CN106654068A - Fabrication method and corresponding apparatus of organic electroluminescence device - Google Patents

Fabrication method and corresponding apparatus of organic electroluminescence device Download PDF

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Publication number
CN106654068A
CN106654068A CN201710049227.9A CN201710049227A CN106654068A CN 106654068 A CN106654068 A CN 106654068A CN 201710049227 A CN201710049227 A CN 201710049227A CN 106654068 A CN106654068 A CN 106654068A
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quantum dot
layer
light emitting
organic
emitting layer
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CN106654068B (en
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宋莹莹
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BOE Technology Group Co Ltd
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115OLEDs 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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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention relates to a fabrication method and a corresponding apparatus of an organic electroluminescence device, and aims to solve the problem of a self quenching phenomenon of a quantum dot device caused by agglomeration easily in the existing quantum dot display apparatus. The fabrication method comprises the steps of forming a positive electrode, a hole injection layer and a hole transport layer on a substrate; coating the hole transport layer with a whole layer of quantum dot solution comprising an organic semiconductor material; baking the coated quantum dot solution to enable groups on a core-shell structure of the quantum dots and the organic semiconductor material to be subjected to a polymerization reaction to form a solid-state quantum dot light emitting layer; and forming a hole barrier layer, an electron transport layer, an electron injection layer and a negative electrode on the quantum dot light emitting layer in sequence. By adding the organic semiconductor material, which is subjected to the polymerization reaction with the groups on the core-shell structure of the quantum dots, to the quantum dot solution, the quantum dots can be uniformly fixed in the light emitting layer through polymerization in the baking process, thereby reducing the quenching phenomenon caused by agglomeration of the quantum dots, improving light emitting efficiency and prolonging service life.

Description

A kind of preparation method and related device of organic electroluminescence device
Technical field
The present invention relates to display base plate technical field, more particularly to a kind of preparation method and phase of organic electroluminescence device Answer device.
Background technology
Light emitting diode with quantum dots display device is based on the one kind grown up on the basis of organic light-emitting display device New Display Technique, except for the difference that, its electroluminescence layer uses quantum dot layer.Existing light emitting diode with quantum dots shows The ray structure of device includes anode, hole injection layer, hole transmission layer, quantum dot light emitting layer, hole blocking layer, electric transmission Layer, electron injecting layer and negative electrode.Compared with common organic light-emitting diode display, quanta point electroluminescent have light peak width, The advantages of color saturation height, colour gamut width.
At present, light emitting diode with quantum dots display device still be present, due between nano-particle and solvent Interaction and the volatilization of solvent molecule quantum dot can be caused to reunite, while quantum dot layer is also received in the reunion of quantum dot The impact of thickness, it is more thick be susceptible to reunite, energy transfer can occur after reunion, energy loses in other forms, So that quantum dot occurs self-quenching phenomenon, quantum dot device efficiency is caused to decline, service life shortens.
In sum, quantum dot device easily occurs to quench certainly because of reunion in current light emitting diode with quantum dots display device Going out, phenomenon, light efficiency be low, short life.
The content of the invention
The preparation method and related device of a kind of organic electroluminescence device provided in an embodiment of the present invention, to solve mesh Quantum dot device easily occurs that self-quenching phenomenon, light efficiency be low, the life-span because of reunion in front light emitting diode with quantum dots display device Short problem.
A kind of preparation method of organic electroluminescence device provided in an embodiment of the present invention, including:
Anode, hole injection layer and hole transmission layer are formed on substrate;
Quantum dot solution of the flood comprising organic semiconducting materials is coated on the hole transport layer;
Quantum dot solution to coating is toasted, and makes the group and the organic semiconductor material on quantum dot core shell structure There is polymerisation in material, form the quantum dot light emitting layer of a flood solid-state;
Hole blocking layer, electron transfer layer, electron injecting layer and negative electrode are sequentially formed on the quantum dot light emitting layer.
The method for making organic electroluminescence device provided in an embodiment of the present invention, adding in quantum dot solution can With the machine semi-conducting material that the group on quantum dot core shell structure occurs polymerisation, thus to being coated on hole transmission layer Quantum dot solution when being toasted, quantum dot can be uniformly fixed in quantum dot light emitting layer by way of polymerization Portion, so as to reduce the quenching phenomenon produced because of quantum dot reunion, improves luminous efficiency, increases the service life.
Preferably, containing one or more polymerisable groups in the organic semiconducting materials;
The polymerisable group includes one or more in following groups:
Thiazolinyl or diene functional groups, alkynyl or diine functional group, sulfydryl, amino.
Preferably, the quantum dot solution also includes:Can dissolve the organic solvent of the organic semiconducting materials, Yi Jiyin Send out agent.
Preferably, organic solvent or alcohols solvent of the organic solvent for aromatics;
The organic solvent includes one or more in following solvent:
Methyl benzoate, methyl phenyl ethers anisole or cyclohexyl benzene.
Preferably, the mass percent of quantum dot described in the quantum dot solution is 1%-20%;It is described organic partly to lead The mass percent of body material is 10%-30%;The mass percent of the initiator is 0.1%-0.5%;It is remaining for institute State organic solvent.
Preferably, coating quantum dot solution by following method:
Spin-coating method, inkjet printing, slot coated or bar shaped are coated with.
Preferably, the temperature of the baking is not higher than 150 DEG C;The time of the baking is less than 60min.
A kind of organic electroluminescence device provided in an embodiment of the present invention, including:The anode being successively set on substrate, it is empty Cave implanted layer, hole transmission layer, quantum dot light emitting layer, hole blocking layer, electron transfer layer, electron injecting layer and negative electrode;
Wherein, the quantum dot light emitting layer is polymerized by the group on quantum dot core shell structure with organic semiconducting materials Reaction is formed.
Preferably, 3-10 of the distance between each adjacent quantum dot in the quantum dot light emitting layer for lateral size of dots Times.
A kind of display device provided in an embodiment of the present invention, the display device includes provided in an embodiment of the present invention above-mentioned Arbitrary organic electroluminescence device.
Description of the drawings
The step of Fig. 1 is a kind of preparation method of organic electroluminescence device provided in an embodiment of the present invention flow chart;
Fig. 2 is a kind of structural representation of organic electroluminescence device provided in an embodiment of the present invention.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, is not whole embodiments.Based on this Embodiment in invention, the every other reality that those of ordinary skill in the art are obtained under the premise of creative work is not made Example is applied, the scope of protection of the invention is belonged to.
Wherein, film thickness and region shape do not reflect its actual proportions in accompanying drawing, and purpose is the schematically illustrate present invention Content.
A kind of organic electroluminescence device provided in an embodiment of the present invention, is the base in existing organic electroluminescence device Improvement on plinth, to quantum dot light emitting layer.The present invention add in quantum dot solution can with quantum dot core shell structure on There is the machine semi-conducting material of polymerisation in group, thus toast in the quantum dot solution to being coated on hole transmission layer When, quantum dot can be uniformly fixed on the inside of quantum dot light emitting layer by way of polymerization.
Due in current light emitting diode with quantum dots display device quantum dot device easily occur because of reunion self-quenching show As, light efficiency is low, short life, thus the embodiment of the present invention first describes a kind of preparation method of organic electroluminescence device, then has The structure of the organic electroluminescence device that body introduction is made using the method.Its concrete preparation method is carried out in detail first below Explanation.
As shown in figure 1, for a kind of organic electroluminescence device provided in an embodiment of the present invention preparation method the step of flow Cheng Tu, specifically can be realized using following steps:
Step 101, forms anode, hole injection layer and hole transmission layer on substrate;
Step 102, coats quantum dot solution of the flood comprising organic semiconducting materials on hole transmission layer;
Step 103, the quantum dot solution to coating is toasted, and the group on quantum dot core shell structure is partly led with organic There is polymerisation in body material, form the quantum dot light emitting layer of a flood solid-state;
Step 104, sequentially forms hole blocking layer, electron transfer layer, electron injecting layer and the moon on quantum dot light emitting layer Pole.
At present, due in current light emitting diode with quantum dots display device quantum dot device easily occur because of reunion from quenching Going out, phenomenon, light efficiency be low, short life.
Based on this, the preparation method of above-mentioned organic electroluminescence device provided in an embodiment of the present invention, in quantum dot solution In add the machine semi-conducting material that polymerisation can occur with the group on quantum dot core shell structure, thus to being coated to When quantum dot solution on hole transmission layer is toasted, quantum dot can be uniformly fixed on quantum dot by way of polymerization The inside of luminescent layer, so as to reduce the quenching phenomenon produced because of quantum dot reunion, improves luminous efficiency, increases the service life.
In the specific implementation, the preparation method of organic electroluminescence device provided in an embodiment of the present invention, can be by appointing Meaning mode makes anode and negative electrode, and here is not limited.The embodiment of the present invention is mainly walked to the making of quantum dot light emitting layer Suddenly it is improved.
Specifically, in execution step 102, after hole transmission layer is formed on substrate, then apply on hole transmission layer Cover quantum dot solution of the flood comprising organic semiconducting materials;The mode of specific coating quantum dot solution, can be according to reality Border needs to be selected, preferably, coating quantum dot solution by following method:Spin-coating method, inkjet printing, slot coated or bar Shape is coated with.
Wherein, organic semiconducting materials can occur polymerisation, specific material with the group on quantum dot core shell structure Material, can be chosen according to actual needs.Preferably, containing one or more polymerisable bases in organic semiconducting materials Group;Polymerisable group includes one or more in following groups:Thiazolinyl or diene functional groups, alkynyl or diine functional group, Sulfydryl, amino.
Further, in execution step 103, after quantum dot solution has been coated on hole transmission layer, to coating Quantum dot solution is toasted, so that the group on quantum dot core shell structure occurs polymerisation, mesh with organic semiconducting materials The quantum dot light emitting layer for being the position for fixing quantum dot, forming a flood solid-state, prevent quantum dot reunite it is luminous be quenched it is existing As.When being toasted, the temperature and time of baking can be according to actual needs grasped, the temperature of baking is generally not more than 200 DEG C; Preferably, the temperature of baking is not higher than 150 DEG C;The time of baking is less than 60min.
In the specific implementation, as shown in Fig. 2 for a kind of structure of organic electroluminescence device provided in an embodiment of the present invention Schematic diagram, the organic electroluminescence device that the embodiment of the present invention makes is empty except including the anode 202 being arranged on substrate 201 Cave implanted layer 203, hole transmission layer 204, quantum dot light emitting layer 205, hole blocking layer 206, electron transfer layer 207, electronics note Enter layer 208 and negative electrode 209.And in addition to quantum dot light emitting layer, the concrete preparation method of other film layers, here is not limited.
In the specific implementation, in for making the quantum dot solution of quantum dot light emitting layer, except including quantum dot and organic Outside semi-conducting material, preferably, quantum dot solution also includes:The organic solvent of dissolvable organic semiconducting materials, and cause Agent.
Wherein, organic solvent can dissolve organic semiconducting materials, but can not dissolve other film layers being in contact with it, compared with Good, organic solvent is the organic solvent or alcohols solvent of aromatics;Organic solvent includes one or more in following solvent: Methyl benzoate, methyl phenyl ethers anisole or cyclohexyl benzene.
In order to preferably make the group on the quantum dot core shell structure in quantum dot solution occur with organic semiconducting materials Polymerisation, needs the ratio for controlling organic semiconducting materials and quantum dot in quantum dot solution, in making quantum dot light emitting layer The distance between each adjacent quantum dot is 3-10 times of lateral size of dots.Preferably, in quantum dot solution quantum dot quality Percentage is 1%-20%;The mass percent of organic semiconducting materials is 10%-30%;The mass percent of initiator is 0.1%-0.5%;It is remaining for organic solvent.
Specifically, when quantum dot solution is prepared, organic semiconducting materials, organic solvent, amount are included in quantum dot solution Son point and initiator etc., using front mixing 2-5h, the range of speeds is 200-500rpmin to the solution.
In the specific implementation, the quantum dot adopted in the quantum dot solution that the embodiment of the present invention is used, there is nucleocapsid to tie for it Structure, the organo-functional group of core shell structure includes thiazolinyl or diene functional groups, alkynyl or diine functional group, sulfydryl, amino etc.;Quantum The material of point includes in CdS, CdSe, CdTe, ZnS, ZnTe, HgSe, InAs, AlAs, AlP, AlSb, GaP and GaAs etc. Plant or various;And the diameter of quantum dot is generally 1nm-10nm.
Based on same inventive concept, the embodiment of the present invention is additionally provided a kind of organic electroluminescence made by said method and is sent out Optical device, due to principle and the organic electroluminescence provided in an embodiment of the present invention of the organic electroluminescence device solve problem The preparation method of part is similar, therefore the enforcement of the organic electroluminescence device may refer to the enforcement of method, repeats part no longer Repeat.
As shown in Fig. 2 organic electroluminescence device provided in an embodiment of the present invention includes:It is successively set on substrate 201 Anode 202, hole injection layer 203, hole transmission layer 204, quantum dot light emitting layer 205, hole blocking layer 206, electric transmission Layer 207, electron injecting layer 208 and negative electrode 209;Wherein, quantum dot light emitting layer 205 by the group on quantum dot core shell structure with have There is polymerisation and formed in machine semi-conducting material.
In the specific implementation, preferably, the ratio by controlling organic semiconducting materials and quantum dot material, quantum dot The distance between each adjacent quantum dot in photosphere is 3-10 times of lateral size of dots, can prevent quantum dot reunion and from Quenching phenomenon, obtains higher quantum efficiency.
Based on same inventive concept, the embodiment of the present invention additionally provides a kind of display device, and the display device is including this Any of the above-described organic electroluminescence device that bright embodiment is provided.Due to the principle and reality of the present invention of the display device solve problem The organic electroluminescence device for applying example offer is similar, therefore the enforcement of the display device may refer to organic electroluminescence device Implement, repeat part and repeat no more.
In sum, the method for making organic electroluminescence device provided in an embodiment of the present invention, in quantum dot solution Adding can occur the machine semi-conducting material of polymerisation with the group on quantum dot core shell structure, thus to the quantum When point solution is toasted, quantum dot can be uniformly fixed on the inside of quantum dot light emitting layer by way of polymerization, so as to The quenching phenomenon produced because of quantum dot reunion is reduced, luminous efficiency is improved, is increased the service life.
Obviously, those skilled in the art can carry out the essence of various changes and modification without deviating from the present invention to the present invention God and scope.So, if these modifications of the present invention and modification belong to the scope of the claims in the present invention and its equivalent technologies Within, then the present invention is also intended to comprising these changes and modification.

Claims (10)

1. a kind of preparation method of organic electroluminescence device, it is characterised in that include:
Anode, hole injection layer and hole transmission layer are formed on substrate;
Quantum dot solution of the flood comprising organic semiconducting materials is coated on the hole transport layer;
Quantum dot solution to coating is toasted, and the group on quantum dot core shell structure is sent out with the organic semiconducting materials Raw polymerisation, forms the quantum dot light emitting layer of a flood solid-state;
Hole blocking layer, electron transfer layer, electron injecting layer and negative electrode are sequentially formed on the quantum dot light emitting layer.
2. the method for claim 1, it is characterised in that can gather comprising one or more in the organic semiconducting materials The group of conjunction;
The polymerisable group includes one or more in following groups:
Thiazolinyl or diene functional groups, alkynyl or diine functional group, sulfydryl, amino.
3. the method for claim 1, it is characterised in that the quantum dot solution also includes:Can dissolve described organic half The organic solvent of conductor material, and initiator.
4. method as claimed in claim 3, it is characterised in that the organic solvent is molten for the organic solvent or alcohols of aromatics Agent;
The organic solvent includes one or more in following solvent:
Methyl benzoate, methyl phenyl ethers anisole or cyclohexyl benzene.
5. method as claimed in claim 3, it is characterised in that the mass percent of quantum dot described in the quantum dot solution For 1%-20%;The mass percent of the organic semiconducting materials is 10%-30%;The mass percent of the initiator is 0.1%-0.5%;Remaining solution is organic solvent.
6. the method for claim 1, it is characterised in that quantum dot solution is coated by following method:
Spin-coating method, inkjet printing, slot coated or bar shaped are coated with.
7. the method for claim 1, it is characterised in that the temperature of the baking is not higher than 150 DEG C;The baking when Between be less than 60min.
8. a kind of organic electroluminescence device, it is characterised in that include:The anode being successively set on substrate, hole injection layer, Hole transmission layer, quantum dot light emitting layer, hole blocking layer, electron transfer layer, electron injecting layer and negative electrode;
Wherein, by the group on quantum dot core shell structure and organic semiconducting materials there is polymerisation in the quantum dot light emitting layer Formed.
9. organic electroluminescence device as claimed in claim 8, it is characterised in that each phase in the quantum dot light emitting layer The distance between adjacent quantum dot is 3-10 times of lateral size of dots.
10. a kind of display device, it is characterised in that the display device includes organic as described in any one of claim 8-9 Electroluminescent device.
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