CN110797475A - Method for preparing double-layer film, quantum dot light-emitting diode and preparation method thereof - Google Patents
Method for preparing double-layer film, quantum dot light-emitting diode and preparation method thereof Download PDFInfo
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- CN110797475A CN110797475A CN201810863609.XA CN201810863609A CN110797475A CN 110797475 A CN110797475 A CN 110797475A CN 201810863609 A CN201810863609 A CN 201810863609A CN 110797475 A CN110797475 A CN 110797475A
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- H—ELECTRICITY
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
- H10K50/156—Hole transporting layers comprising a multilayered structure
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- H—ELECTRICITY
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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- H—ELECTRICITY
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
Abstract
The invention discloses a method for preparing a double-layer film, a quantum dot light-emitting diode and a preparation method thereof, wherein the method for preparing the double-layer film comprises the following steps: preparing a lower layer film on a substrate by a solution method; heating the substrate and the lower layer film to a certain temperature, and simultaneously heating the precursor solution of the upper layer film material to a certain temperature; and preparing the upper-layer film from the heated precursor solution of the upper-layer film material by a solution method, wherein the upper-layer film is positioned on the lower-layer film to form a double-layer film. The invention prepares the even and flat double-layer film structure by heating the precursor liquid of the upper layer film material and controlling the temperature of the substrate and the lower layer film, and the method has the advantages of low cost, simple and easily controlled process, good film forming quality and the like. According to the invention, through screening the solvent, the m-xylene which can not damage the lower film is selected as the solvent of the upper layer material, the advantages of poly-TPD and PVK are fully utilized, the efficiency of the quantum dot light-emitting diode is greatly improved, and the starting voltage of the device is reduced.
Description
Technical Field
The invention belongs to the technical field of photoelectric devices, and particularly relates to a method for preparing a double-layer film, a quantum dot light-emitting diode and a preparation method thereof.
Background
Poly [ bis (4-phenyl) (4-butylphenyl) amine ] (poly-TPD) and Polyvinylcarbazole (PVK) are widely used as commonly used hole transport layers in electroluminescent devices, including Organic Light Emitting Diodes (OLEDs), Quantum dot Light emitting diodes (QLEDs), and perovskite Light emitting diodes. In a light emitting diode, one of the most fundamental factors affecting efficiency is carrier balance.
In the light emitting diode prepared by the solution method, the electron transport layer is generally made of zinc oxide with energy level matching and high mobility, however, when poly-TPD and PVK are respectively used as hole transport layers, the defects of the materials cause that the hole transport cannot be matched with the electron transport, so that the carrier imbalance is caused, and the efficiency of the device is finally reduced. Specifically, poly-TPD has a large hole mobility, but a Highest Occupied Molecular Orbital (HOMO) level is shallow, and a level difference with a light emitting layer is large, resulting in a severe energy barrier, which makes the hole transfer to the light emitting layer greatly hindered; the HOMO level of PVK is deeper than poly-TPD, and although the level difference with the light emitting layer is smaller, it has low mobility by itself, thereby causing a low hole transport rate that cannot be matched with electron transport.
In order to utilize the advantages of poly-TPD and PVK as much as possible, the two materials are combined to prepare the double-hole layer with the step energy level, so that the high mobility of poly-TPD is utilized, the deeper HOMO energy level of PVK is utilized, the hole mobility can be improved to a certain extent, the hole mobility can be better matched with electrons, the balance can be better achieved, and the efficiency is finally improved. However, the above-mentioned double hole layer cannot be successfully prepared by a general solution preparation method because poly-TPD and PVK are polymers having similar solubility properties and have substantially the same solvent for dissolving them, and thus, when an upper layer material is prepared, the lower layer material is dissolved by the solvent and damaged. It is therefore desirable to find a specific method for preparing such a double hole layer.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the technical problem that the common solution preparation method in the prior art cannot successfully prepare the double-cavity layer.
To achieve the above object, in a first aspect, embodiments of the present invention provide a method for preparing a bilayer film, the method including the steps of:
(1) preparing a lower layer film on a substrate by a solution method;
(2) heating the substrate and the lower layer film to a certain temperature, and simultaneously heating the precursor solution of the upper layer film material to a certain temperature;
(3) and preparing the upper-layer film from the heated precursor solution of the upper-layer film material by a solution method, wherein the upper-layer film is positioned on the lower-layer film to form a double-layer film.
Specifically, the materials of the double-layer film are poly [ bis (4-phenyl) (4-butylphenyl) amine ] and polyvinylcarbazole.
Specifically, the substrate heating temperature ranges from 40 ℃ to 80 ℃, and the precursor temperature ranges from 70 ℃ to 90 ℃.
Specifically, the solution method includes a spin coating method, a blade coating method, a drop coating method, or a printing method.
Specifically, the lower layer film precursor liquid is chlorobenzene, and the upper layer film precursor liquid is m-xylene.
Specifically, the concentration of the lower layer material precursor liquid is 5-20mg/ml, and the concentration of the upper layer material precursor liquid is 0.5-5 mg/ml.
In order to achieve the above object, in a second aspect, the embodiments of the present invention provide a method for manufacturing a quantum dot light emitting diode, where a double hole transport layer of the quantum dot light emitting diode is a double-layer thin film structure, and the quantum dot light emitting diode is manufactured by the method described above.
In order to achieve the above object, in a third aspect, an embodiment of the present invention provides a quantum dot light emitting diode prepared by the above method for preparing a quantum dot light emitting diode, where the quantum dot light emitting diode sequentially includes, from a bottom layer to a top layer: the organic electroluminescent device comprises a transparent electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and a metal electrode.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
(1) the invention promotes the dissolution of the upper layer film material by heating the precursor solution of the upper layer film material, and further controls the film forming rate of the upper layer film material by controlling the temperature of the substrate and the lower layer film, so that the upper layer film material can be uniformly deposited to prepare a uniform and flat double-layer film.
(2) According to the invention, through screening the solvent, the m-xylene which does not damage the lower film is selected as the solvent of the upper layer material, and the advantages of poly-TPD and PVK are fully utilized, so that the efficiency of the quantum dot light-emitting diode is greatly improved, and the starting voltage of the device is reduced.
Drawings
FIG. 1 is a flow chart of a method for preparing a bilayer film according to the present invention.
FIG. 2 is an AFM image of a poly-TPD film prepared on an ITO/PEDOT: PSS substrate in example one.
Fig. 3 is a schematic structural diagram of a device in which the double hole transport layer is used as a hole transport layer and cadmium selenide cadmium sulfide zinc sulfide (cdse cds zns) is used as a light emitting layer according to the first embodiment.
Fig. 4 is an AFM comparison graph of the PVK thin films obtained in the first comparative example and the first example, fig. 4(a) is an AFM graph of the PVK thin film obtained in the first comparative example, and fig. 4(b) is an AFM graph of the PVK thin film obtained in the first example.
Fig. 5 is a graph comparing external quantum efficiency versus current density curves of quantum dot light emitting diode devices prepared in comparative example one and example one.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
FIG. 1 is a flow chart of a method for preparing a bilayer film according to the present invention. As shown in fig. 1, the method comprises the steps of:
(1) the lower film is prepared on the substrate by a solution method.
The substrate is a substrate or a substrate with one or more adhesion layers. The substrate and the adhesion layer may be selected from conventional materials in the art. For example, in the preparation of quantum dot light emitting diodes, the substrate may be selected from glass, metal, ceramic or high temperature resistant organic polymers, preferably glass. The roughness of the substrate is 1-10nm, preferably 2 nm. The adhesion layer includes a conductive layer and a hole injection layer. The conductive layer is an indium tin oxide layer or fluorine-doped SnO2And (3) a layer. The hole injection layer is PEDOT, PSS layer or nickel oxide layer.
The material of the double-layer film is a polymer, preferably poly [ bis (4-phenyl) (4-butylphenyl) amine ] (poly-TPD) and Polyvinylcarbazole (PVK).
(2) The substrate and the lower layer film are heated to a certain temperature, and meanwhile, the precursor liquid of the upper layer film material is heated to a certain temperature.
The upper layer film material can not be dissolved in the upper layer film precursor solution at normal temperature, is in a turbid state and can not form a film, so that the dissolving of the upper layer film material is promoted by heating the precursor solution of the upper layer film material. However, if only the precursor solution of the upper layer thin film material is heated, the upper layer thin film material is precipitated too fast and aggregated, and the film is formed unevenly, so the invention further controls the film forming rate of the upper layer thin film material by controlling the temperature of the substrate and the lower layer thin film, and the upper layer thin film material is deposited evenly.
The substrate heating temperature is in the range of 40-80 ℃, and the precursor temperature is in the range of 70-90 ℃.
(3) And preparing the upper-layer film from the heated precursor solution of the upper-layer film material by a solution method, wherein the upper-layer film is positioned on the lower-layer film to form a double-layer film.
The solution method includes a spin coating method, a blade coating method, a drop coating method, or a printing method, and preferably a spin coating method.
The lower layer film precursor liquid is chlorobenzene, and the upper layer film precursor liquid is m-xylene. The invention selects the m-xylene which can not damage the lower film as the solvent of the upper layer material through the screening of the solvent.
The concentration of the lower layer material precursor solution is 5-20mg/ml, preferably 10 mg/ml.
The concentration of the precursor solution of the upper layer material is 0.5-5mg/ml, and preferably 1.5 mg/ml.
In the first embodiment, the method for preparing a double-layer film provided by the invention is applied to the preparation of a cadmium selenide cadmium zinc sulfide (CdSeCdSZnS) quantum dot light-emitting diode, and specifically comprises the following steps:
the ITO (indium tin oxide) glass was successively cleaned with ultrasound in a detergent and deionized water for 30 minutes. Then vacuum-dried for 2 hours (105 deg.C), then the ITO (indium tin oxide) glass was put into a plasma reactor for 5 minutes of oxygen plasma treatment, and PEDOT: PSS film was prepared by spin coating in air at 2000 r.p.m.rotational speed and then heat-treated at 120 deg.C for 30 minutes, and then N was put in2In an ambient glove box. 2000r.p.m of poly-TPD chlorobenzene solution of 10mg/ml is coated on a PSS substrate of ITO/PEDOT in a spinning mode, then the heat treatment is carried out for 20min at 140 ℃, the substrate is heated to 60 ℃ after cooling, then PVK meta-xylene solution of 80 ℃ is coated on the PSS/poly-TPD substrate in a spinning mode, then the heat treatment is carried out for 30min at 170 ℃, then quantum dot solution and zinc oxide solution are coated in a spinning mode in sequence, and finally the substrate is conveyed to a vacuum chamber to be evaporated with 100nm of Al.
FIG. 2 is an AFM image of a poly-TPD film prepared on an ITO/PEDOT: PSS substrate in example one. As can be seen from FIG. 2, the poly-TPD film was uniformly flat.
Fig. 3 is a schematic structural diagram of a device in which the double hole transport layer is used as a hole transport layer and cadmium selenide cadmium sulfide zinc sulfide (cdse cds zns) is used as a light emitting layer according to the first embodiment. As can be seen from FIG. 3, poly-TPD and PVK form a stepped energy level, which is more favorable for hole injection.
Comparative example a method for preparing a dual hole transport layer using a conventional spin coating method was provided, which is different from example one only in that the substrate was not heated during the preparation of PVK.
Fig. 4 is an AFM comparison graph of the PVK thin films obtained in the first comparative example and the first example, fig. 4(a) is an AFM graph of the PVK thin film obtained in the first comparative example, and fig. 4(b) is an AFM graph of the PVK thin film obtained in the first example. As shown in FIG. 4, it was found by comparison that the thermal spinning process in the first example significantly improved the uniformity of the PVK film formation on poly-TPD.
Fig. 5 is a graph comparing external quantum efficiency versus current density curves of quantum dot light emitting diode devices prepared in comparative example one and example one. As shown in fig. 5, it is found through comparison that the efficiency of the quantum dot light emitting diode is greatly improved by hot spin coating the obtained double-hole transport layer in the first embodiment, and the method is an effective method for preparing a high-quality multi-hole layer.
The above description is only for the preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present application should be covered within the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (8)
1. A method of making a bilayer film, the method comprising the steps of:
(1) preparing a lower layer film on a substrate by a solution method;
(2) heating the substrate and the lower layer film to a certain temperature, and simultaneously heating the precursor solution of the upper layer film material to a certain temperature;
(3) and preparing the upper-layer film from the heated precursor solution of the upper-layer film material by a solution method, wherein the upper-layer film is positioned on the lower-layer film to form a double-layer film.
2. The method of claim 1, wherein the bilayer film is formed of poly [ bis (4-phenyl) (4-butylphenyl) amine ] and polyvinylcarbazole.
3. The method of claim 1, wherein the substrate is heated at a temperature in the range of 40-80 ℃ and the precursor is heated at a temperature in the range of 70-90 ℃.
4. The method of claim 1, wherein the solution process comprises spin coating, doctor blading, dispensing or printing.
5. The method of claim 1, wherein the lower layer precursor solution is chlorobenzene and the upper layer precursor solution is m-xylene.
6. The method according to claim 5, wherein the lower layer material precursor solution has a concentration of 5 to 20mg/ml, and the upper layer material precursor solution has a concentration of 0.5 to 5 mg/ml.
7. A method for preparing a quantum dot light emitting diode, wherein the double hole transport layer of the quantum dot light emitting diode is a double-layer thin film structure, which is prepared by the method of claims 1 to 6.
8. The quantum dot light-emitting diode prepared by the preparation method of the quantum dot light-emitting diode according to claim 7, wherein the quantum dot light-emitting diode comprises the following components in sequence from the bottom layer to the top layer: the organic electroluminescent device comprises a transparent electrode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and a metal electrode.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112531136A (en) * | 2020-12-08 | 2021-03-19 | 北京交通大学 | Preparation method of organic electroluminescent device multilayer film |
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| CN103904178A (en) * | 2014-04-11 | 2014-07-02 | 浙江大学 | Quantum dot luminescent device |
| CN105161635A (en) * | 2015-07-01 | 2015-12-16 | Tcl集团股份有限公司 | QLED device with self-assembly electron transmission layer, and preparation method for QLED device |
| CN105591036A (en) * | 2016-01-26 | 2016-05-18 | 纳晶科技股份有限公司 | Packaging structure of flexible electroluminescent device and packaging method thereof |
| CN106328823A (en) * | 2016-11-10 | 2017-01-11 | 吉林大学 | Organic thin film, preparation method and application thereof for preparing organic electroluminescence device |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103904178A (en) * | 2014-04-11 | 2014-07-02 | 浙江大学 | Quantum dot luminescent device |
| CN105161635A (en) * | 2015-07-01 | 2015-12-16 | Tcl集团股份有限公司 | QLED device with self-assembly electron transmission layer, and preparation method for QLED device |
| CN105591036A (en) * | 2016-01-26 | 2016-05-18 | 纳晶科技股份有限公司 | Packaging structure of flexible electroluminescent device and packaging method thereof |
| CN106328823A (en) * | 2016-11-10 | 2017-01-11 | 吉林大学 | Organic thin film, preparation method and application thereof for preparing organic electroluminescence device |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112531136A (en) * | 2020-12-08 | 2021-03-19 | 北京交通大学 | Preparation method of organic electroluminescent device multilayer film |
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