CN113130773A - Quantum dot light-emitting diode and preparation method thereof - Google Patents

Quantum dot light-emitting diode and preparation method thereof Download PDF

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Publication number
CN113130773A
CN113130773A CN201911394761.9A CN201911394761A CN113130773A CN 113130773 A CN113130773 A CN 113130773A CN 201911394761 A CN201911394761 A CN 201911394761A CN 113130773 A CN113130773 A CN 113130773A
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quantum dot
dot light
layer
emitting layer
organic layer
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CN113130773B (en
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陈开敏
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TCL Research America Inc
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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]
    • H10K50/11—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
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material

Abstract

The invention discloses a quantum dot light-emitting diode and a preparation method thereof. The quantum dot light emitting diode includes: the organic light-emitting diode comprises an anode, a cathode, a quantum dot light-emitting layer arranged between the anode and the cathode, and an organic layer containing fluorine-containing methyl methacrylate and attached to one side or two sides of the quantum dot light-emitting layer. According to the invention, by additionally arranging the organic layer, the refractive index of the organic layer is lower, so that the refractive index of the quantum dot light-emitting layer can be effectively reduced when the organic layer is arranged on one side or two sides of the quantum dot light-emitting layer, the light loss of the quantum dot light-emitting layer in a device is reduced, and the purpose of brightening the quantum dot light-emitting diode is achieved. Furthermore, when the organic layer is arranged close to one side of the cathode, the organic layer is insulated, so that an electron injection barrier can be increased, the injection balance of electron holes in the device can be improved, the recombination efficiency of current carriers can be improved, and the luminous efficiency of the device can be improved.

Description

Quantum dot light-emitting diode and preparation method thereof
Technical Field
The invention relates to the technical field of quantum dot light-emitting diodes, in particular to a quantum dot light-emitting diode and a preparation method thereof.
Background
A quantum dot light emitting diode (QLED) is a multi-functional layer composite structure composed of a cathode, a hole injection layer, a hole transport layer, a quantum dot light emitting layer, an electron transport layer, and an anode, and when a voltage is applied, electrons and holes are injected from respective electrodes, and they are combined to emit light. Due to the fact that the spectrum of the QLED is continuously adjustable in a visible light region, the QLED has more and more attention on excellent performances such as wide absorption, narrow emission, high color purity and luminous intensity.
Solution processed photovoltaic and electronic devices have the characteristics of low cost of manufacturing equipment and compatibility with lightweight, flexible plastic substrates. The quantum dot light-emitting layer in the quantum dot light-emitting diode is generally formed by a solution processing method, and the film formation by the solution method can cause the thickness of the dried quantum dot light-emitting layer to be uneven, and the unevenness on the surface of the quantum dot light-emitting layer is further shown, so that the final device performance is influenced, the unreasonable brightness emergent angle is caused when the device is lightened, and the visual appearance is that the device brightness is weakened.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, an object of the present invention is to provide a quantum dot light emitting diode and a method for manufacturing the same, which aims to solve the problem of poor brightness when the conventional quantum dot light emitting diode is turned on to a certain extent.
The technical scheme of the invention is as follows:
a quantum dot light emitting diode, comprising: the quantum dot light-emitting diode comprises an anode, a cathode and a quantum dot light-emitting layer arranged between the anode and the cathode;
one side of the two opposite sides of the quantum dot light-emitting layer is provided with an organic layer containing fluorine-containing methyl methacrylate, and the organic layer is positioned between the anode and the quantum dot light-emitting layer or between the cathode and the quantum dot light-emitting layer; or
The organic light-emitting diode is characterized in that two opposite sides of the quantum dot light-emitting layer are respectively provided with an organic layer containing fluorine-containing methyl methacrylate, the organic layer arranged on one of the two opposite sides of the quantum dot light-emitting layer is positioned between the anode and the quantum dot light-emitting layer, and the organic layer arranged on the other of the two opposite sides of the quantum dot light-emitting layer is positioned between the cathode and the quantum dot light-emitting layer.
A preparation method of a quantum dot light-emitting diode comprises the following steps:
preparing a quantum dot light emitting layer;
obtaining an organic solution of a fluorine-containing methyl methacrylate material, depositing the organic solution on one of the two opposite sides of the quantum dot light-emitting layer, and drying to obtain an organic layer containing fluorine-containing methyl methacrylate; or
And obtaining an organic solution of the fluorine-containing methyl methacrylate material, respectively depositing the organic solution on two opposite sides of the dried quantum dot light-emitting layer, and drying to obtain the organic layer containing the fluorine-containing methyl methacrylate.
Has the advantages that: according to the invention, by additionally arranging the organic layer containing the fluorine-containing methyl methacrylate, the refractive index of the organic layer is lower, so that the refractive index of the quantum dot light-emitting layer can be effectively reduced by arranging the organic layer on one side or two sides of the quantum dot light-emitting layer, the light loss of the quantum dot light-emitting layer in a device is reduced, and the effect of brightening the quantum dot light-emitting diode is achieved.
Drawings
Fig. 1 is a schematic structural diagram of a quantum dot light emitting diode according to an embodiment of the present invention.
Fig. 2 is another schematic structural diagram of a quantum dot light emitting diode according to an embodiment of the present invention.
Fig. 3 is a schematic structural diagram of a quantum dot light emitting diode according to an embodiment of the present invention.
Fig. 4 is a schematic diagram of light transmission of a quantum dot light emitting diode without an organic layer.
Fig. 5 is a schematic diagram of light transmission of a quantum dot light emitting diode including an organic layer.
Fig. 6 is a schematic structural view of an organic layer formed by stacking a plurality of organic sublayers.
Fig. 7 is a schematic flow chart of a method for manufacturing a quantum dot light emitting diode according to an embodiment of the present invention.
Detailed Description
The invention provides a quantum dot light-emitting diode and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a quantum dot light-emitting diode, which comprises: the cathode comprises an anode 1, a cathode 4 and a quantum dot light-emitting layer 3 arranged between the anode 1 and the cathode 4; one side of the two opposite sides of the quantum dot light-emitting layer 3 is provided with an organic layer 2 containing fluorine-containing methyl methacrylate, and the organic layer 2 is positioned between the anode 1 and the quantum dot light-emitting layer 3 (see fig. 1) or the organic layer 2 is positioned between the cathode 4 and the quantum dot light-emitting layer 3 (see fig. 2); or
The two opposite sides of the quantum dot light-emitting layer 3 are respectively provided with an organic layer 2 containing fluorine-containing methyl methacrylate, the organic layer 2 arranged on one of the two opposite sides of the quantum dot light-emitting layer 3 is positioned between the anode 1 and the quantum dot light-emitting layer 3, and the organic layer 2 arranged on the other of the two opposite sides of the quantum dot light-emitting layer 3 is positioned between the cathode 4 and the quantum dot light-emitting layer 3 (see fig. 3). In other words, in this embodiment, the organic layer containing the fluorine-containing methyl methacrylate may be added on one side of the quantum dot light emitting layer, or the organic layer containing the fluorine-containing methyl methacrylate may be added on both sides of the quantum dot light emitting layer.
The quantum dot light emitting diode may have various forms, and may further include one or more layers of a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer, an electron transport layer, an isolation protective layer, and the like.
In the prior art, a quantum dot light emitting layer in a quantum dot light emitting diode is generally formed by a solution processing method, and film formation by a solution method can cause uneven thickness of the dried quantum dot light emitting layer and uneven surface of the quantum dot light emitting layer, which not only can affect the final device performance, but also can cause unreasonable emergent angle of brightness when the device is lighted, and visually represents that the device brightness is weakened. In this embodiment, by additionally providing the organic layer containing fluorine-containing methyl methacrylate, the refractive index of the organic layer is low, and the refractive index of the quantum dot light-emitting layer can be effectively reduced by being arranged on one side or two sides of the quantum dot light-emitting layer, so that the light loss of the quantum dot light-emitting layer in a device is reduced, and the purpose of brightening the quantum dot light-emitting diode is achieved.
Specifically, as shown in fig. 4, when the organic layer is not included, light emitted from the quantum dot light emitting layer 3 is transmitted to the first functional layer 5 (e.g., an electron transport layer) and the second functional layer 6 (e.g., an electron injection layer) of the device, and due to the unevenness of the surface of the quantum dot light emitting layer 3, the emitted light is irradiated in multiple directions, which causes light loss. As shown in fig. 5, when the organic layer 2 is included and the refractive index of the organic layer 2 is low, the incident angle R is larger when the light emitted from the quantum dot light emitting layer 3 is transmitted from the organic layer 2 to the first functional layer 5 and the second functional layer 6 of the device0Greater than angle of refraction R1Thereby, the effect of gathering light rays is generated, the loss of light in the device is reduced, and the effect of brightening the device is achieved.
In one embodiment, an organic layer comprising fluoro methyl methacrylate is disposed on one of the opposite sides of the quantum dot light emitting layer, the organic layer being between the cathode and the quantum dot light emitting layer. In this embodiment, the organic layer is disposed between the quantum dot light emitting layer and the cathode, and the organic layer is insulating, so that an electron injection barrier can be increased, thereby facilitating improvement of injection balance of electron holes in the device (electrons are easier to inject than holes in general), improving recombination efficiency of carriers, and improving light emitting efficiency of the device.
In one embodiment, the orthographic projection area of the organic layer on the quantum dot light-emitting layer covers the quantum dot light-emitting layer, so that the refractive index of the quantum dot light-emitting layer is reduced to the maximum, the light loss of the quantum dot light-emitting layer in a device is reduced, and the purpose of brightening the quantum dot light-emitting diode is achieved.
In one embodiment, as shown in fig. 6, the organic layer includes a plurality of organic sub-layers, the plurality of organic sub-layers are stacked, the total number of organic sub-layers is denoted as n, and n is a positive integer greater than or equal to 2. For example, n may be 2, 3, or 4, etc. The refractive index of the quantum dot light-emitting layer can be reduced for multiple times by adopting the organic sublayers, so that the light loss of the quantum dot light-emitting layer in the device is reduced as much as possible, and the purpose of brightening the quantum dot light-emitting diode is achieved.
In one embodiment, the organic layer has a thickness of 1 to 10 nm.
In one embodiment, the fluorine-containing methyl methacrylate includes, but is not limited to, one or more of trifluoroethyl methacrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl methacrylate, tridecafluorooctyl methacrylate, and the like.
In a specific embodiment, the quantum dot light emitting diode comprises a substrate, an anode, a hole injection layer, a hole transport layer, a quantum dot light emitting layer, an organic layer, an electron transport layer, an electron injection layer and a cathode which are sequentially stacked.
The embodiment of the invention provides a preparation method of a quantum dot light-emitting diode, which comprises the following steps:
preparing a quantum dot light emitting layer;
obtaining an organic solution of a fluorine-containing methyl methacrylate material, depositing the organic solution on one of the two opposite sides of the quantum dot light-emitting layer, and drying to obtain an organic layer containing fluorine-containing methyl methacrylate; or
And obtaining an organic solution of the fluorine-containing methyl methacrylate material, respectively depositing the organic solution on two opposite sides of the dried quantum dot light-emitting layer, and drying to obtain the organic layer containing the fluorine-containing methyl methacrylate.
In this embodiment, by additionally providing the organic layer containing fluorine-containing methyl methacrylate, the refractive index of the organic layer is low, and the refractive index of the quantum dot light-emitting layer can be effectively reduced by being arranged on one side or two sides of the quantum dot light-emitting layer, so that the light loss of the quantum dot light-emitting layer in a device is reduced, and the purpose of brightening the quantum dot light-emitting diode is achieved.
In one embodiment, a method of fabricating a quantum dot light emitting diode includes:
providing an anode on which the quantum dot light emitting layer is prepared;
preparing a cathode on the organic layer under the condition that the organic layer is deposited on one side of the two opposite sides of the quantum dot light-emitting layer, which is far away from the anode; or
Providing a cathode, preparing the quantum dot light-emitting layer on the cathode, and preparing an anode on the organic layer under the condition that the organic layer is deposited on one side of the two opposite sides of the quantum dot light-emitting layer, which is far away from the cathode.
The following describes a method for manufacturing the quantum dot light emitting diode in detail, taking an example that the organic layer is disposed on one side of the two opposite sides of the quantum dot light emitting layer, which is far away from the anode.
Referring to fig. 7, fig. 7 is a schematic flow chart of a method for manufacturing a quantum dot light emitting diode according to an embodiment of the present invention, as shown in fig. 7, including the steps of:
s10, providing an anode;
s20, preparing a quantum dot light-emitting layer on the anode;
s30, obtaining an organic solution of a fluorine-containing methyl methacrylate material, depositing the organic solution on the quantum dot light-emitting layer, and drying to obtain an organic layer containing fluorine-containing methyl methacrylate;
and S40, preparing a cathode on the organic layer to obtain the quantum dot light-emitting diode.
In this embodiment, by additionally providing the organic layer containing fluorine-containing methyl methacrylate, the refractive index of the organic layer is low, and the organic layer is arranged on one side of the quantum dot light-emitting layer, so that the refractive index of the quantum dot light-emitting layer can be effectively reduced, the light loss of the quantum dot light-emitting layer in a device is reduced, and the purpose of brightening the quantum dot light-emitting diode is achieved. Furthermore, the organic layer is insulated, so that an electron injection barrier can be increased, the injection balance of electron holes in the device is favorably improved (generally, electrons are easier to inject than holes), the recombination efficiency of carriers is improved, and the luminous efficiency of the device is improved. In addition, the method provided by the embodiment is simple and convenient to operate, and is suitable for a small-batch device manufacturing process and a large-scale display screen manufacturing process.
In one embodiment, in step S30, the concentration of the organic solution containing fluoromethyl methacrylate is 5 to 50 mg/mL.
In one embodiment, the organic solution of fluorine-containing methyl methacrylate is prepared by dissolving fluorine-containing methyl methacrylate in a polar solvent. Specifically, the polar solvent may include, but is not limited to, one or more of acetone, chlorobenzene, ethanol, DMSO, and the like.
Further in one embodiment, the polar solvent is acetone or chlorobenzene. On one hand, the fluorine-containing methyl methacrylate can be uniformly dispersed in acetone or chlorobenzene, and on the other hand, the fluorine-containing methyl methacrylate solution is favorably and uniformly cast and deposited on the quantum dot light-emitting layer to form an ideal thickness (1-10 nm).
In step S30, in one embodiment, the method for depositing the organic solution containing fluoro methyl methacrylate includes, but is not limited to, one or more of spin coating, doctor blading, inkjet printing, and magnetron sputtering.
The invention is further illustrated by the following specific examples.
Comparative example 1
A quantum dot light emitting diode without an organic layer, the quantum dot light emitting diode structure is as follows:
ITO/PEDOT PSS/PVK/blue QDs/ZnO/Al.
Example 1
A quantum dot light emitting diode comprising an organic layer, the quantum dot light emitting diode having the structure:
ITO/PEDOT PSS/PVK/blue QDs/trifluoroethyl methacrylate/ZnO/Al.
The electrode is prepared by an evaporation method, and the PEDOT, namely PSS, PVK, ODs, trifluoroethyl methacrylate and ZnO are prepared by a spin coating method, wherein the thickness of the trifluoroethyl methacrylate is 8 nm.
It should be noted that the conditions were completely the same except that the quantum dot light emitting diode in example 1 included an organic layer and the quantum dot light emitting diode in comparative example 1 did not include an organic layer.
The performance tests of the two devices (quantum dot light emitting diode) of example 1 and comparative example 1 show that the light emitting region is 0.04m at a current of 2mA2The luminance of the device of example 1 was 6000cd/m2The luminance of the device of comparative example 1 was 5000cd/m2Namely, the brightness of the device is improved by 20% after the organic layer is added.
Comparative example 2
A quantum dot light emitting diode without an organic layer, the quantum dot light emitting diode structure is as follows:
ITO/PEDOT PSS/TFB/green QDs/ZnO/Ag.
Example 2
A quantum dot light emitting diode comprising an organic layer, the quantum dot light emitting diode having the structure:
ITO/PEDOT PSS/TFB/green QDs/tridecyl methacrylate/ZnO/Ag.
The electrode is prepared by an evaporation method, PEDOT, PSS and TFB are prepared by a spin coating method, QDs, tridecafluorooctyl methacrylate and ZnO are prepared by an ink-jet printing method, and the thickness of the tridecafluorooctyl methacrylate is 4 nm.
It should be noted that the conditions were completely the same except that the quantum dot light emitting diode in example 2 included an organic layer and the quantum dot light emitting diode in comparative example 2 did not include an organic layer.
Performance tests of the two devices of example 2 and comparative example 2 revealed that the light-emitting region was 0.04m at a current of 2mA2The luminance of the device of example 2 was 12000cd/m2The luminance of the device of comparative example 2 was 8000cd/m2Namely, the brightness of the device is improved by 50% after the organic layer is added.
In summary, according to the quantum dot light emitting diode and the preparation method thereof provided by the invention, by additionally arranging the organic layer containing fluorine-containing methyl methacrylate, the refractive index of the organic layer is lower, so that the refractive index of the quantum dot light emitting layer can be effectively reduced when the organic layer is arranged on one side or two sides of the quantum dot light emitting layer, thereby reducing the light loss of the quantum dot light emitting layer in the device and achieving the purpose of brightening the quantum dot light emitting diode. Furthermore, when the organic layer is arranged close to one side of the cathode, the organic layer is insulated, so that an electron injection barrier can be increased, the injection balance of electron holes in the device can be improved, the recombination efficiency of current carriers can be improved, and the luminous efficiency of the device can be improved.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims (10)

1. A quantum dot light emitting diode, comprising: the quantum dot light-emitting diode comprises an anode, a cathode and a quantum dot light-emitting layer arranged between the anode and the cathode;
one side of the two opposite sides of the quantum dot light-emitting layer is provided with an organic layer containing fluorine-containing methyl methacrylate, and the organic layer is positioned between the anode and the quantum dot light-emitting layer or between the cathode and the quantum dot light-emitting layer; or
The organic light-emitting diode is characterized in that two opposite sides of the quantum dot light-emitting layer are respectively provided with an organic layer containing fluorine-containing methyl methacrylate, the organic layer arranged on one of the two opposite sides of the quantum dot light-emitting layer is positioned between the anode and the quantum dot light-emitting layer, and the organic layer arranged on the other of the two opposite sides of the quantum dot light-emitting layer is positioned between the cathode and the quantum dot light-emitting layer.
2. The quantum dot light-emitting diode of claim 1, wherein an orthographic area of the organic layer on the quantum dot light-emitting layer covers the quantum dot light-emitting layer.
3. The quantum dot light-emitting diode of claim 1, wherein the organic layer comprises a plurality of organic sub-layers, the plurality of organic sub-layers being arranged one above the other, and/or,
the thickness of the organic layer is 1-10 nm.
4. The quantum dot light-emitting diode of claim 1, wherein the fluorine-containing methyl methacrylate comprises one or more of trifluoroethyl methacrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl methacrylate, and tridecyl octyl methacrylate.
5. The quantum dot light-emitting diode of claim 1, wherein the quantum dot light-emitting diode comprises the anode, a hole injection layer, a hole transport layer, the quantum dot light-emitting layer, the organic layer, an electron transport layer, an electron injection layer and the cathode, which are sequentially stacked.
6. A preparation method of a quantum dot light-emitting diode is characterized by comprising the following steps:
preparing a quantum dot light emitting layer;
obtaining an organic solution of a fluorine-containing methyl methacrylate material, depositing the organic solution on one of the two opposite sides of the quantum dot light-emitting layer, and drying to obtain an organic layer containing fluorine-containing methyl methacrylate; or
And obtaining an organic solution of the fluorine-containing methyl methacrylate material, respectively depositing the organic solution on two opposite sides of the dried quantum dot light-emitting layer, and drying to obtain the organic layer containing the fluorine-containing methyl methacrylate.
7. The method for preparing a quantum dot light-emitting diode according to claim 6, wherein the method comprises:
providing an anode on which the quantum dot light emitting layer is prepared;
preparing a cathode on the organic layer under the condition that the organic layer is deposited on one side of the two opposite sides of the quantum dot light-emitting layer, which is far away from the anode; or
Providing a cathode, preparing the quantum dot light-emitting layer on the cathode, and preparing an anode on the organic layer under the condition that the organic layer is deposited on one side of the two opposite sides of the quantum dot light-emitting layer, which is far away from the cathode.
8. The method for preparing a quantum dot light-emitting diode according to claim 6, wherein the concentration of the fluorine-containing methyl methacrylate organic solution is 5-50 mg/mL.
9. The method for preparing a quantum dot light-emitting diode according to claim 6, wherein the organic solution containing the fluorine-containing methyl methacrylate is prepared by dissolving the fluorine-containing methyl methacrylate in a polar solvent.
10. The method of claim 9, wherein the polar solvent is acetone or chlorobenzene.
CN201911394761.9A 2019-12-30 2019-12-30 Quantum dot light-emitting diode and preparation method thereof Active CN113130773B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107238973A (en) * 2017-07-19 2017-10-10 苏州星烁纳米科技有限公司 Quantum dot film and preparation method thereof
CN107603614A (en) * 2017-09-12 2018-01-19 华中科技大学 A kind of preparation method of metal halide perovskite quantum dot

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107238973A (en) * 2017-07-19 2017-10-10 苏州星烁纳米科技有限公司 Quantum dot film and preparation method thereof
CN107603614A (en) * 2017-09-12 2018-01-19 华中科技大学 A kind of preparation method of metal halide perovskite quantum dot

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