CN113054117A - Light emitting diode and preparation method thereof - Google Patents

Light emitting diode and preparation method thereof Download PDF

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CN113054117A
CN113054117A CN201911383557.7A CN201911383557A CN113054117A CN 113054117 A CN113054117 A CN 113054117A CN 201911383557 A CN201911383557 A CN 201911383557A CN 113054117 A CN113054117 A CN 113054117A
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layer
fullerene derivative
cerium
depositing
solution
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CN113054117B (en
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何斯纳
吴龙佳
吴劲衡
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TCL Research America Inc
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—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]
    • H10K50/11—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
    • H10K71/00—Manufacture or treatment specially adapted for 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • 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

Abstract

The invention belongs to the technical field of display, and particularly relates to a light-emitting diode and a preparation method thereof. The present invention provides a light emitting diode comprising: an anode and a cathode disposed opposite to each other, a light emitting layer disposed between the anode and the cathode, and an electron transport layer disposed between the cathode and the light emitting layer, the electron transport layer including: the fullerene derivative layer is arranged on the surface of the cerium dioxide layer, which is far away from the light-emitting layer; wherein, the fullerene derivative layer is made of [6,6] -phenyl-C61-isopropyl butyrate and/or [6,6] -phenyl-C61-butyric acid, so that the luminous efficiency of the light-emitting diode is improved.

Description

Light emitting diode and preparation method thereof
Technical Field
The invention belongs to the technical field of display, and particularly relates to a light-emitting diode and a preparation method thereof.
Background
Quantum Dot Light Emitting Diodes (QLEDs) are electroluminescent devices, and have the advantages of unique optical size dependence, narrow emission peak, high luminous efficiency, high color purity, and the like, so that the Quantum Dot Light Emitting Diodes have a wide application prospect in the fields of solid-state lighting, flat panel display, and the like, and are widely concerned by academia and industry.
Currently, QLEDs mainly include: the 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 light-emitting layer. The light-emitting principle mainly comprises the following steps: under the drive of an external electric field, electrons and holes are respectively injected from the cathode and the anode, and then are combined in the light-emitting layer to form excitons for light emission. The electron transfer efficiency and the energy level structure of the electron transport layer directly determine the electron injection efficiency, which plays a crucial role in the light emitting efficiency of the QLED, and finding a suitable electron transport layer to improve the light emitting efficiency of the QLED becomes the research focus of those skilled in the art.
Disclosure of Invention
The present invention is directed to a light emitting diode, so as to improve the light emitting efficiency of the light emitting diode.
The invention also aims to provide a preparation method of the light-emitting diode.
In order to achieve the purpose, the invention adopts the following technical scheme:
a light emitting diode comprising: an anode and a cathode disposed opposite each other, a light emitting layer disposed between the anode and the cathode, an electron transport layer disposed between the cathode and the light emitting layer, the electron transport layer comprising: the luminescent layer comprises a cerium dioxide layer and a fullerene derivative layer, wherein the fullerene derivative layer is arranged on the surface of the cerium dioxide layer, which is far away from the luminescent layer;
wherein the material of the fullerene derivative layer comprises [6,6] -phenyl-C61-iso-methyl butyrate and/or [6,6] -phenyl-C61-butyric acid.
The electron transport layer of the light emitting diode provided by the invention comprises a cerium dioxide layer and a fullerene derivative layer, wherein the fullerene derivative layer is arranged on the surface of the cerium dioxide layer away from the light emitting layer, and the fullerene derivative layer is made of [6,6] material]-phenyl-C61-butyric acid isopropyl ester (PCBM) and/or [6,6]]-phenyl-C61-butyric acid (PCBA). Introducing a fullerene derivative layer on the surface of the cerium dioxide layer, wherein the positions of conduction bands of PCBM and PCBA are lower than that of CeO2And the position of the conduction band of PCBM and PCBA and CeO2Near the Fermi level of CeO2Layer and fullerene derivatizationWhen the object layers are in good electric contact, the energy level of the fullerene derivative layer can be leveled, and electrons can be better transmitted to CeO from the cathode through the fullerene derivative layer2The conduction band reduces the electron injection potential barrier, reduces the contact resistance and promotes the electrons to be injected into the electron transport layer from the cathode; meanwhile, the fullerene derivative has a conjugated cage-shaped carbon molecular structure, has excellent electron holding capacity and high electron transfer performance, and the fullerene derivative layer and the cerium dioxide layer are compounded to form the electron transmission layer, so that the electron transmission efficiency in the light-emitting diode can be obviously improved, and the light-emitting efficiency of the light-emitting diode is improved.
Correspondingly, the preparation method of the light-emitting diode comprises the following steps:
obtaining a substrate, the substrate comprising: an anode and a light emitting layer disposed on the anode;
depositing a cerium dioxide layer on the light-emitting layer and depositing a fullerene derivative layer on the cerium dioxide layer to form an electron transport layer; the material of the fullerene derivative layer comprises [6,6] -phenyl-C61-iso-methyl butyrate and/or [6,6] -phenyl-C61-butyric acid;
depositing a cathode on the fullerene derivative layer;
or, the preparation method of the light emitting diode comprises the following steps:
depositing a fullerene derivative layer on a cathode and depositing a cerium oxide layer on the fullerene derivative layer to form an electron transport layer; the material of the fullerene derivative layer comprises [6,6] -phenyl-C61-iso-methyl butyrate and/or [6,6] -phenyl-C61-butyric acid;
depositing a light emitting layer on the ceria layer and depositing the anode on the light emitting layer.
According to the preparation method of the light-emitting diode, the electron transmission layer is formed by depositing the cerium dioxide layer and the fullerene derivative layer, and the preparation method is simple, simple and convenient to operate and easy for mass production. The method deposits the fullerene derivative layer on the cerium dioxide layer or deposits the cerium dioxide layer on the fullerene derivative layer, thereby reducing the electron injection barrier, reducing the contact resistance, promoting the electrons to be injected into the electron transmission layer from the cathode, improving the electron transmission efficiency in the light-emitting diode and further improving the light-emitting efficiency of the light-emitting diode.
Drawings
Fig. 1 is a schematic structural diagram of a light emitting diode according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a light emitting diode according to an embodiment of the present invention;
fig. 3 is a flowchart of a method for manufacturing a light emitting diode according to an embodiment of the present invention;
fig. 4 is a flowchart of a method for manufacturing a light emitting diode 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.
A light emitting diode comprising: an anode and a cathode disposed opposite each other, a light emitting layer disposed between the anode and the cathode, an electron transport layer disposed between the cathode and the light emitting layer, the electron transport layer comprising: the luminescent layer comprises a cerium dioxide layer and a fullerene derivative layer, wherein the fullerene derivative layer is arranged on the surface of the cerium dioxide layer, which is far away from the luminescent layer;
wherein the material of the fullerene derivative layer comprises [6,6] -phenyl-C61-iso-methyl butyrate and/or [6,6] -phenyl-C61-butyric acid.
Specifically, as shown in fig. 1, the electron transport layer includes: the luminescent layer comprises a cerium dioxide layer and a fullerene derivative layer, wherein the fullerene derivative layer is arranged on the surface of the cerium dioxide layer, which faces away from the luminescent layer, and the material of the fullerene derivative layer comprises [6,6] -phenyl-C61-isopropyl butyrate and/or [6,6] -phenyl-C61-butyric acid.
Cerium oxide (CeO)2) The material is a direct band gap wide band gap semiconductor material with the band gap width of 2.6-3.4eV, and is a cheap light rare earth oxide. Since CeO2The light-emitting diode with the cerium dioxide layer as the electron transport layer has the defect of low electron injection efficiency and low light-emitting efficiency.
The fullerene derivative has a conjugated cage-like carbon molecular structure of fullerene, has excellent electron holding capacity and high electron transfer performance. Different from the scheme of taking the cerium dioxide layer or the fullerene derivative layer as the electron transport layer, the fullerene derivative layer is introduced on the surface of the cerium dioxide layer, and the position (4.3eV) of the conduction band of PCBA is lower than that of CeO2(2.8eV), and the position of the conduction band of PCBA and CeO2Near the Fermi level of CeO2When the layer and the fullerene derivative layer have good electric contact, the energy level of the fullerene derivative layer can be leveled, and electrons can be better transmitted to CeO from the cathode through the fullerene derivative layer2The conduction band of (2) reduces an electron injection barrier, reduces contact resistance, and promotes electron injection from the cathode into the electron transport layer.
In the light-emitting diode, the fullerene derivative layer is made of [6,6] -phenyl-C61-isopropyl butyrate and/or [6,6] -phenyl-C61-butyric acid. In some embodiments, the material of the fullerene derivative layer is preferably [6,6] -phenyl-C61-butyric acid (PCBA). PCBA is a product formed by PCBM hydrolysis under an alkaline condition, PCBA can generate double-tooth bonding with one or two cerium atoms of a cerium dioxide layer interface through carboxyl, so that the interface between the fullerene derivative layer and the cerium dioxide layer is more tightly combined, and the electron injection efficiency of the electron transport layer can be further improved.
In one embodiment, the electron transport layer is a ceria layer and a fullerene derivative layer, and the fullerene derivative layer is disposed on a surface of the ceria layer away from the light emitting layer.
In one embodiment, the fullerene derivative layer in the quantum dot light emitting diode has a thickness of 10-30 nm; the fullerene derivative layer is too thin to well cover the adjacent layer; the fullerene derivative layer is too thick to be beneficial to the transmission efficiency of the electron transport layer, and may affect the device performance, so the overall effect in the range of 10-30nm is the best. Further, the thickness of the electron transport layer is 40-80 nm; the thickness of the ceria layer is 30-50 nm.
In the light emitting diode, the materials of the anode, the light emitting layer and the cathode can refer to a conventional light emitting diode, and can also be respectively selected to be specific materials.
As an embodiment, the material of the anode is selected from at least one of indium doped tin oxide (ITO), fluorine doped tin oxide (FTO), tin doped zinc oxide (ZTO).
In one embodiment, the material of the light emitting layer is selected to be quantum dots. The quantum dots comprise IV group quantum dots, II-VI group quantum dots, II-V group quantum dots, III-VI group quantum dots, IV-VI group quantum dots, I-III-VI group quantum dots, II-IV-VI group quantum dots and II-IV-V group quantum dots, have quantum dot characteristics and high luminous efficiency. In some embodiments, the luminescent quantum dots are oil-soluble quantum dots, including binary phase, ternary phase, and quaternary phase quantum dots. Wherein the binary phase quantum dots include CdS, CdSe, CdTe, InP, AgS, PbS, PbSe, HgS, etc., but are not limited thereto, and the ternary phase quantum dots include ZnXCd1-XS、CuXIn1-XS、ZnXCd1-XSe、ZnXSe1-XS、ZnXCd1-XTe、PbSeXS1-XAnd the like, but not limited thereto, the quaternary phase quantum dots include ZnXCd1-XS/ZnSe、CuXIn1-XS/ZnS、ZnXCd1-XSe/ZnS、CuInSeS、ZnXCd1-XTe/ZnS、PbSeXS1-Xand/ZnS, etc., but are not limited thereto. The quantum dots can be any one of common red, green and blue quantum dots or other yellow light quantum dots, and can be cadmium-containing or cadmium-free quantum dots. The quantum dot light emitting layer of the material has the characteristics of wide and continuous excitation spectrum distribution, high emission spectrum stability and the like. In some embodiments, the particle size of the quantum dots is 20-60nm, and the color of the light emitting diode can be adjusted by controlling the size.
In one embodiment, the material of the cathode comprises at least one of Al, Cu, Mo, Au, Ag. In some embodiments, the cathode has a thickness of 15-30 nm.
The structure of the light emitting diode can refer to the conventional technology in the field, for example, in some embodiments, the light emitting diode is a positive structure, and the anode is connected with a substrate to serve as a bottom electrode; in some embodiments, the light emitting diode is an inverted structure, and the cathode is connected to the substrate as a bottom electrode. Further, in addition to the functional film layers such as the cathode, the anode, the light-emitting layer, and the electron transport layer, a hole functional layer such as a hole transport layer, a hole injection layer, and a hole blocking layer may be provided between the anode and the light-emitting layer, and an electron functional layer such as an electron injection layer and an electron blocking layer may be provided between the cathode and the light-emitting layer.
As one embodiment, as shown in fig. 2, the light emitting diode includes an anode L01, a hole injection layer L02, a hole transport layer L03, a quantum dot light emitting layer L04, an electron transport layer L05, and a cathode L06, which are sequentially stacked. In some embodiments, the anode is 30-110nm thick, the hole injection layer is 30-100nm thick, the hole transport layer is 30-100nm thick, the quantum dot light-emitting layer is 10-100nm thick, the electron transport layer is 40-80nm thick, and the cathode is 90-110nm thick.
To sum up, in the light emitting diode provided by the embodiment of the present invention, the electron transport layer includes a cerium oxide layer and a fullerene derivative layer, the fullerene derivative layer is disposed on a surface of the cerium oxide layer away from the light emitting layer, and the fullerene derivative layer is made of [6,6]]-phenyl-C61-butyric acid isopropyl ester (PCBM) and/or [6,6]]-phenyl-C61-butyric acid (PCBA). Introducing a fullerene derivative layer on the surface of the cerium dioxide layer, wherein the positions of conduction bands of PCBM and PCBA are lower than that of CeO2And the position of the conduction band of PCBM and PCBA and CeO2Near the Fermi level of CeO2When the layer and the fullerene derivative layer have good electric contact, the energy level of the fullerene derivative layer can be leveled, and electrons can be better transmitted to CeO from the cathode through the fullerene derivative layer2The conduction band reduces the electron injection barrier and the connectionA contact resistance to facilitate electron injection from the cathode into the electron transport layer; meanwhile, the fullerene derivative has a conjugated cage-shaped carbon molecular structure, has excellent electron holding capacity and high electron transfer performance, and the fullerene derivative layer and the cerium dioxide layer are compounded to form the electron transmission layer, so that the electron transmission efficiency in the light-emitting diode can be obviously improved, and the light-emitting efficiency of the light-emitting diode is improved.
Based on the technical scheme, the embodiment of the invention also provides a preparation method of the light-emitting diode.
Accordingly, a method for manufacturing a light emitting diode, as shown in fig. 3, includes the following steps:
s01, obtaining a substrate, wherein the substrate comprises: an anode and a light emitting layer disposed on the anode;
s02, depositing a cerium dioxide layer on the light-emitting layer and depositing a fullerene derivative layer on the cerium dioxide layer to form an electron transport layer; the material of the fullerene derivative layer comprises [6,6] -phenyl-C61-iso-methyl butyrate and/or [6,6] -phenyl-C61-butyric acid;
s03, depositing a cathode on the fullerene derivative layer;
or, as shown in fig. 4, the method for manufacturing the light emitting diode includes the following steps:
s01', depositing a fullerene derivative layer on a cathode and depositing a cerium oxide layer on the fullerene derivative layer to form an electron transport layer; the material of the fullerene derivative layer comprises [6,6] -phenyl-C61-iso-methyl butyrate and/or [6,6] -phenyl-C61-butyric acid;
s02', depositing a light emitting layer on the cerium oxide layer, and depositing the anode on the light emitting layer.
Specifically, the kinds of the anode and the light emitting layer in step S01 are substantially the same as those described above, and are not described in detail herein for the sake of brevity.
In some embodiments, the anode is an ITO substrate, which may be obtained by depositing a light-emitting layer on the ITO substrate. In a further embodiment, in order to obtain a high-quality quantum dot light emitting diode, the ITO substrate needs to be subjected to a pretreatment process. The basic specific processing steps include: cleaning the whole ITO substrate with a cleaning agent to primarily remove stains on the surface, then sequentially carrying out ultrasonic cleaning in deionized water, acetone, absolute ethyl alcohol and deionized water for 20min respectively to remove impurities on the surface, and finally blowing the ITO substrate with high-purity nitrogen to obtain the ITO substrate.
Specifically, in step S02, the deposition method may refer to a conventional deposition method in the art, such as depositing a ceria layer and a fullerene derivative layer on the light-emitting layer by using a magnetron sputtering method, a chemical vapor deposition method, an evaporation method, a spin coating method, an inkjet printing method, and the like.
As an embodiment, the step of depositing a cerium oxide layer on the light emitting layer and depositing a fullerene derivative layer on the cerium oxide layer includes:
s021, obtaining a cerium dioxide solution, depositing the cerium dioxide solution on the light-emitting layer by adopting a spin coating method or an ink-jet printing method, and performing first drying treatment to prepare a cerium dioxide layer;
s022, obtaining a fullerene derivative solution, depositing the fullerene derivative solution on the cerium dioxide layer by adopting a spin coating method or an ink-jet printing method, and performing second drying treatment to prepare the fullerene derivative layer.
In step S021, the cerium oxide solution contains cerium oxide, and its preparation may refer to a conventional procedure in the art, for example, commercially available cerium oxide is dispersed in alcohol.
In addition, the cerium oxide solution may also be a cerium oxide-containing reaction solution prepared by a sol-gel method, and in some embodiments, the preparation of cerium oxide of the cerium oxide solution includes the steps of:
s0211, obtaining a cerium precursor and alcohol, dissolving the cerium precursor in the alcohol, and preparing a cerium precursor solution with the concentration of 0.5-1 mol/L;
s0212, providing alkali, mixing the alkali and the cerium precursor solution according to the molar ratio of (3-5) to 1 of the alkali to cerium atoms in the cerium precursor solution, and reacting at 60-80 ℃ for 2-10 hours to obtain a cerium dioxide solution.
In step S0211, the cerium precursor is dissolved in the alcohol to form an alcoholysis product, and the cerium oxide is prepared by a subsequent alcoholysis reaction. And dissolving the cerium precursor in the alcohol to prepare a cerium precursor solution with the concentration of 0.5-1 mol/L. Wherein the cerium precursor is used to provide cerium atoms, such as in some embodiments, the cerium precursor includes at least one of cerium sulfate, cerium nitrate, and cerium chloride. The alcohol is used as a solvent for the cerium precursor and as a reaction solvent for a subsequent alcoholysis reaction, and in some embodiments, the alcohol is selected from at least one of methanol, ethanol, isopropanol, propanol, butanol, pentanol, and hexanol. In a further embodiment, in order to sufficiently dissolve the cerium precursor in the alcohol, a method of heating and stirring, for example, adding the cerium precursor to ethanol, methanol or propanol, and stirring at 60 to 80 ℃, is employed.
In step S0212, the alkali and the cerium precursor solution are mixed according to the molar ratio of the alkali to the cerium atoms in the cerium precursor solution of (3-5):1, and then the mixture is reacted at 60-80 ℃ for 2-10 hours to obtain a cerium dioxide solution.
Wherein the base comprises an organic base and/or an inorganic base, and in some embodiments, the organic base is selected from one of ethanolamine, diethanolamine, triethanolamine, and ethylenediamine; in some embodiments, the inorganic base is selected from potassium hydroxide, sodium hydroxide, lithium hydroxide, and the like. Preferably, the base is selected from at least one of potassium hydroxide, sodium hydroxide and ethanolamine.
The step of mixing the base with the cerium precursor solution in a molar ratio of the base to the cerium atoms in the cerium precursor solution of (3-5):1 may be performed by referring to a conventional procedure in the art. In some embodiments, the base is added to the cerium precursor solution in the form of a lye. The lye is a solution of alkali dissolved in an alcohol including, but not limited to, isopropanol, ethanol, propanol, butanol, pentanol, hexanol, and the like.
In some embodiments, in the step of mixing the base with the cerium precursor solution in a ratio of (3-5):1, the molar ratio of the base to the cerium atoms in the cerium precursor solution is 3.0:1, 3.5:1, 4.0:1, 4.5:1, 5.0: 1. By controlling the molar ratio of the alkali to the cerium atoms in the cerium precursor solution in the reaction to be in the range, a cerium dioxide layer obtained by subsequent reaction can be more compact and compact, and the particle distribution is more uniform; meanwhile, in the proportion range, the pH of the reaction liquid can be made to be 12-13, so that the influence on the generation of cerium dioxide caused by overhigh or overlow pH of the reaction system is avoided. When the molar ratio of the base to the cerium atoms is less than 3.5:1, the cerium salt is excessive, the alkali liquor is less, and the generated cerium hydroxide is insufficient; when the molar ratio of base to cerium atoms is greater than 4.5:1, too high a pH results in a slower polycondensation rate in the system.
In some embodiments, in the step of reacting at 60-80 ℃ for 2-4 hours, the reaction temperature is 60, 62, 65, 68, 69, 70, 71, 73, 75, 80 ℃ and the reaction time is 2, 3, 4 hours.
A first drying process is performed to remove the solvent, so that cerium oxide is deposited on the light emitting layer, thereby forming a cerium oxide layer. The first drying process may be performed according to conventional methods in the art, and in some embodiments, the first drying process includes an annealing process at 300 ℃ and 200 ℃ to obtain a dense ceria layer with good crystallinity.
In step S022, the fullerene derivative solution is dissolved with fullerene derivatives, and the preparation thereof may refer to the conventional operation in the art, such as in some embodiments, commercially available fullerene derivative is dissolved in alcohol. Wherein the solvent for dissolving the fullerene derivative may be the same as or different from the solvent for the cerium oxide solution.
In some embodiments, the concentration of the fullerene derivative in the fullerene derivative solution is 1-3 mg/mL. In some embodiments, the concentration of PCBM in the PCBM solution is 1, 1.3, 1.5, 1.7, 2.0, 2.1, 2.3, 2.5, 2.7, 2.9, 3 mg/mL.
In some embodiments, the fullerene derivative is PCBA, the preparation of which comprises: dispersing PCBM in organic solvent, adding alkali according to the molar ratio of alkali to PCBM of (1-1.5) to 1, and stirring at 60-90 deg.C for 2-3 hr; adding a proper amount of dilute hydrochloric acid to neutralize unreacted alkali, cooling to room temperature, and separating out a solid; and (5) carrying out suction filtration, washing with water and drying in an oven. Wherein the organic solvent includes, but is not limited to, diethyl ether, chloroform, carbon tetrachloride, and the like.
Performing a second drying process to remove the solvent, so that the fullerene derivative is deposited on the cerium oxide layer, thereby forming a fullerene derivative layer. The step of performing the second drying treatment may be performed according to conventional methods in the art, and in some embodiments, the second drying treatment includes an annealing treatment at 100-150 ℃.
In step S03, the step of depositing the cathode on the fullerene derivative layer may be performed by referring to conventional operations in the art, such as depositing the cathode on the fullerene derivative layer by magnetron sputtering, chemical vapor deposition, evaporation, spin coating, inkjet printing, and the like, wherein the cathode is made of substantially the same material as the cathode described above.
Specifically, in step S01', the steps of depositing the fullerene derivative layer on the cathode and depositing the cerium oxide layer on the fullerene derivative layer may refer to the conventional operations in the art, such as depositing the fullerene derivative layer and the cerium oxide layer on the cathode by using magnetron sputtering, chemical vapor deposition, evaporation, spin coating, inkjet printing, etc., which are different from the above step S02 mainly in that: the fullerene derivative layer is deposited on the cathode and then the cerium dioxide layer is deposited, and the fullerene derivative layer, the cerium dioxide layer and the cathode are basically the same as those described above, and are not repeated here.
As an embodiment, the steps of depositing a fullerene derivative layer on a cathode and depositing a ceria layer on the fullerene derivative layer include:
s011', obtaining a fullerene derivative solution, depositing the fullerene derivative solution on the cathode by adopting a spin-coating method or an ink-jet printing method, and carrying out third drying treatment to prepare the fullerene derivative layer;
s012' obtaining a cerium oxide solution, depositing the cerium oxide solution on the fullerene derivative layer by using a spin coating method or an inkjet printing method, and performing a fourth drying process to prepare the cerium oxide layer.
The materials of the fullerene derivative solution and the cerium dioxide solution and the preparation methods thereof are basically the same as those described above, and are not repeated here.
In addition, the third drying process is for promoting deposition of a fullerene derivative on the cathode. The third drying process may refer to the second drying process described above, and in some embodiments, the third drying process includes an annealing process at 150 ℃ and 100 ℃ to obtain a dense ceria layer with good crystallinity.
The fourth drying process is for promoting deposition of ceria on the fullerene derivative layer. The fourth drying process may refer to the first drying process described above, and in some embodiments, the fourth drying process includes an annealing process at 200-300 ℃ to obtain a dense ceria layer with good crystallinity.
In summary, the method for manufacturing the light emitting diode according to the embodiment of the invention deposits the cerium dioxide layer and the fullerene derivative layer on the light emitting layer to form the electron transport layer, and has the advantages of simple method, simple operation and easy mass production. According to the method provided by the embodiment of the invention, the fullerene derivative layer is deposited on the cerium dioxide layer, or the cerium dioxide layer is deposited on the fullerene derivative layer, so that the electron injection barrier is reduced, the contact resistance is reduced, the electron injection from the cathode to the electron transmission layer is promoted, the electron transmission efficiency in the light-emitting diode is improved, and the light-emitting efficiency of the light-emitting diode is improved.
In order that the above details of the practice and operation of the present invention will be clearly understood by those skilled in the art, and the advanced nature of the light emitting diode and the method of making the same according to the embodiments of the present invention will be apparent, the practice of the present invention will be illustrated by the following examples.
Example 1
This example produced a multilayer structure comprising the following steps:
1) preparation of CeO2Solutions of
Cerium sulfate was added to 50mL of ethanol and dissolved at 70 ℃ with stirring to prepare a 0.5M cerium sulfate solution. Then, 10mL of a potassium hydroxide-ethanol solution (molar ratio, OH) was added to the cerium sulfate solution-：Ce4+4: pH 12) and stirring at 70 ℃ for 4h to obtain CeO2And (3) solution.
2) PCBM was dispersed in 10mL ethanol, and 10mL of potassium hydroxide-ethanol solution was added (molar ratio of potassium hydroxide to PCBM was 1.5: 1, pH 12), stirred at 70 ℃ for 2 h; adding appropriate amount of dilute hydrochloric acid to adjust pH to 5, and stirring for 30 min; after the reaction is finished, cooling to room temperature to separate out a solid; carrying out suction filtration, washing with water and drying in an oven; the product was dissolved in ether solvent to form a PCBA solution at a concentration of 1.5 mg/mL.
3) Adding CeO2Depositing the solution on a substrate by adopting a spin coating method or an ink-jet printing method, and annealing at 250 ℃ to form the cerium dioxide layer;
4) the PCBA solution is deposited on the cerium dioxide layer by adopting a spin coating method or an ink-jet printing method, and is annealed at 150 ℃ to prepare the PCBA layer.
Example 2
This example produced a multilayer structure comprising the following steps:
1) preparation of CeO2Solutions of
Cerium nitrate was added to 50mL of methanol, and dissolved with stirring at 60 ℃ to prepare a cerium nitrate solution having a concentration of 0.8M. Then, 10mL of an ethanolamine-methanol solution (molar ratio, ethanolamine: Ce) was added to the cerium nitrate solution4+4.5: pH 13) and stirring at 60 ℃ for 4h to obtain CeO2And (3) solution.
2) PCBM was dissolved in ethanol to form a PCBM solution at a concentration of 2 mg/mL.
3) Adding CeO2Depositing the solution on a substrate by adopting a spin coating method or an ink-jet printing method, and annealing at 200 ℃ to form the cerium dioxide layer;
4) depositing a PCBM solution on the cerium dioxide layer by using a spin-coating method or an ink-jet printing method, and annealing at 120 ℃ to prepare the PCBM layer.
Example 3
This example produced a multilayer structure comprising the following steps:
1) preparation of CeO2Solutions of
Cerium chloride was added to 50mL of propanol and dissolved at 80 ℃ with stirring to prepare a 1M cerium sulfate solution. Then, 10mL of sodium hydroxide-propanol solution (molar ratio, OH) was added to the cerium chloride solution-：Ce4+3.5: pH 13) and stirring at 80 ℃ for 4h to obtain CeO2And (3) solution.
2) PCBM was dispersed in 10mL of propanol, and 10mL of sodium hydroxide-propanol solution (molar ratio of sodium hydroxide to PCBM 1: 1, pH 12), stirred at 80 ℃ for 2 h; adding appropriate amount of dilute hydrochloric acid to adjust pH to 4, and stirring for 30 min; after the reaction is finished, cooling to room temperature to separate out a solid; carrying out suction filtration, washing with water and drying in an oven; the product was dissolved in chloroform solvent to form a PCBA solution with a concentration of 2.5 mg/mL.
3) Adding CeO2Depositing the solution on a substrate by adopting a spin coating method or an ink-jet printing method, and annealing at 250 ℃ to form the cerium dioxide layer;
4) and depositing the PCBA solution on the cerium dioxide layer by adopting a spin coating method or an ink-jet printing method, and annealing at 100 ℃ to prepare the fullerene derivative layer.
Example 4
This embodiment prepares a quantum dot light emitting diode, including: the 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, an electron transport layer arranged between the cathode and the quantum dot light-emitting layer, a hole transport layer arranged between the anode and the quantum dot light-emitting layer, and a hole injection layer arranged between the anode and the hole transport layer. Wherein the anode is connected with the substrate as a bottom electrode, the substrate is made of glass sheet, the anode is made of ITO substrate, the hole injection layer is made of PEDOT, PSS and blankThe hole transmission layer is made of TFB, and the quantum dot light-emitting layer is made of CdXZn1-XS/ZnS quantum dot, and the electron transport layer is made of PCBA/CeO2The cathode is made of Al.
The preparation method of the quantum dot light-emitting diode specifically comprises the following steps:
1) providing an ITO substrate, and depositing a hole injection layer, a hole transport layer and a quantum dot light emitting layer on the ITO substrate in sequence;
2) the CeO obtained in example 1 was added2Depositing the solution on the luminescent layer by adopting a spin coating method or an ink-jet printing method, and annealing at 250 ℃ to form the cerium dioxide layer;
3) the PCBA solution prepared in example 1 was deposited on the ceria layer using a spin-coating method or an ink-jet printing method, and annealed at 150 ℃ to prepare the fullerene derivative layer.
4) Depositing a cathode on the fullerene derivative layer.
Example 5
This embodiment prepares a quantum dot light emitting diode, including: the 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, an electron transport layer arranged between the cathode and the quantum dot light-emitting layer, a hole transport layer arranged between the anode and the quantum dot light-emitting layer, and a hole injection layer arranged between the anode and the hole transport layer. The anode is connected with a substrate as a bottom electrode, the substrate is made of a glass sheet, the anode is made of an ITO (indium tin oxide) substrate, the hole injection layer is made of PEDOT (Poly ethylene terephthalate): PSS (styrene), the hole transport layer is made of TFB (thin film transistor), and the quantum dot light-emitting layer is made of blue light CdXZn1-XThe S/ZnS quantum dot and the electron transport layer are made of PCBM/CeO2The cathode is made of Al.
The preparation method of the quantum dot light-emitting diode specifically comprises the following steps:
1) providing an ITO substrate, and depositing a hole injection layer, a hole transport layer and a quantum dot light emitting layer on the ITO substrate in sequence;
2) the CeO obtained in example 2 was added2Solution miningDepositing the cerium dioxide layer on the luminescent layer by using a spin coating method or an ink-jet printing method, and annealing at 200 ℃ to form the cerium dioxide layer;
3) the PCBM solution prepared in example 2 was deposited on the ceria layer by spin coating or inkjet printing, and annealed at 120 ℃ to prepare the fullerene derivative layer.
4) Depositing a cathode on the fullerene derivative layer.
Example 6
This embodiment prepares a quantum dot light emitting diode, including: the 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, an electron transport layer arranged between the cathode and the quantum dot light-emitting layer, a hole transport layer arranged between the anode and the quantum dot light-emitting layer, and a hole injection layer arranged between the anode and the hole transport layer. The anode is connected with a substrate as a bottom electrode, the substrate is made of a glass sheet, the anode is made of an ITO (indium tin oxide) substrate, the hole injection layer is made of PEDOT (Poly ethylene terephthalate): PSS (styrene), the hole transport layer is made of TFB (thin film transistor), and the quantum dot light-emitting layer is made of blue light CdXZn1-XS/ZnS quantum dot, and the electron transport layer is made of PCBA/CeO2The cathode is made of Al.
The preparation method of the quantum dot light-emitting diode specifically comprises the following steps:
1) providing an ITO substrate, and depositing a hole injection layer, a hole transport layer and a quantum dot light emitting layer on the ITO substrate in sequence;
2) the CeO obtained in example 3 was added2Depositing the solution on the luminescent layer by adopting a spin coating method or an ink-jet printing method, and annealing at 250 ℃ to form the cerium dioxide layer;
3) the PCBA solution prepared in example 3 was deposited on the ceria layer using spin coating or inkjet printing, and annealed at 100 ℃ to prepare the fullerene derivative layer.
4) Depositing a cathode on the fullerene derivative layer.
Example 7
This example prepares a quantum dot light emitting diode, which is different from example 1 in that: the cathode is connected to the substrate as a bottom electrode, and the rest is basically the same as that in embodiment 1, and the description thereof is omitted.
Example 8
This example prepares a quantum dot light emitting diode, which is different from example 2 in that: the cathode is connected to the substrate as a bottom electrode, and the rest of the process is substantially the same as that of embodiment 2, and the description thereof is omitted.
Example 9
This example prepares a quantum dot light emitting diode, which is different from example 3 in that: the cathode is connected to the substrate as a bottom electrode, and the rest is basically the same as that in embodiment 3, and the description thereof is omitted.
Comparative example 1
This comparative example prepared an electron transport film, which was different from example 2 in that: the material of the electron transport layer is CeO2(available from sigma), the rest of which is substantially the same as that of example 2, and will not be described in detail.
Comparative example 2
This comparative example prepared an electron transport film, which was different from example 2 in that: the material of the electron transport layer is PCBM (from sigma), and the rest is basically the same as that in embodiment 2, and is not described in detail here.
The multilayer structures prepared in examples 1 to 3, the quantum dot light emitting diodes prepared in examples 4 to 9, and the electron transport films prepared in comparative examples 1 to 2 were subjected to performance tests according to the following test indexes and test methods:
(1) electron mobility: testing the current density (J) -voltage (V) of the quantum dot light-emitting diode, drawing a curve relation diagram, fitting a Space Charge Limited Current (SCLC) region in the relation diagram, and then calculating the electron mobility according to a well-known Child's law formula:
J＝(9/8)εrε0μeV2/d3
wherein J represents current density in mAcm-2；εrDenotes the relative dielectric constant,. epsilon0Represents the vacuum dielectric constant; mu.seIndicating electricityMobility, in cm2V-1s-1(ii) a V represents the drive voltage, in units of V; d represents the film thickness in m.
(2) Resistivity: the resistivity of the electron transport film is measured by the same resistivity measuring instrument.
(3) External Quantum Efficiency (EQE): measured using an EQE optical test instrument.
Note: the electron mobility and the resistivity are tested to be single-layer thin film structure devices; the external quantum efficiency test is a QLED device.
The test results are shown in table 1:
TABLE 1
Figure BDA0002342897330000161
As can be seen from table 1 above, the multilayer structures provided in examples 1 to 3 of the present invention have a resistivity significantly lower than those of the electron transport films in comparative examples 1 and 2, and an electron mobility significantly higher than that of the electron transport film made of the metal compound nanomaterial in comparative example 1.
The external quantum efficiency of the quantum dot light emitting diodes provided in examples 4 to 9 is significantly higher than that of the quantum dot light emitting diodes prepared from the electron transport films provided in comparative examples 1 and 2, which indicates that the quantum dot light emitting diodes obtained in the examples have better luminous efficiency.
It is noted that the embodiments provided by the present invention all use blue light quantum dots CdXZn1-XS/ZnS is used as a material of a luminescent layer, is based on that a blue light luminescent system uses more systems (the blue light quantum dot luminescent diode has more reference value because high efficiency is difficult to achieve), and does not represent that the invention is only used for the blue light luminescent system.
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 (11)

1. A light emitting diode comprising: an anode and a cathode disposed opposite to each other, a light-emitting layer disposed between the anode and the cathode, and an electron transport layer disposed between the cathode and the light-emitting layer, wherein the electron transport layer comprises: the luminescent layer comprises a cerium dioxide layer and a fullerene derivative layer, wherein the fullerene derivative layer is arranged on the surface of the cerium dioxide layer, which is far away from the luminescent layer;
wherein the material of the fullerene derivative layer comprises [6,6] -phenyl-C61-iso-methyl butyrate and/or [6,6] -phenyl-C61-butyric acid.
2. The led of claim 1, wherein the electron transport layer comprises a ceria layer and a fullerene derivative layer, and the fullerene derivative layer is disposed on a surface of the ceria layer facing away from the light-emitting layer.
3. The led of claim 1, wherein the thickness of the ceria layer is 30-50 nm; and/or
The fullerene derivative layer has a thickness of 10-30 nanometers.
4. The light-emitting diode according to any one of claims 1 to 3, wherein the fullerene derivative layer is made of [6,6] -phenyl-C61-butyric acid.
5. A preparation method of a light-emitting diode is characterized by comprising the following steps:
obtaining a substrate, the substrate comprising: an anode and a light emitting layer disposed on the anode;
depositing a cerium dioxide layer on the light-emitting layer and depositing a fullerene derivative layer on the cerium dioxide layer to form an electron transport layer; the material of the fullerene derivative layer comprises [6,6] -phenyl-C61-iso-methyl butyrate and/or [6,6] -phenyl-C61-butyric acid;
depositing a cathode on the fullerene derivative layer;
or, the preparation method of the light emitting diode comprises the following steps:
depositing a fullerene derivative layer on a cathode and depositing a cerium oxide layer on the fullerene derivative layer to form an electron transport layer; the material of the fullerene derivative layer comprises [6,6] -phenyl-C61-iso-methyl butyrate and/or [6,6] -phenyl-C61-butyric acid;
depositing a light emitting layer on the ceria layer and depositing the anode on the light emitting layer.
6. The method of claim 5, wherein the steps of depositing a layer of cerium oxide over the light-emitting layer and depositing a layer of fullerene derivative over the layer of cerium oxide comprise:
obtaining a cerium dioxide solution, depositing the cerium dioxide solution on the luminescent layer by adopting a spin coating method or an ink-jet printing method, and performing first drying treatment to prepare the cerium dioxide layer;
obtaining a fullerene derivative solution, depositing the fullerene derivative solution on the cerium dioxide layer by adopting a spin coating method or an ink-jet printing method, and performing second drying treatment to prepare the fullerene derivative layer;
alternatively, the steps of depositing a fullerene derivative layer on a cathode and depositing a ceria layer on the fullerene derivative layer comprise:
obtaining a fullerene derivative solution, depositing the fullerene derivative solution on the cathode by adopting a spin-coating method or an ink-jet printing method, and performing third drying treatment to prepare a fullerene derivative layer;
and obtaining a cerium dioxide solution, depositing the cerium dioxide solution on the fullerene derivative layer by adopting a spin coating method or an ink-jet printing method, and performing fourth drying treatment to prepare the cerium dioxide layer.
7. The method of claim 6, wherein the preparing of the cerium oxide solution comprises the steps of:
obtaining a cerium precursor and alcohol, dissolving the cerium precursor in the alcohol, and preparing a cerium precursor solution with the concentration of 0.5-1 mol/L;
and (2) providing alkali, mixing the alkali and the cerium precursor solution according to the molar ratio of (3-5) to 1 of the alkali to cerium atoms in the cerium precursor solution, and then reacting at 60-80 ℃ for 2-4 hours to obtain a cerium dioxide solution.
8. The production method according to claim 7, wherein the cerium precursor includes at least one of cerium sulfate, cerium nitrate, and cerium chloride; and/or
The alkali is at least one selected from potassium hydroxide, sodium hydroxide and ethanolamine.
9. The production method according to any one of claims 6 to 8, wherein a concentration of the fullerene derivative in the fullerene derivative solution is 1 to 3 mg/mL; and/or
The fullerene derivative layer is made of [6,6] -phenyl-C61-butyric acid.
10. The method according to any one of claims 6 to 8, wherein the first drying treatment comprises an annealing treatment at 200-300 ℃; and/or
The second drying treatment comprises an annealing treatment at 100-200 ℃.
11. The production method according to any one of claims 6 to 8, wherein the thickness of the ceria layer is 30 to 50 nm; and/or
The fullerene derivative layer has a thickness of 10-30 nanometers.
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