode comprises the following steps:
depositing a hole injection layer on the anode substrate, depositing a hole transport layer on the hole injection layer, and depositing a quantum dot light-emitting layer on the hole transport layer;
spin-coating a graphene/ZnO composite material solution on a quantum dot light-emitting layer, and placing the quantum dot light-emitting layer in a heatable device, wherein the heatable device comprises a bottom plate and a top plate which are oppositely and parallelly arranged, and the substrate deposited with the mixed solution is placed in the closable device in parallel with the bottom plate. Heating the sealable device to enable the heating temperature of the bottom plate to be 60 ℃ and the heating temperature of the top plate to be 80 ℃, and drying to form an electron transmission layer of the composite graphene/ZnO with low top ZnO concentration and high bottom ZnO concentration;
and depositing a cathode on the electron transport layer, and packaging to finish the preparation of the device.
Example 2
The difference from the embodiment 1 is that the heating temperature of the bottom plate is 60 ℃, the heating temperature of the top plate is 100 ℃, and the substrate deposited with the mixed solution is arranged between h/3 and 2h/3 by taking the height between the bottom plate and the top plate as h.
Example 3
The difference from the embodiment 1 is that the heating temperature of the bottom plate is 60 ℃, the heating temperature of the top plate is 120 ℃, and the substrate deposited with the mixed solution is arranged between h/3 and 2h/3 by taking the height between the bottom plate and the top plate as h.
Example 4
The difference from the embodiment 1 is that the heating temperature of the bottom plate is 70 ℃, the heating temperature of the top plate is 90 ℃, and the substrate deposited with the mixed solution is arranged between h/3 and 2h/3, wherein the height between the bottom plate and the top plate is h.
Example 5
The difference from the embodiment 1 is that the heating temperature of the bottom plate is 70 ℃, the heating temperature of the top plate is 105 ℃, and the substrate deposited with the mixed solution is arranged between h/3 and 2h/3, wherein the height between the bottom plate and the top plate is h.
Example 5
The difference from the embodiment 1 is that the heating temperature of the bottom plate is 70 ℃, the heating temperature of the top plate is 120 ℃, and the substrate deposited with the mixed solution is arranged between h/3 and 2h/3 by taking the height between the bottom plate and the top plate as h.
Example 6
The difference from the embodiment 1 is that the heating temperature of the bottom plate is 80 ℃, the heating temperature of the top plate is 120 ℃, and the substrate deposited with the mixed solution is arranged between h/3 and 2h/3 by taking the height between the bottom plate and the top plate as h.
Example 7
A quantum dot light emitting diode comprises a substrate, an anode and a cathode arranged on the substrate, and a laminated structure arranged between the anode and the cathode, wherein the laminated structure comprises a hole injection layer, a hole transport layer, a quantum dot light emitting layer and an electron transport layer which are combined in a laminated mode, the hole injection layer is arranged adjacent to the anode, and the electron transport layer is arranged adjacent to the cathode.
The preparation method of the quantum dot light-emitting diode comprises the following steps:
depositing a hole injection layer on the anode substrate, depositing a hole transport layer on the hole injection layer, and depositing a quantum dot light-emitting layer on the hole transport layer;
the method comprises the steps of coating a graphene/ZnO composite material solution on a quantum dot light-emitting layer in a spinning mode, placing the quantum dot light-emitting layer on a hot plate, heating the quantum dot light-emitting layer under the condition that the hot plate is externally connected with a positive voltage and the temperature is 80 ℃, and drying the composite material solution to form an electron transmission layer of composite graphene/ZnO with low top ZnO concentration and high bottom ZnO concentration;
and depositing a cathode on the electron transport layer, and packaging to finish the preparation of the device.
Example 8
The difference from the embodiment 2 is that the graphene/ZnO composite material solution is spin-coated on the quantum dot light-emitting layer, placed on a hot plate, externally connected with a positive voltage, heated at 90 ℃, and dried to form the graphene/ZnO composite electron transport layer with low ZnO concentration at the top and high ZnO concentration at the bottom.
Example 9
The difference from the embodiment 2 is that the graphene/ZnO composite material solution is spin-coated on the quantum dot light-emitting layer, placed on a hot plate, externally connected with a positive voltage, heated at a temperature of 100 ℃, and dried to form the graphene/ZnO composite electron transport layer with low ZnO concentration at the top and high ZnO concentration at the bottom.
Example 10
The difference from the embodiment 2 is that the graphene/ZnO composite material solution is spin-coated on the quantum dot light-emitting layer, placed on a hot plate, externally connected with a positive voltage, heated at a temperature of 110 ℃, and dried to form the graphene/ZnO composite electron transport layer with low ZnO concentration at the top and high ZnO concentration at the bottom.
Example 11
The difference from the embodiment 2 is that the graphene/ZnO composite material solution is spin-coated on the quantum dot light-emitting layer, placed on a hot plate, externally connected with a positive voltage, heated at 120 ℃, and dried to form the graphene/ZnO composite electron transport layer with low ZnO concentration at the top and high ZnO concentration at the bottom.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (13)
1. The composite material is characterized by comprising nano zinc oxide and graphene, wherein the graphene accounts for 0.1-10 wt% of the total weight of the composite material as 100%.
2. The composite material of claim 1, wherein the graphene is present in an amount of 3% to 10% by weight, based on 100% by weight of the total composite material.
3. The film is characterized in that the material of the film comprises a composite material, the composite material is nano zinc oxide and graphene, and the weight percentage of the graphene is 0.1% -10% based on 100% of the total weight of the composite material.
4. The film of claim 3, wherein the graphene is present in an amount of 3% to 10% by weight, based on 100% by weight of the total composite.
5. The film of claim 3 or 4, wherein the weight percent of the graphene is graded in a direction perpendicular to the film.
6. A method for preparing a film, comprising the steps of:
dispersing the nano zinc oxide and the graphene in an organic solvent according to the proportion that the graphene accounts for 0.1-10% of the total weight of the graphene and the nano zinc oxide, and carrying out ultrasonic treatment after mixing to obtain a mixed solution;
and depositing the mixed solution on the surface of a substrate, and drying to form a film.
7. The method for preparing a thin film according to claim 6, wherein the mixed solution is deposited on the surface of a substrate and dried to form a film by:
depositing the mixed solution on the surface of a substrate, and placing the substrate deposited with the mixed solution in a heatable device, wherein the heatable device comprises a bottom plate and a top plate which are oppositely and parallelly arranged, and the substrate deposited with the mixed solution is placed in the closable device in parallel with the bottom plate;
and heating the closable device.
8. The method for producing a film according to claim 7, wherein in the step of heat-treating the closable device, the temperature of the bottom plate is 60 to 80 ℃, the temperature of the top plate is 80 to 120 ℃, and the temperature difference between the bottom plate and the top plate is 20 ℃ or more in the heatable device.
9. The method for preparing a thin film according to claim 6, wherein the mixed solution is deposited on the surface of a substrate and dried to form a film by:
and depositing the mixed solution on the surface of a substrate, placing the substrate deposited with the mixed solution on a hot plate, and carrying out heating treatment under the condition that the hot plate is externally connected with a positive voltage to prepare the film.
10. The method for preparing a thin film according to claim 9, wherein the step of performing the heat treatment under the condition that the hot plate is externally connected with a positive voltage is performed at a temperature of 80 to 120 ℃.
11. A quantum dot light emitting diode comprising an anode and a cathode which are oppositely arranged, a quantum dot light emitting layer arranged between the anode and the cathode, and an electron transport layer arranged between the cathode and the quantum dot light emitting layer, wherein the material of the electron transport layer is the composite material as claimed in any one of claims 1 or 2, or the electron transport layer is the thin film as claimed in any one of claims 3 to 5.
12. The qd-led of claim 11, wherein the amount of graphene in the electron transport layer increases from the qd-light emitting layer to the cathode.
13. A preparation method of a quantum dot light-emitting diode is characterized by comprising the following steps:
dispersing the nano zinc oxide and the graphene in an organic solvent according to the proportion that the graphene accounts for 0.1-10% of the total weight of the graphene and the nano zinc oxide, and carrying out ultrasonic treatment after mixing to obtain a mixed solution;
and providing a first substrate, depositing the mixed solution on the surface of the first substrate, drying to form a film, and preparing the electron transport layer.
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