CN110459687A - Organic electroluminescence device and preparation method thereof, display panel - Google Patents
Organic electroluminescence device and preparation method thereof, display panel Download PDFInfo
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- CN110459687A CN110459687A CN201910688626.9A CN201910688626A CN110459687A CN 110459687 A CN110459687 A CN 110459687A CN 201910688626 A CN201910688626 A CN 201910688626A CN 110459687 A CN110459687 A CN 110459687A
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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
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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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
- H10K50/15—Hole transporting layers
- H10K50/155—Hole transporting layers comprising dopants
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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]
- H10K50/17—Carrier injection 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]
- H10K50/18—Carrier blocking layers
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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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Abstract
The present invention relates to a kind of organic electroluminescence devices and preparation method thereof, display panel.Wherein, organic electroluminescence device includes the first electrode being stacked, hole transporting unit, luminescent layer, electron-transport unit and second electrode；The luminescent layer includes light emitting host material, guest materials and the first antioxidant.Above-mentioned organic electroluminescence device inhibits or alleviates light emitting guest material in the oxygenolysis of high energy excitation state, to improve the service life of organic electroluminescence device by adulterating the first antioxidant in luminescent layer, by sacrificing the first antioxidant.
Description
Technical field
The present invention relates to display fields, more particularly to a kind of organic electroluminescence device and preparation method thereof, display surface
Plate.
Background technique
With the development of display technology, OLED (OrganicLight-Emitting Diode, organic luminescent device) is because of it
Have many advantages, such as that low in energy consumption, fast response time, high resolution, temperature range are wide, is increasingly becoming the mainstream in display market.Currently,
The service life is shorter at ambient and elevated temperatures for OLED device, as OLED device is in the continuous deterioration of operational process, the performance of device by
Gradual change is poor, eventually leads to component failure.Therefore, OLED device at room temperature or elevated temperatures the service life it is low problem it is urgently to be resolved.
Summary of the invention
Based on this, it is necessary to for OLED device service life low problem at room temperature or elevated temperatures, provide a kind of organic electroluminescence
Luminescent device and preparation method thereof, display panel.
A kind of organic electroluminescence device, including be stacked first electrode, hole transporting unit, luminescent layer, electronics
Transmission unit and second electrode；
The luminescent layer includes light emitting host material, guest materials and the first antioxidant.
Above-mentioned organic electroluminescence device is anti-oxidant by sacrificing first by adulterating the first antioxidant in luminescent layer
Agent inhibits or alleviates light emitting guest material in the oxygenolysis of high energy excitation state, to improve the use of organic electroluminescence device
Service life.
The doping concentration of first antioxidant is 0.001%~5% in one of the embodiments,；
Under high energy excitation state, first antioxidant is oxidized to inhibit or alleviate the oxidation of the guest materials point
Solution.
The hole transporting unit and/or the electron-transport unit include the second antioxygen in one of the embodiments,
Agent.
First antioxidant and second antioxidant include tertiary butyl to benzene in one of the embodiments,
At least one of diphenol, propylgallate, butylated hydroxy anisole, dibutyl hydroxy toluene, vitamin E, vitamin C.
The hole transporting unit includes being stacked in the hole in the first electrode in one of the embodiments,
Implanted layer, hole transmission layer and electronic barrier layer, second antioxidant are doped in the hole injection layer and the hole
Any in transport layer is in one or more layers.
The electron-transport unit includes being stacked to hinder in the hole on the luminescent layer in one of the embodiments,
Barrier, electron transfer layer and electron injecting layer, second antioxidant are doped in the hole blocking layer.
A kind of display panel, including aforementioned organic electroluminescence device.
A kind of preparation method of organic electroluminescence device, comprising the following steps:
Substrate is provided, forms first electrode on the substrate；
Hole transporting unit is formed on the first electrode；
Vapor deposition forms the luminescent layer doped with the first antioxidant on the hole transporting unit；
Electron-transport unit and second electrode are sequentially formed, on the light-emitting layer to form the organic electroluminescence
Part.
The vapor deposition on the hole transporting unit is formed doped with first antioxygen in one of the embodiments,
The luminescent layer of agent includes:
First antioxidant is pre-mixed, and co-evaporation with luminescent material, is formed doped with described anti-oxidant
The luminescent layer of agent；Or
The antioxidant is deposited respectively with the luminescent material and is deposited simultaneously, is formed doped with the antioxidant
The luminescent layer.
The hole transporting unit and/or the electron-transport unit include the second antioxygen in one of the embodiments,
Agent, first antioxidant and second antioxidant are identical or different.
The preparation method of above-mentioned organic electroluminescence device, it is anti-oxidant by being adulterated in luminescent layer and other functional layers
Agent inhibits or alleviates light emitting guest material in the oxygenolysis of high energy excitation state, to improve organic by sacrificing antioxidant
The service life of electroluminescent device.
Detailed description of the invention
Fig. 1 is the organic electroluminescence device structural schematic diagram that one embodiment of the application provides；
Fig. 2 is the organic electroluminescence device preparation method flow chart that one embodiment of the application provides.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawing to the present invention
Specific embodiment be described in detail.Many details are explained in the following description in order to fully understand this hair
It is bright.But the invention can be embodied in many other ways as described herein, those skilled in the art can be not
Similar improvement is done in the case where violating intension of the present invention, therefore the present invention is not limited by the specific embodiments disclosed below.
It should be noted that it can directly on the other element when element is referred to as " being set to " another element
Or there may also be elements placed in the middle.When an element is considered as " connection " another element, it, which can be, is directly connected to
To another element or it may be simultaneously present centering elements.Term as used herein " vertical ", " horizontal ", " left side ",
" right side " and similar statement for illustrative purposes only, are not meant to be the only embodiment.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body is not to be to limit the present invention.
In the process of running, anode provides hole to OLED device, and cathode provides electronics, and electrons and holes are compound in luminescent layer
It releases energy.The light-emitting guest of luminescent layer absorbs energy from ground state transition to excitation state, when light-emitting guest transits to excitation state
It loses electronics namely light-emitting guest is oxidized.The oxidation of light-emitting guest will lead to device performance and gradually be deteriorated, or even failure, contracting
Short device lifetime.
To solve the above problems, referring to Figure 1, one embodiment of the application provides a kind of organic electroluminescence device,
The problem of can alleviating or light-emitting guest is inhibited to aoxidize.The organic electroluminescence device of the application includes the first electricity being stacked
Pole 110, hole transporting unit 120, luminescent layer 130, electron-transport unit 140 and second electrode 150.
Wherein, first electrode 110 is anode, and the material of first electrode 110 can be inorganic material, for example, tin indium oxide
(ITO), the higher metal of the work functions such as the metal oxides such as indium zinc oxide (IZO) or gold, silver (Ag), copper.
Hole transporting unit 120 includes being stacked in hole injection layer 121, hole transmission layer in first electrode 110
122 and electronic barrier layer 123.Hole injection layer 121 can be using the stronger material preparation of Hole injection capacity, for example, HATCN
(six cyano -1,4,5,8,9,12- of 2,3,6,7,10,11-, six azepine benzophenanthrene) or p-doping material.P-doping material can be with
NPB ((the 1- naphthalene of N, N '-two is entrained in including F4-TCNQ (tetra- cyanogen dimethyl-parabenzoquinone of 2,3,5,6- tetra- fluoro- 7,7', 8,8'-)
Base)-N, diphenyl -1 N ' -, 1 '-biphenyl -4-4 '-diamines) the inner material formed, 121 thickness of hole injection layer can beHole transmission layer 122 can use the stronger p-type organic semiconducting materials of cavity transmission ability, such as triphen
Aminated compounds, triphenylamine compound may include NPB, TPD (bis- (3- aminomethyl phenyl)-N, N'- diphenyl biphenyl of N, N'-
Amine), any one in TAPC (4,4'- cyclohexyl two [N, N- bis- (4- aminomethyl phenyl) aniline]).Electronic barrier layer 123 can
With the p-type organic semiconducting materials deeper using lumo energy, such as TCTA (three (- 9 bases of 4- carbazole-phenyl) amine).
Electron-transport unit 140 includes being stacked hole blocking layer 141, electron transfer layer 142 on luminescent layer 130
With electron injecting layer 143.Hole blocking layer 141 can be using the organic type n semiconductor material deeper with HOMO energy level, such as
T2T (2,4,6- tri- (1,1'- xenyl) -1,3,5- triazine) etc..The material of electron transfer layer 142 can be electron transport ability
Preferable n-type organic semiconducting materials, such as TPBi (1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene), Alq3 (three
(8-hydroxyquinoline) close aluminium), BAlq (bis- (2- methyl -8-hydroxyquinoline-N1, O8)-(1,1'- biphenyl -4- hydroxyl) aluminium), BCP
At least one of (bathocuproine), 3TPYMB (three [2,4,6- trimethyl -3- (3- pyridyl group) phenyl] borines).Electron injecting layer
143 material may include metal or metallic compound of low work function, such as lithium fluoride (LiF), ytterbium (Yb), terbium (Tm) etc..
Luminescent layer 130 includes material of main part, guest materials and the first antioxidant.Material of main part is for dispersing object material
Material, prevents guest material concentration is higher from causing to be quenched, while can also transmit electrons and holes.Guest materials for absorb electronics and
The energy discharged when hole-recombination, and the object material from ground state transition to excitation state, since excitation state is unstable, therefore under excitation state
Material molecule can inactivate back to ground state and issue photon.Guest materials includes fluorescent dye or phosphorescent coloring.Wherein, fluorescent dye
It may include 4- (dintrile methyl) -2- butyl -6- (the long Lip river pyridine -9- vinyl of 1,1,7,7- tetramethyl) -4H- pyrans, diformazan
Base quinacridone, 5,6,11,12- tetraphenyl naphthonaphthalene, 2,3,6,7- tetrahydro -1,1,7,7- tetramethyl -1H, 5H, 11H-10-
(2-[4-morpholinodithio base)-quinolizino [9,9A, 1GH] cumarin, 4,4'- bis- (2,2- diphenylethyllene) -1,1'- biphenyl, 4,4'-
In bis- [4- (di-p-tolyl amino) styryl] biphenyl and bis- (9- ethyl -3- carbazole the vinyl) -1,1'- biphenyl of 4,4'-
Any one.Phosphorescent coloring may include that bis- (4,6- difluorophenyl pyridinato-N, C2) pyridinecarboxylics close iridium, bis- (4,6- difluoros
Phenylpyridine)-four (1- pyrazolyl) boric acid close iridium, bis- (4,6- bis- fluoro- 5- cyano-phenyl pyridine-N, C2) pyridine carboxylic acids close iridium,
Two (2 ', 4 '-difluorophenyl) pyridines] (tetrazolium pyridine) conjunction iridium, two (2- methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones)
Close iridium, two (1- phenyl isoquinolin quinoline) (acetylacetone,2,4-pentanediones) close iridium, acetopyruvic acid two (2- phenylpyridine) iridium, three (1- phenyl-isoquinoline
Quinoline) close at least one of iridium and three (2- phenylpyridines) conjunction iridium.
Since exciton is compound not exclusively, and light-emitting guest oxidizable decomposition under excitation state, lead to organic electroluminescence
The service life reduction of part, therefore, by the way that the first antioxidant to be doped in luminescent layer, under high energy excitation state, first is anti-oxidant
The volatile de-electromation of agent is oxidized, and then the first antioxidant can be sacrificed when luminous, saves light-emitting guest from damage, inhibits or alleviate hair
Light object oxygenolysis under high energy excitation state, improves the service life of organic electroluminescence device.
Organic electroluminescence device provided by the above embodiment in luminescent layer by adulterating the first antioxidant, by sacrificial
The first antioxidant of domestic animal inhibits or alleviates light emitting guest material in the oxygenolysis of high energy excitation state, to improve organic electroluminescence hair
The service life of optical device.
In one of the embodiments, the type of the first antioxidant include tert-butylhydroquinone, propylgallate,
At least one of butylated hydroxy anisole, dibutyl hydroxy toluene, vitamin E, vitamin C.Antioxidant is in luminescent layer
Doping concentration can be 0.001%~5%.Experimental result is shown, identical in doping concentration using identical display device
In the case of, adulterate the white light display part longest-lived of tert-butylhydroquinone, up to 11,000 hour or more.
It may also comprise the second antioxidant in hole transporting unit 120 in one of the embodiments,.
Specifically, hole transporting unit 120 includes being stacked in the hole injection layer 121 in first electrode 110, hole
Transport layer 122 and electronic barrier layer 123.Second antioxidant can be doped in hole injection layer 121 and hole transmission layer 122
At least one layer in.Since hole injection layer 121 and hole transmission layer 122 are chronically at oxidation state, easily it is oxidized and deteriorates point
The oxidation stability of hole injection layer 121 and hole transmission layer 122 can be improved by the way that the second antioxidant is added in solution, thus
Improve device lifetime.In the present embodiment, the type of the second antioxidant can be identical as the first antioxidant or with first
Antioxidant is different.Similar, the type of the second antioxidant includes tert-butylhydroquinone, propylgallate, butyl hydroxyl
At least one of base anisole, dibutyl hydroxy toluene, vitamin E, vitamin C.
It in one of the embodiments, also may include the second antioxidant in electron-transport unit 140.
Specifically, electron-transport unit 140 includes the hole blocking layer 141 being stacked on luminescent layer 130, electronics biography
Defeated layer 142 and electron injecting layer 143.Antioxidant can be doped in hole blocking layer 141.Similar, due to hole barrier
Layer 141 is chronically at oxidation state, is easily oxidized and deteriorates decomposition, by the way that the second antioxidant is added, hole barrier can be improved
The oxidation stability of layer 141, to improve device lifetime.
The second antioxygen can be adulterated in hole transporting unit 120 and electron-transport unit 140 in one of the embodiments,
The second antioxidant is adulterated in agent, i.e. hole injection layer 121, hole transmission layer 122 and hole blocking layer 141.While in
The second antioxidant is adulterated in hole injection layer 121, hole transmission layer 122, hole blocking layer 141 and luminescent layer 130, it can be into one
Step improves the service life of organic electroluminescence device.
The another embodiment of the application provides a kind of display panel, including aforementioned organic electroluminescence device.The present embodiment
In display panel can be in liquid crystal display panel, LED display panel or organic LED display panel
Any one.
Display panel provided by the above embodiment, organic electroluminescence device in luminescent layer by adulterating the first antioxygen
Agent inhibits or alleviates light emitting guest material in the oxygenolysis of high energy excitation state, to mention by sacrificing the first antioxidant
The service life of high organic electroluminescence device.
Referring to Fig. 2, the another embodiment of the application provides a kind of preparation method of organic electroluminescence device, including with
Lower step:
S100: substrate is provided, forms first electrode on substrate.
Wherein, substrate can be rigid substrates and be also possible to flexible base board.It is formed with driving circuit on substrate, has with driving
Machine lumination of light emitting diode.The first electrode formed on substrate is anode, and material can be indium tin oxide.The present embodiment
In, the mode that vapor deposition can be used forms first electrode on substrate.
S200: hole transporting unit is formed on the first electrode.
Hole transporting unit includes the hole injection layer, hole transmission layer and electronic blocking being sequentially formed in first electrode
Layer.The method that vapor deposition can be used forms above-mentioned functional layer on the first electrode.
Further, in the present embodiment, at least one layer in hole injection layer and hole transmission layer can adulterate the second antioxygen
Agent.Preferably, the second antioxidant can be adulterated simultaneously in hole injection layer and hole transmission layer.It, can be by second when preparation
Antioxidant is pre-mixed in proportion with hole-injecting material or hole mobile material, and under certain temperature condition and vacuum degree
On co-evaporation to first electrode.Or can use different evaporation sources, the second antioxidant and hole note is deposited simultaneously respectively
Enter material formation doped with the hole injection layer of antioxidant, or the second antioxidant and hole transport material is deposited simultaneously respectively
Material forms the hole transmission layer doped with the second antioxidant, to improve the service life of hole injection layer or hole transmission layer, improves
The service life of device.Then it adopts vapor deposition method to form electronic barrier layer on the hole transport layer.
S300: vapor deposition forms hair doped with the photosphere of the first antioxidant on hole transporting unit.
In one embodiment, luminescent material includes light emitting host and light-emitting guest, by light emitting host, light-emitting guest and
First antioxidant is pre-mixed in proportion, then at certain temperature and vacuum degree condition, by light emitting host, light-emitting guest
With antioxidant co-evaporation to electronic blocking layer surface, the luminescent layer doped with the first antioxidant is formed.
In another embodiment, luminescent material and the first antioxidant can be deposited respectively, utilizes different steamings
It rises in same vapor deposition chamber while the first antioxidant and luminescent material is deposited, by controlling the temperature of different evaporation sources,
Regulate and control evaporation rate, and then controls doping concentration of first antioxidant in luminescent layer.
In the present embodiment, the doping concentration of the first antioxidant can be 0.001%~5%.Due to the first antioxidant
Doping concentration range float smaller to the antioxidant effect coverage of device, therefore do not need strict control process conditions i.e.
Device performance can be achieved, the process window of device is big.
S400: electron-transport unit and second electrode are formed, once on the light-emitting layer to form organic electroluminescence device.
Then hole blocking layer, electron transfer layer and electron injecting layer is successively deposited in luminous layer surface and forms electron-transport
Unit.
It further, can be doped with the second antioxidant in hole blocking layer in the present embodiment.It can be anti-oxidant by second
The material of agent and functional layer is pre-mixed, and then co-evaporation forms the functional layer doped with the second antioxidant.It can also benefit
With different evaporation sources, while hole barrier materials and the second antioxidant are deposited, form hole blocking layer.Wherein, second is anti-
Oxidant can be identical or different with the first antioxidant as the first antioxidant.
Second electrode finally is deposited in electron-transport cell surface, forms organic electroluminescence device.
The preparation method of organic electroluminescence device provided by the above embodiment, by luminescent layer and other functional layers
Adulterate antioxidant, by sacrifice antioxidant inhibit or alleviate light emitting guest material high energy excitation state oxygenolysis, from
And improve the service life of organic electroluminescence device.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of organic electroluminescence device, which is characterized in that including be stacked first electrode, hole transporting unit, hair
Photosphere, electron-transport unit and second electrode；
The luminescent layer includes light emitting host material, guest materials and the first antioxidant.
2. organic electroluminescence device according to claim 1, which is characterized in that the hole transporting unit and/or institute
Stating electron-transport unit includes the second antioxidant.
3. organic electroluminescence device according to claim 1, which is characterized in that the doping of first antioxidant is dense
Degree is 0.001%~5%；
Under high energy excitation state, first antioxidant is oxidized to inhibit or alleviate the oxygenolysis of the guest materials.
4. organic electroluminescence device according to any one of claim 1-3, which is characterized in that described first is anti-oxidant
Agent and second antioxidant include tert-butylhydroquinone, propylgallate, butylated hydroxy anisole, dibutyl hydroxyl
At least one of base toluene, vitamin E, vitamin C.
5. organic electroluminescence device according to claim 4, which is characterized in that the hole transporting unit includes stacking
Hole injection layer, hole transmission layer and the electronic barrier layer being set in the first electrode, the second antioxidant doping
Any in the hole injection layer and the hole transmission layer is in one or more layers.
6. organic electroluminescence device according to claim 5, which is characterized in that the electron-transport unit includes stacking
Hole blocking layer, electron transfer layer and the electron injecting layer being set on the luminescent layer, second antioxidant are doped in
In the hole blocking layer.
7. a kind of display panel, which is characterized in that including organic electroluminescence device of any of claims 1-6.
8. a kind of preparation method of organic electroluminescence device, which comprises the following steps:
Substrate is provided, forms first electrode on the substrate；
Hole transporting unit is formed on the first electrode；
Vapor deposition forms the luminescent layer doped with the first antioxidant on the hole transporting unit；
Electron-transport unit and second electrode are sequentially formed on the light-emitting layer.
9. according to the method described in claim 8, it is characterized in that, the vapor deposition on the hole transporting unit forms doping
The luminescent layer for having first antioxidant includes:
First antioxidant is pre-mixed, and co-evaporation with luminescent material, is formed doped with the antioxidant
The luminescent layer；Or
The antioxidant is deposited respectively with the luminescent material and is deposited simultaneously, the institute doped with the antioxidant is formed
State luminescent layer.
10. according to the method described in claim 9, it is characterized in that, the hole transporting unit and/or the electron-transport list
Member includes the second antioxidant, and first antioxidant and second antioxidant are identical or different.
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Application publication date: 20191115 |