CN111146347A - Electroluminescent device and preparation method thereof - Google Patents
Electroluminescent device and preparation method thereof Download PDFInfo
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- CN111146347A CN111146347A CN201811299837.5A CN201811299837A CN111146347A CN 111146347 A CN111146347 A CN 111146347A CN 201811299837 A CN201811299837 A CN 201811299837A CN 111146347 A CN111146347 A CN 111146347A
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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
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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
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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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/82—Cathodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides an electroluminescent device, which comprises a substrate, and at least one quantum dot electroluminescent unit and at least one organic electroluminescent unit which are arranged on the substrate, wherein the quantum dot electroluminescent unit comprises a first anode and a first cathode which are oppositely arranged, a quantum dot light-emitting layer arranged between the first anode and the first cathode, and a first electron transmission layer arranged between the quantum dot light-emitting layer and the first cathode; the organic electroluminescent unit comprises a second anode and a second cathode which are oppositely arranged, an organic light-emitting layer arranged between the second anode and the second cathode, and a second electron transport layer arranged between the organic light-emitting layer and the second cathode; the material of the first electron transport layer is selected from cross-linking type electron transport materials, and the material of the second electron transport layer is selected from cross-linking type electron transport materials.
Description
Technical Field
The invention belongs to the technical field of luminous display, and particularly relates to an electroluminescent device and a preparation method thereof.
Background
Because Quantum dots have the characteristics of adjustable size, narrow Light Emitting line width, high Light Emitting efficiency and the like, Quantum Dot Light Emitting diodes (QLEDs) using Quantum dots as Light Emitting layers become the next generation of display and solid state lighting Light sources with great potential. Quantum dot electroluminescence has advantages of good color purity, high luminescence quantum efficiency, fast response speed, and the like, and has attracted much attention in recent years. After years of research and development, the external quantum efficiency of the current highest red and green QLED is over or close to 20% from the publicly reported literature data, which indicates that the internal quantum efficiency of the red and green quantum dot light-emitting diode is actually close to the theoretical limit. However, the current electro-optic conversion efficiency of the blue quantum dot light emitting diode, which is one of the essential three primary colors for color display, is much lower than that of the red and green quantum dot light emitting diode, thereby limiting the application of the quantum dot light emitting diode in color display.
In addition, the service life of the quantum dot light-emitting diode devices with three colors of red, green and blue is also greatly different. From the publicly reported literature data, the initial luminance of the red quantum dot light emitting diode device is 100cd/m2Under working conditions, the half-brightness service life exceeds 10 ten thousand hours or even longer; however, the half-brightness life of green and blue quantum dot light emitting diode devices is far lower than that of red devices, especially quantum dot light emitting diode devices, and the half-life reported in public only reaches dozens to hundreds of hours, and there is a great difference from practical level.
Technologies based on organic light emitting materials, such as electroluminescent (OLED) materials and device structures, have been developed for almost thirty years, and compared with QLEDs, the performance of some organic electroluminescent materials is better than that of quantum dots, such as higher light emitting efficiency or longer lifetime. Therefore, the high-performance organic light-emitting material can be used for making up the performance defects of the quantum dots and the quantum dot light-emitting diode device.
The quantum dot electroluminescent and organic electroluminescent mixed light-emitting structure can give full play to the advantages of two different types of light-emitting, and the quantum dot electroluminescent and organic electroluminescent can adopt an inverted device structure. In order to be compatible with the solution processing technology and prevent the damage of the solvent to the lower layer in the subsequent manufacturing process of the luminescent layer and other functional layers, the electronic transmission layer at the bottom layer of the inverted device usually adopts oxide nanoparticles as the electronic transmission material, such as ZnO nanoparticles and ZnMgO nanoparticles. Such nanoparticles have poor film-forming interfaces and often require additional interface-modifying layers to improve the interfacial properties.
Disclosure of Invention
The invention aims to provide an electroluminescent device and a preparation method thereof, and aims to solve the problem of poor film forming interface of oxide nanoparticles serving as an electron transport material in the conventional electroluminescent device.
In order to achieve the purpose, the invention adopts the following technical scheme:
an electroluminescent device comprising a substrate, and at least one quantum dot electroluminescent unit and at least one organic electroluminescent unit disposed on the substrate,
the quantum dot electroluminescent unit comprises a first anode and a first cathode which are oppositely arranged, a quantum dot light-emitting layer arranged between the first anode and the first cathode, and a first electron transport layer arranged between the quantum dot light-emitting layer and the first cathode;
the organic electroluminescent unit comprises a second anode and a second cathode which are oppositely arranged, an organic light-emitting layer arranged between the second anode and the second cathode, and a second electron transport layer arranged between the organic light-emitting layer and the second cathode;
wherein the first anode and the second anode are disposed on the substrate, or the first cathode and the second cathode are disposed on the substrate;
the materials of the first anode and the second anode are the same or different, the materials of the first cathode and the second cathode are the same or different, the material of the first electron transport layer is selected from a crosslinking type electron transport material, the material of the second electron transport layer is selected from a crosslinking type electron transport material, and the materials of the first electron transport layer and the second electron transport layer are the same or different.
And, a method of making an electroluminescent device, comprising the steps of:
providing a substrate, preparing a cathode and a pixel defining layer on the substrate, forming a pixel groove formed by surrounding the cathode as a bottom and the pixel defining layer, and presetting a quantum dot light-emitting area and an organic light-emitting area;
depositing a cross-linking type electron transport material on the surface of the cathode of the quantum dot light emitting region, and heating the cathode in an inert environment to cross-link the cross-linking type electron transport material to prepare a first electron transport layer; depositing a cross-linking type electron transport material on the surface of the cathode of the organic light-emitting region, heating the organic light-emitting region in an inert environment to cross-link the cross-linking type electron transport material, and preparing a second electron transport layer
Preparing a luminescent layer on the surface of the electron transport layer, and preparing an anode on the luminescent layer, wherein a quantum dot luminescent layer is prepared on the first electron transport layer, and an organic luminescent layer is prepared on the second electron transport layer.
A method for preparing an electroluminescent device comprises the following steps:
providing a substrate, preparing an anode and a pixel defining layer on the substrate, forming a pixel groove formed by surrounding the anode as a bottom and the pixel defining layer, and presetting a quantum dot light-emitting area and an organic light-emitting area;
preparing a quantum dot light-emitting layer on the surface of an anode of the quantum dot light-emitting region, depositing a cross-linking type electron transport material on the surface of the quantum dot light-emitting layer, and heating under an inert environment to enable the cross-linking type electron transport material to be cross-linked to prepare a first electron transport layer; preparing an organic light-emitting layer on the surface of an anode of the organic light-emitting region, depositing a cross-linking type electron transport material on the surface of the organic light-emitting layer, and heating the organic light-emitting layer in an inert environment to cross-link the cross-linking type electron transport material to prepare a second electron transport layer;
and preparing a cathode on the surfaces of the first electron transport layer and the second electron transport layer.
The invention provides a luminescent device based on quantum dot electroluminescence and organic electroluminescence, which can give full play to the advantages of quantum dots and organic materials and realize photoelectric display with more excellent performance. Specifically, the electroluminescent device provided by the invention firstly adopts a combined mixed light-emitting mode of organic electroluminescence and quantum dot electroluminescence, so that the comprehensive display performance of the display can be further improved, and particularly, the light-emitting efficiency and the service life of weak electroluminescent units such as blue light-emitting electroluminescent diodes are improved. Secondly, the invention adopts the cross-linking type electron transport material, the material formed after cross-linking has good chemical stability, can effectively resist the corrosion from the solvent of the upper layer in the preparation process, particularly the corrosion from the solvent of the organic light-emitting layer or the quantum dot light-emitting layer in the light-emitting device, particularly the corrosion from the solvent of the organic light-emitting layer, thereby improving the interface performance, satisfying the electron transport efficiency of the device, leading the light-emitting efficiency of the organic light-emitting layer to be more matched with the light-emitting efficiency of the quantum dot light-emitting layer, and further obtaining better mixed light-emitting display. In addition, the organic material has a good film forming interface, an additional interface modification layer is not needed, the process compatibility is good, the process can be simplified, and the manufacturing cost is reduced. In summary, the color display device based on the quantum dot electroluminescent and organic electroluminescent mixed light-emitting structure not only has high-performance display, but also can be compatible with a manufacturing process in the manufacturing process, and the manufacturing cost is saved.
The preparation method of the electroluminescent device provided by the invention only needs to adjust the type of the luminescent layer material on the one hand and carry out heating treatment after depositing the cross-linking type electron transport material on the other hand on the basis of the preparation process of the conventional electroluminescent device so as to enable the material to be cross-linked. The method provided by the invention does not need an additional interface modification layer, has good process compatibility and simple process, can reduce the manufacturing cost, and most importantly, can obtain the electroluminescent device with good interface performance and high luminous efficiency.
Drawings
Fig. 1 is a schematic structural diagram of an electroluminescent device provided in embodiments 1 and 2 of the present invention;
fig. 2 is a schematic structural diagram of an electroluminescent device provided in embodiments 3 and 4 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The embodiment of the invention provides an electroluminescent device, which comprises a substrate, and at least one quantum dot electroluminescent unit and at least one organic electroluminescent unit which are arranged on the substrate,
the quantum dot electroluminescent unit comprises a first anode and a first cathode which are oppositely arranged, a quantum dot light-emitting layer arranged between the first anode and the first cathode, and a first electron transport layer arranged between the quantum dot light-emitting layer and the first cathode;
the organic electroluminescent unit comprises a second anode and a second cathode which are oppositely arranged, an organic light-emitting layer arranged between the second anode and the second cathode, and a second electron transport layer arranged between the organic light-emitting layer and the second cathode;
wherein the first anode and the second anode are disposed on the substrate, or the first cathode and the second cathode are disposed on the substrate;
the materials of the first anode and the second anode are the same or different, the materials of the first cathode and the second cathode are the same or different, the material of the first electron transport layer is selected from a crosslinking type electron transport material, the material of the second electron transport layer is selected from a crosslinking type electron transport material, and the materials of the first electron transport layer and the second electron transport layer are the same or different.
The embodiment of the invention provides a luminescent device based on quantum dot electroluminescence and organic electroluminescence, which can give full play to the advantages of quantum dots and organic materials and realize photoelectric display with more excellent performance. Specifically, in the electroluminescent device provided in the embodiment of the present invention, firstly, a combined mixed light emitting manner of organic electroluminescence and quantum dot electroluminescence is adopted, so that the comprehensive display performance of the display can be further improved, and particularly, the light emitting efficiency and the service life of a weak electroluminescent unit such as a blue light emitting electroluminescent diode are improved. In addition, the embodiment of the invention adopts the cross-linking type electron transport material, the material formed after cross-linking has good chemical stability, can effectively resist the corrosion from an upper solvent in the preparation process, particularly the corrosion from an organic light emitting layer or a quantum dot light emitting layer solvent in a light emitting device, particularly the corrosion from the organic light emitting layer solvent, thereby improving the interface performance, satisfying the electron transport efficiency of the device, enabling the light emitting efficiency of the organic light emitting layer to be more matched with the light emitting efficiency of the quantum dot light emitting layer, and further obtaining better mixed light emitting display. In addition, the organic material has a good film forming interface, an additional interface modification layer is not needed, the process compatibility is good, the process can be simplified, and the manufacturing cost is reduced. In summary, the color display device based on the quantum dot electroluminescent and organic electroluminescent mixed light-emitting structure in the embodiment of the invention not only has high-performance display, but also can be compatible with the manufacturing process in the manufacturing process, thereby saving the manufacturing cost.
In the embodiment of the invention, the electroluminescent device comprises a plurality of pixel units, each pixel unit comprises a plurality of sub-pixel units, and the plurality of sub-pixel units comprise at least one quantum dot electroluminescent unit and at least one organic electroluminescent unit. Specifically, the plurality of sub-pixel units include at least one quantum dot electroluminescent unit and at least one organic electroluminescent unit, which are understood as that luminescent layer materials in the electroluminescent units are not completely the same, and include quantum dot luminescent materials and organic luminescent materials, that is, the luminescent materials in the quantum dot electroluminescent units are quantum dot materials, and the luminescent materials in the organic electroluminescent units are organic materials. In a preferred embodiment, the electroluminescent device comprises a plurality of pixel units, each pixel unit comprises three sub-pixel units, and the three sub-pixel units are a red light quantum dot light-emitting unit, a green light quantum dot light-emitting unit and a blue light organic light-emitting unit respectively.
The electroluminescent device can at least select any one color of luminescent device as the quantum dot electroluminescent unit in principle, and can also at least select any one color of luminescent device as the organic electroluminescent unit. Preferably, in the electroluminescent device, the quantum dot electroluminescent unit includes a red light quantum dot electroluminescent unit and a green light quantum dot electroluminescent unit, and the organic electroluminescent unit includes a blue light organic electroluminescent unit, so as to improve and make up for the deficiency of the blue light quantum dot electroluminescent, and improve the overall luminescent performance of the luminescent device. More preferably, the electroluminescent device comprises a plurality of pixel units, each pixel unit comprises a red quantum dot light-emitting unit, a green quantum dot light-emitting unit and a blue organic light-emitting unit, so that the interface performance of the electron transport layers (the first electron transport layer and the second electron transport layer) is improved, and the luminous efficiency of the blue device is improved.
Specifically, in the embodiment of the present invention, the materials of the first anode and the second anode are the same or different, and the materials of the first cathode and the second cathode are the same or different. Preferably, in order to improve material compatibility and further improve device stability, and to simplify a process flow, the materials of the first anode and the second anode are the same, that is, the quantum dot electroluminescent unit and the organic electroluminescent unit share an anode; the first cathode and the second cathode are made of the same material, namely the quantum dot electroluminescent unit and the organic electroluminescent unit share a cathode.
Preferably, the electroluminescent device may further include one or more functional layers of a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, and the like. Wherein the content of the first and second substances,
the substrate provided by the embodiment of the invention is arranged at one end of the anode or the cathode and is used for bearing the whole electroluminescent device. Specifically, the first anode and the second anode are disposed on the substrate, or the first cathode and the second cathode are disposed on the substrate.
A hole transport layer is located between the (quantum dot or organic) light emitting layer and the anode;
a hole injection layer is located between the hole transport layer and the anode or, in the case where no hole transport layer is provided, between the (quantum dot or organic) light emitting layer and the anode; the hole injection layer can further improve the luminous efficiency of each luminous unit so as to further reduce the power consumption.
An electron blocking layer is located between the (quantum dot or organic) light emitting layer and the hole transport layer, or in the case where the hole transport layer is not provided, a hole injection layer is located between the (quantum dot or organic) light emitting layer and the anode;
the hole blocking layer is positioned between the (quantum dot or organic) light emitting layer and the electron transport layer, or between the (quantum dot or organic) light emitting layer and the cathode without the electron transport layer;
the electron injection layer is located between the electron transport layer and the cathode, or in case no electron transport layer is provided, the hole blocking layer is located between the (quantum dot or organic) light emitting layer and the cathode.
In an embodiment of the present invention, the electroluminescent device further includes a pixel defining layer for separating adjacent light emitting cells. I.e. adjacent electroluminescent cells are separated by a pixel-defining layer. The pixel defining layer can also limit the material solution to accurately flow into a designated light-emitting unit sub-pixel area in the process of solution method process manufacturing, so that the reduction of light-emitting purity caused by color cross is prevented.
As a preferred embodiment, as shown in fig. 1, the electroluminescent device structure includes a substrate 100, a cathode 110 disposed on the substrate and a pixel defining layer 300 for separating adjacent light-emitting pixel units, an electron transport layer 120 disposed on the cathode 110, and a light-emitting layer disposed on the electron transport layer 120, wherein 210, 220, 230 respectively represent a red light-emitting layer, a green light-emitting layer, and a blue light-emitting layer, and at least one of 210, 220, and 230 is a quantum dot light-emitting layer and at least one is an organic light-emitting layer, a hole transport layer 130 disposed on the light-emitting layer, and an anode 140 disposed on the hole transport layer 130, and the material of the electron transport layer is selected from cross-linked electron transport materials.
As a more preferred embodiment, as shown in fig. 2, the electroluminescent device structure includes a substrate 100, a cathode 110 and a pixel defining layer 300 disposed on the substrate for separating adjacent light-emitting pixel units, an electron transport layer 120 disposed on the cathode 110, a light-emitting layer disposed on the electron transport layer 120, wherein 210, 220, 230 respectively represent a red light-emitting layer, a green light-emitting layer, and a blue light-emitting layer, and at least one of 210, 220, and 230 is a quantum dot light-emitting layer and at least one is an organic light-emitting layer, a hole transport layer 130 disposed on the light-emitting layer, a hole injection layer 135 disposed on the hole transport layer 130, and an anode 140 disposed on the hole injection layer 135, the material of the electron transport layer being selected from cross-linking type electron transport materials.
In addition to the above structure, the crosslinked electron-transporting material is preferably at least one of a phenylpyridine-based crosslinked electron-transporting material, a phenylbenzimidazole-based crosslinked electron-transporting material, a triphenylphosphine-based crosslinked electron-transporting material, and a triazole-based crosslinked electron-transporting material. The structure formed by crosslinking the optimal crosslinking type electron transport material has good chemical stability, can avoid the influence on the interface performance caused by the corrosion of a solvent when an upper functional layer is prepared, and particularly can avoid the influence on the luminous efficiency of a device caused by the corrosion of the solvent in a quantum dot luminescent material solution or an organic luminescent material solution. In addition, the preferable crosslinking type electron transport material has better compatibility, can be simultaneously used in a quantum dot electroluminescent unit and an organic electroluminescent unit, and has better stability.
Further preferably, the phenylpyridine-based cross-linked electron transport material is selected from at least one compound of the following formula:
DV-24 PyTAZ: 2, 4-bis (4- (4- (4- (tert-butyl) phenyl) -5- (4- (((4-vinylbenzyl) oxy) methyl) phenyl) -4H-1,2, 4-triazol-3-yl) phenyl) pyridine;
DV-25 PyTAZ: 2, 5-bis (4- (4- (4- (tert-butyl) phenyl) -5- (4- (((4-vinylbenzyl) oxy) methyl) phenyl) -4H-1,2, 4-triazol-3-yl) phenyl) pyridine;
DV-26 PyTAZ: 2, 6-bis (4- (4- (4- (tert-butyl) phenyl) -5- (4- (((4-vinylbenzyl) oxy) methyl) phenyl) -4H-1,2, 4-triazol-3-yl) phenyl) pyridine;
DV-35 PyTAZ: 3, 5-bis (4- (4- (4- (tert-butyl) phenyl) -5- (4- (((4-vinylbenzyl) oxy) methyl) phenyl) -4H-1,2, 4-triazol-3-yl) phenyl) pyridine.
The preferred phenylpyridine crosslinked electron transport material with the structure has better chemical stability.
In the embodiment of the present invention, preferably, the thickness of the first electron transport layer is 10 to 200 nm; preferably, the thickness of the second electron transport layer is 10 to 200 nm. In order to simplify the manufacturing process, it is preferable that the thickness of the first electron transport layer is the same as the thickness of the second electron transport layer.
The substrate is preferably a transparent substrate, and may be a glass substrate or a flexible substrate.
The luminescent material is selected according to the type of the luminescent layer, and when the luminescent layer is a quantum dot luminescent layer, the quantum dot luminescent material is selected. Specifically, the quantum dot luminescent material may be selected from group II-IV compound semiconductors including, but not limited to, CdS, CdSe, CdS/ZnS, CdSe/CdS/ZnS; and may also be selected from group III-V compound semiconductors or group IV-VI compound semiconductors, including but not limited to GaAs, InP, PbS/ZnS, PbSe/ZnS; the quantum dot light-emitting material can also be selected from semiconductor nanocrystals of I-III-VI2 groups and the like, and the quantum dot light-emitting material can be of a uniform mixing type, a gradient mixing type, a core-shell type or a combined type. The quantum dot light-emitting material may contain a dopant, and the doping method may be self-doping.
When the light emitting layer is an organic light emitting layer, a conventional organic light emitting material is selected. Preferably, a solution-processed organic light emitting material is used, so that a film can be formed during the preparation process by a solution process such as inkjet printing. For example, when the blue electroluminescent unit is an organic electroluminescent unit, the material of the blue organic light emitting layer in the blue electroluminescent unit is selected from diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives or fluorene derivatives. The preferred material of the blue organic light emitting layer not only has better processability, but also has better blue light emitting performance.
The hole transport material may be selected from organic hole transport materials such as poly (p-phenylene vinylene) (PPv), polythiophene, polysilane, triphenylmethane, triarylamine, hydrazone, pyrazoline, carbazole, butadiene, and the like, or NiO, MoO3The inorganic hole transport material and its composite may be selected from doped compositeSynthetic structures, for example, doped hole transport materials formed by doping at least one of F4-TCNQ (2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanoquinonedimethane), HAT-CN (2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene) to NPB (N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine), TPD (N, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine), MoO3Doped hole transport materials formed by doping NPB, TPD and the like.
The anode is made of metal material, including but not limited to metals such as Al, Au, Ag, Pt, Cu, Mo, Ni, Mg, etc., and may also be alloy.
The electroluminescent device provided by the embodiment of the invention can be prepared by the following method.
The embodiment of the invention also provides a preparation method of the electroluminescent device.
As a specific embodiment, the method for manufacturing the electroluminescent device comprises the following steps:
s01, providing a substrate, preparing a cathode and a pixel defining layer on the substrate, forming a pixel groove formed by surrounding the cathode as a bottom and the pixel defining layer, and presetting a quantum dot light-emitting area and an organic light-emitting area;
s02, depositing a cross-linking type first electron transmission material on the surface of a cathode of the quantum dot light emitting region, and heating the cathode in an inert environment to enable the cross-linking type electron transmission material to be cross-linked to prepare an electron transmission layer; depositing a cross-linking type electron transport material on the surface of the cathode of the organic light-emitting region, and heating the material in an inert environment to cross-link the cross-linking type electron transport material to prepare a second electron transport layer;
s03, preparing a light-emitting layer on the surface of the electron transport layer, and preparing an anode on the light-emitting layer, wherein a quantum dot light-emitting layer is prepared on the first electron transport layer, and an organic light-emitting layer is prepared on the second electron transport layer.
Specifically, in step S01, the cathode and the pixel defining layer are formed on the substrate by a conventional method. The quantum dot light-emitting area and the organic light-emitting area are preset according to product requirements or design requirements.
In step S02, a cross-linked electron transport material is deposited on the surface of the cathode in the quantum dot light emitting region, and a cross-linked electron transport material is deposited on the surface of the cathode in the organic light emitting region, so as to respectively prepare a first electron transport layer and a second electron transport layer. The crosslinking type electron transmission material is realized by adopting a solution processing method and preferably adopting an ink-jet printing mode, and not only is the process simple, but also a film layer with uniform thickness and higher flatness is easy to obtain. Further, the heat treatment is carried out in an inert atmosphere, wherein the temperature of the heat treatment is determined according to the type of the specific crosslinking type electron transport material, and is preferably such that the crosslinking of the material is achieved without damaging the electron transport material and the underlying structure material thereof.
In step S03, a light-emitting layer is formed on the surface of the electron transport layer, preferably by a solution processing method. At this time, different light emitting materials may be deposited according to different types of electroluminescent units. Specifically, a quantum dot light emitting layer is prepared on the first electron transport layer, and an organic light emitting layer is prepared on the second electron transport layer.
The anode is prepared on the luminous layer by adopting a vacuum plating mode.
Further, before the anode is prepared, a hole transport layer is preferably prepared on the light emitting layer by a solution processing method or a vacuum evaporation process.
As another embodiment, a method for manufacturing an electroluminescent device includes the steps of:
E01. providing a substrate, preparing an anode and a pixel defining layer on the substrate, forming a pixel groove formed by surrounding the anode as a bottom and the pixel defining layer, and presetting a quantum dot light-emitting area and an organic light-emitting area;
E02. preparing a quantum dot light-emitting layer on the surface of an anode of the quantum dot light-emitting region, depositing a cross-linking type electron transport material on the surface of the quantum dot light-emitting layer, and heating under an inert environment to enable the cross-linking type electron transport material to be cross-linked to prepare a first electron transport layer; preparing an organic light-emitting layer on the surface of the anode of the organic light-emitting region, depositing a cross-linking type electron transport material on the surface of the organic light-emitting layer, and heating the organic light-emitting layer in an inert environment to cross-link the cross-linking type electron transport material to prepare a second electron transport layer;
E03. and preparing a cathode on the surfaces of the first electron transport layer and the second electron transport layer.
Specifically, in step E01, the anode and the pixel defining layer on the substrate can be prepared by conventional methods, and the anode is preferably prepared by vacuum plating. The quantum dot light-emitting area and the organic light-emitting area are preset according to product requirements or design requirements.
In step E02, the quantum dot light-emitting layer is formed on the surface of the anode of the quantum dot light-emitting region, and the organic light-emitting layer is formed on the surface of the anode of the organic light-emitting region, preferably by a solution processing method. Further, before the light-emitting layer is formed, it is preferable to form a hole transport layer on the surface of the anode by a solution processing method or a vacuum evaporation process.
And the cross-linking type electron transmission material is deposited on the surface of the quantum dot light emitting layer, the cross-linking type electron transmission material is deposited on the surface of the organic light emitting layer, and the solution processing method is adopted, preferably, the ink-jet printing mode is adopted, so that the process is simple, and a film layer with uniform thickness and high flatness is easily obtained. Further, the heat treatment is carried out in an inert atmosphere, wherein the temperature of the heat treatment is determined according to the type of the specific crosslinking type electron transport material, and is preferably such that the crosslinking of the material is achieved without damaging the electron transport material and the underlying structure material thereof.
In step E03, cathodes are prepared on the surfaces of the first electron transport layer and the second electron transport layer, and are preferably achieved by vacuum plating.
The preparation method of the electroluminescent device provided by the embodiment of the invention only needs to adjust the type of the luminescent layer material on the one hand and perform heating treatment after depositing the cross-linking type electron transport material on the other hand on the basis of the preparation process of the conventional electroluminescent device so as to enable the material to be cross-linked. The method provided by the embodiment of the invention does not need an additional interface modification layer, has good process compatibility and simple process, can reduce the manufacturing cost, and most importantly, can obtain the electroluminescent device with good interface performance and high luminous efficiency.
The following description will be given with reference to specific examples.
Example 1
An electroluminescent device, as shown in fig. 1, includes a substrate 100 (glass substrate), a cathode 110(ITO transparent cathode) and a pixel defining layer 300 for separating adjacent light-emitting pixel units provided on the substrate, an electron transport layer 120(DV-26PyTAZ) provided on the cathode 110, a light-emitting layer provided on the electron transport layer 120, wherein 210, 220, 230 respectively denote a red light-emitting layer, a green light-emitting layer, and a blue light-emitting layer, 210 is a red quantum dot light-emitting layer, 220 is a green quantum dot light-emitting layer, 230 is a blue organic light-emitting layer, 130 is a hole transport layer, a hole transport layer 130 provided on the light-emitting layer, and an anode 140 provided on the hole transport layer 130.
The preparation method of the electroluminescent device comprises the following steps:
providing a substrate with ITO electrodes and pixel defining layers
Preparing the DV-26PyTAZ electronic transmission layer 120 on the substrate through ink-jet printing, fully printing all pixels, and removing the organic solvent through a vacuum drying method; heating to 230 ℃ under the inert gas environment for 20-40 minutes to fully crosslink the electron transport material and prepare an electron transport layer;
respectively printing a red quantum dot light-emitting layer 210, a green quantum dot light-emitting layer 220 and a blue organic light-emitting layer 230 in different pixel pits by ink-jet printing, and drying in vacuum;
heating to 140 ℃ under the inert gas environment for 20-40 minutes; vacuum evaporation is carried out on the hole transport layer 130 on the light-emitting layer, and all pixels are evaporated; the anode 140 is prepared on the hole transport layer 130 by vacuum evaporation.
Example 2
Example 2 differs from example 1 in that: 210 is a red quantum dot light emitting layer, 220 is a green organic light emitting layer, and 230 is a blue organic light emitting layer.
Example 3
An electroluminescent device, as shown in fig. 2, is different from embodiment 1 in that a hole injection layer 135 is interposed between a hole transport layer 130 and an anode 140.
The preparation method of the electroluminescent device comprises the following steps:
providing a substrate with ITO electrodes and pixel defining layers
Preparing the DV-26PyTAZ electronic transmission layer 120 on the substrate through ink-jet printing, fully printing all pixels, and removing the organic solvent through a vacuum drying method; heating to 230 ℃ under the inert gas environment for 20-40 minutes to fully crosslink the electron transport material and prepare an electron transport layer;
respectively printing a red quantum dot light-emitting layer 210, a green quantum dot light-emitting layer 220 and a blue organic light-emitting layer 230 in different pixel pits by ink-jet printing, and drying in vacuum;
heating to 140 ℃ under the inert gas environment for 20-40 minutes; vacuum evaporation is carried out on the hole transport layer 130 on the light-emitting layer, and all pixels are evaporated; vacuum evaporating the hole injection layer 135 on the hole transport layer 130, and evaporating all pixels; the anode 140 is prepared by vacuum evaporation on the hole injection layer 135.
Example 4
Example 4 differs from example 3 in that: 210 is a red quantum dot light emitting layer, 220 is a green organic light emitting layer, and 230 is a blue organic light emitting layer.
The results show that the electroluminescent devices prepared by combining the red and green quantum dots are more stable than quantum dot electroluminescent displays using quantum dots in three colors by fully utilizing the pure luminescent color of the red and green quantum dots and utilizing the characteristic that the blue organic electroluminescent service life is longer than that of the blue quantum dots. Example 2 and example 4, the green organic light emitting material had initial luminance of 1000cd/m2Has a brightness reduced to 95% and a lifetime over 3000 h, much longer than that of green quantum dots (under the same conditions, T95 is less than 500 h), and combines high-efficiency blue organic luminescent material and red organic luminescent materialThe quantum dot electroluminescence and the electroluminescent device prepared by combination realize the mixed luminescence display with better reliability.
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 (10)
1. An electroluminescent device comprising a substrate, and at least one quantum dot electroluminescent unit and at least one organic electroluminescent unit disposed on the substrate,
the quantum dot electroluminescent unit comprises a first anode and a first cathode which are oppositely arranged, a quantum dot light-emitting layer arranged between the first anode and the first cathode, and a first electron transport layer arranged between the quantum dot light-emitting layer and the first cathode;
the organic electroluminescent unit comprises a second anode and a second cathode which are oppositely arranged, an organic light-emitting layer arranged between the second anode and the second cathode, and a second electron transport layer arranged between the organic light-emitting layer and the second cathode;
wherein the first anode and the second anode are disposed on the substrate, or the first cathode and the second cathode are disposed on the substrate;
the materials of the first anode and the second anode are the same or different, the materials of the first cathode and the second cathode are the same or different, the material of the first electron transport layer is selected from a crosslinking type electron transport material, the material of the second electron transport layer is selected from a crosslinking type electron transport material, and the materials of the first electron transport layer and the second electron transport layer are the same or different.
2. The electroluminescent device according to claim 1, wherein the cross-linked electron transport material is at least one selected from the group consisting of phenylpyridine cross-linked electron transport materials, phenylbenzimidazole cross-linked electron transport materials, triphenylphosphine cross-linked electron transport materials, and triazole cross-linked electron transport materials.
3. The electroluminescent device according to claim 2, wherein the phenylpyridine-based cross-linked electron transport material is at least one selected from the group consisting of compounds having the following structures:
4. an electroluminescent device as claimed in claim 1, characterized in that the thickness of the first electron transport layer is from 10 to 200 nm.
5. An electroluminescent device as claimed in claim 1, characterized in that the thickness of the second electron transport layer is from 10 to 200 nm.
6. The electroluminescent device of claim 1, wherein the quantum dot electroluminescent unit comprises a red quantum dot electroluminescent unit and a green quantum dot electroluminescent unit, and the organic electroluminescent unit comprises a blue organic electroluminescent unit.
7. The electroluminescent device according to claim 6, wherein the material of the blue organic light emitting layer in the blue electroluminescent unit is selected from diarylanthracene derivatives, stilbene aromatic derivatives, pyrene derivatives or fluorene derivatives.
8. An electroluminescent device as claimed in any one of claims 1 to 7, wherein the first anode and the second anode are the same and the first cathode and the second cathode are the same.
9. An electroluminescent device as claimed in any one of claims 1 to 7, further comprising a pixel-defining layer for separating adjacent light-emitting cells.
10. A method for preparing an electroluminescent device is characterized by comprising the following steps:
providing a substrate, preparing a cathode and a pixel defining layer on the substrate, forming a pixel groove formed by surrounding the cathode as a bottom and the pixel defining layer, and presetting a quantum dot light-emitting area and an organic light-emitting area;
depositing a cross-linking type electron transport material on the surface of the cathode of the quantum dot light emitting region, and heating the cathode in an inert environment to cross-link the cross-linking type electron transport material to prepare a first electron transport layer; depositing a cross-linking type electron transport material on the surface of the cathode of the organic light-emitting region, and heating the material in an inert environment to cross-link the cross-linking type electron transport material to prepare a second electron transport layer;
preparing a luminescent layer on the surface of the electron transport layer, and preparing an anode on the luminescent layer, wherein a quantum dot luminescent layer is prepared on the first electron transport layer, and an organic luminescent layer is prepared on the second electron transport layer.
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