CN109473562A - A kind of organic electroluminescence device - Google Patents
A kind of organic electroluminescence device Download PDFInfo
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- CN109473562A CN109473562A CN201811398407.9A CN201811398407A CN109473562A CN 109473562 A CN109473562 A CN 109473562A CN 201811398407 A CN201811398407 A CN 201811398407A CN 109473562 A CN109473562 A CN 109473562A
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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
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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
- H10K50/165—Electron transporting layers comprising dopants
Abstract
This application discloses a kind of organic electroluminescence devices, including luminescent layer and positioned at the hole transport functional layer and electron-transport functional layer of the luminescent layer two sides, doped with semiconductor material in the hole transport functional layer or the electron-transport functional layer of electroluminescent device light-emitting surface side.The application by the hole transport functional layer or the electron-transport functional layer of the luminescent device (OLED device) close to electroluminescent device light-emitting surface side doped with semiconductor material, so that the carrier mobility of luminescent device haves a qualitative leap, the service life of luminescent device has also obtained the promotion of matter, the carrier transport ability for reaching setting thickness simultaneously promotes the ultraviolet light that layer also effectively absorbs certain specific wavelengths, to significantly promote the reliability and service life of OLED Related product, application space also can increase.
Description
Technical field
The present disclosure relates generally to technical field of organic electroluminescence, and in particular to a kind of organic electroluminescence device.
Background technique
OLED (Organic Light Emitting Diode, Organic Light Emitting Diode) refer to organic semiconducting materials and
Luminescent material is under electric field driven, the phenomenon that injection by carrier with composite guide photoluminescence.Its principle is to use transparent/translucent
Metal/metal oxide electrode and metal/metal oxide electrode drive respectively as the anode and cathode of device in external electrical field
Under dynamic, carrier (electrons and holes) is injected into electrons and holes transfer function layer, electrons and holes point from cathode and anode respectively
Not Jing Guo electrons and holes transfer function layer be transmitted to luminescent layer, and exciton (exciton) is formed in luminescent material, in exciton
It disappears after limited electron-hole is compound, energy radiates (emission wavelength is limited to luminescent material characteristic) in the form of visible light.
Radiant light can be observed from transparent/translucent electrode side.This principle of luminosity is widely applied in illumination and display screen.
But most organic materials are sensitive to high-energy light, and the high-energy light source being primarily present in general environment is the energy that shines
Amount mainly falls in 2.8-4.1 electron-volts of energy；Some materials are possible to the high-energy light because in environment in OLED device
Source causes to decay in turn, the rule of decaying are as follows: the illumination of high-energy light source and the product of irradiation time magnitude are close to a fixed value.
The some proportion that the upper decaying of OLED illumination application reaches original brightness can be defined as the service life of OLED illumination, if OLED device is answered
It can largely be irradiated by high-energy light with (such as automobile-used or aviation lighting), then high-energy light source therein can accelerate to shield the old of body
Change, shortens its service life.
In the prior art, it influences to improve the scheme of OLED screen body life time to be in OLED screen for reducing ultraviolet light irradiation
External or internal setting can stop the device or material of ultraviolet light, and be setting in screen body outer barrier high-energy light source mostly
Meter, such as use external lamp housing, anti-ultraviolet material, reflecting layer etc..These schemes can improve OLED device to a certain extent
Service life.But the design of above-mentioned blocking high-energy light source affects the beauty of OLED device to a certain extent, increases
The cost of OLED device.
Summary of the invention
In view of drawbacks described above in the prior art or deficiency, OLED device sheet can inherently be improved by being intended to provide one kind
The anti-high-energy light source irradiation ability of body and the organic electroluminescence device for not influencing design.
First aspect the application provides a kind of organic electroluminescence device, including luminescent layer and is located at the luminescent layer two sides
Hole transport functional layer and electron-transport functional layer,
The hole transport functional layer or the electron-transport function close to electroluminescent device light-emitting surface side
Doped with semiconductor material in layer, the semiconductor material of the doping is the resistance of the light in 350nm-450nm to wave-length coverage
Gear rate is more than or equal to 40%.
According to technical solution provided by the embodiments of the present application, the semiconductor material includes metal, metal oxide, carbon
The organic metal misfit of material, the organic material of high electron affinity or low free ability, high electron affinity or low free ability
At least one of object.
According to technical solution provided by the embodiments of the present application,
It is more than or equal to 40nm doped with the thickness of the hole transport functional layer of the semiconductor material, alternatively,
It is more than or equal to 40nm doped with the thickness of the electron-transport functional layer of the semiconductor material.
According to technical solution provided by the embodiments of the present application, the volume percent range of the semiconductor material of the doping is
2%-50%.
According to technical solution provided by the embodiments of the present application, doped in the hole transport functional layer of the semiconductor material
The optical energy gap of material is doped between 2.6-3.4 electron-volts,
Alternatively,
Doped be doped in the electron-transport functional layer of the semiconductor material optical energy gap of material between
2.6-3.4 electron-volt.
According to technical solution provided by the embodiments of the present application, doped with the semiconductor material hole transport functional layer with
Protective layer is equipped between the luminescent layer,
Alternatively,
Doped between the electron-transport functional layer and luminescent layer of the semiconductor material be equipped with protective layer.
According to technical solution provided by the embodiments of the present application, the carrier transmission characteristics of material in the protective layer,
With in the hole transport functional layer doped with the semiconductor material to be doped material consistent；
Or
With in the electron-transport functional layer doped with the semiconductor material to be doped material consistent.
According to technical solution provided by the embodiments of the present application, the thickness of the protective layer is more than or equal to 10nm.
The application passes through in the described of the close electroluminescent device light-emitting surface side of luminescent device (OLED device)
Doped with semiconductor material in hole transport functional layer or the electron-transport functional layer, inherently make OLED device in height
Still there is very strong carrier transport ability under the irradiation of mild high-energy light, so that the service life of OLED device is extended,
Service life especially under high temperature and high-energy light irradiation also can to significantly promote the reliability of OLED Related product
Increase application space.When the concentration of semiconductor material reaches setting concentration, the carrier mobility of luminescent device has matter
Leap, so that the service life of luminescent device has also obtained the promotion of matter；So that the technical solution of the application can not influence original
Have improve under the premise of OLED device structure and production technology carrier (electronics or hole) mobility in OLED device and
Service life under the service life of OLED device, especially hot environment and ultraviolet irradiation environment, experiments have shown that the application
Technical solution make OLED screen body normal service life improve at least 50%, high-temperature operation service life at least improves
30%, ultraviolet irradiation lower device lifetime promotes at least 2 times；
Reach the hole transport functional layer and electron-transport functional layer doped with semiconductor material of setting thickness simultaneously
The ultraviolet light for effectively absorbing certain specific wavelengths, the blocking that can also play 50% or more to some other ultraviolet light wave band are made
With；
Therefore the technical solution of the application and traditional uvioresistant design scheme reverse thinking, from raising OLED device sheet
The carrier transmission performance of body is set about so that the carrier in OLED device still just has very by force after high temperature and high radiation
Transmission characteristic, improve its service life under high temperature and ultraviolet irradiation environment from the positive performance for improving OLED device；So that
The service life of OLED luminescent device and stability have a qualitative leap.
Protective layer in technical scheme can effectively avoid influence of the semiconductor material to luminescent layer, be effectively prevented from
The generation of quenching phenomenon in luminescent layer.Especially when protective layer is using the hole transport functional layer or electronics where semiconductor material
In transfer function layer when being doped material preparation, better effect, technique is simpler.
Detailed description of the invention
By reading a detailed description of non-restrictive embodiments in the light of the attached drawings below, the application's is other
Feature, objects and advantages will become more apparent upon:
Fig. 1 is the structural schematic diagram of the first embodiment of the application organic electroluminescence device；
Fig. 2 is the structural schematic diagram of second of embodiment of the application organic electroluminescence device；
Fig. 3 is the structural schematic diagram of the third embodiment of the application organic electroluminescence device；
Fig. 4 is the structural schematic diagram of the 4th kind of embodiment of the application organic electroluminescence device；
Fig. 5 is the structural schematic diagram of the reference object into experiment three of experiment one in the application；
Figure label: 10, substrate；20, first electrode；30, hole transport functional layer；60, second electrode；40, luminescent layer；
50, electron-transport functional layer；70, protective layer.
Specific embodiment
The application is described in further detail with reference to the accompanying drawings and examples.It is understood that this place is retouched
The specific embodiment stated is used only for explaining related invention, rather than the restriction to the invention.It also should be noted that in order to
Convenient for description, part relevant to invention is illustrated only in attached drawing.
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.The application is described in detail below with reference to the accompanying drawings and in conjunction with the embodiments.
Please referring to Fig. 1 is a kind of a kind of structural schematic diagram of embodiment of organic electroluminescence device of the application, including successively
Substrate 10, first electrode 20, organic layer, second electrode 60 and the encapsulating structure (being not drawn into figure) being superposed；It is described organic
Layer includes luminescent layer 40, hole transport functional layer 30 and electron-transport functional layer 50 positioned at 40 two sides of luminescent layer；Close to described
Doped with semiconductor in the hole transport functional layer or the electron-transport functional layer of electroluminescent device light-emitting surface side
Material, the semiconductor material are more than or equal to 40% to wave-length coverage for the blocking rate of the light in 350nm-450nm.
The light that wavelength is 350-450nm is range of the black light to dark blue light, this is sunlight irradiation earth atmosphere ring
Higher-energy wave band present in border (the cosmic ray majority of higher energy is sharply reduced because atmosphere acts on), 350-
The light of 450nm wave band causes significant impact to organic semiconducting materials, this is substantially unavoidable problem, and this Shen
Voluntarily the light of 350-450nm please can be absorbed after the middle semiconductor material adulterated, the hole that balance control is doped passes
The charge transmission of transmission function layer or electron-transport functional layer and ultraviolet ray ageing performance, allow product lifecycle substantially
It does not have because ultraviolet light leads to the problem of aging.
Doped with setting matcoveredn 70 between the electron-transport functional layer 50 and the luminescent layer 40 of semiconductor material, or
Person is doped with setting matcoveredn 70 between the hole transport functional layer 30 and the luminescent layer 40 of semiconductor material.
The semiconductor material of doping makes in the transfer function layer being doped that there are a large amount of charges, and luminescent layer is theoretically deposited
In a large amount of excitons, exciton dominates luminous efficiency and the characteristics of luminescence, however exciton is easy to and charge reciprocation, this reciprocation
Ji temper is easily caused to go out；Exciton is easy and charge reciprocation, but the formation of exciton is also (hole and electricity since charge
Son respectively enters luminescent layer, and the excited state before electronics and hole-recombination shine is known as exciton), therefore we need protective layer to have
Standby same transmission characteristic, but characteristic is poorer than doped layer, and the accumulation of charge can be allowed to appear in the junction of doped layer and protective layer in this way,
Charge needed for luminescent layer can be supplied again simultaneously, which generates exciton, can effectively reduce exciton and charge because of the separation of protective layer
Reciprocation Zao Cheng temper go out effect.Therefore the interior carrier transport of the protective layer designed in above-described embodiment of the application
When characteristic is consistent with the carrier transmission characteristics of transfer function layer that it is entrained in, charge and exciton reciprocation can be reduced；
Can also confinement exciton rest in luminescent layer, avoid the generation of quenching phenomenon.
Above-mentioned hole transport functional layer 30 is made of the material for being able to achieve hole transport, such as can be p-type hole
Transport layer, above-mentioned electron-transport functional layer 50 are made of the material for being able to achieve electron-transport, such as can be N-type electronics biography
Defeated layer.
Above-mentioned organic electroluminescence device is OLED luminescent device；OLED luminescent device has bottom emission, such as Fig. 1 and
Shown in Fig. 2, namely from 20 side of first electrode shine, also have from top surface shine, as shown in Figure 3 and Figure 4, i.e., from second electrode side
60 shine；Arrow direction is light emission direction in figure, and the organic layer between first electrode 20 and second electrode 60 can be PIN
Structure, as shown in figures 1 and 3；It is also possible to NIP structure, as shown in Figure 2 and Figure 4；Namely OLED luminescent device can be Fig. 1
To four kinds of structures between Fig. 4, regardless of structure, semiconductor material is entrained between light-emitting surface and luminescent layer 40.
Hole transport functional layer can be by least one in hole injection layer HI, hole transmission layer HT, electronic barrier layer EBL
A layering composition, electron-transport functional layer can by electron injecting layer EI, electron transfer layer ET and hole blocking layer HBL extremely
Few layering composition；
When semiconductor material is entrained in hole transport functional layer, semiconductor material can be entrained in hole injection
Layer HI, hole transmission layer HT, in electronic barrier layer EBL any one, in any two or three layerings；
When semiconductor material is entrained in hole transport functional layer, semiconductor material can also independently form one
Layer, is inserted in the layering of hole transport functional layer or positioned at the two sides of hole transport functional layer；
When semiconductor material is entrained in electron-transport functional layer, semiconductor material can be entrained in electron injecting layer
In EI, electron transfer layer ET and hole blocking layer HBL any one, any two or three layering in；
When semiconductor material is entrained in electron-transport functional layer, semiconductor material can also independently form one layer,
It is inserted in the layering of electron-transport functional layer or positioned at the two sides of electron-transport functional layer；
The semiconductor material includes organic material of metal, metal oxide, carbon materials, high electron affinity or low free energy
At least one of material or organic metal misfit object.
The semiconductor material includes MoO3, F16-CuPc, F4-TCNQ, TCNQ, HATCN HATNA-Cl6, HATNA-
At least one of F6, HATNA, TNAP2, NDP-9ReO3, Rb2CO3, Cs2CO3, CsN3, Li, Liq etc..
Such as hole transport functional layer just need to arrange in pairs or groups high electron affinity material such as F16-CuPc, F4-TCNQ,
TCNQ, HATCN HATNA-Cl6, HATNA-F6, HATNA, TNAP2, NDP-9 etc..
Electron-transport functional layer just arrange in pairs or groups it is low it is free can material such as ReO3, Rb2CO3, Cs2CO3, CsN3, Li, Liq etc..
Below with four groups of description of test:
Experiment one:
Reference object: common green phosphorescent system OLED device, structure are as shown in Figure 5；
Experimental subjects: its structure is as shown in Figure 1, doping concentration is 8% in the hole transport functional layer 30 of reference object
Molybdenum oxide (MoO3) form carrier transport ability and promote layer, the doping concentration of molybdenum oxide (MoO3) refers to molybdenum oxide
(MoO3) percentage of the volume of entire hole transport functional layer 30, mixing in the other embodiments in the application are spatially accounted for
Miscellaneous concentration also herewith defines；Carrier transport ability promoted layer with a thickness of 40nm, the material of main part of hole transport functional layer, i.e.,
Being doped material is cavitation material NPB, and optical energy gap is 2.6 electron-volts, and protective layer also uses cavitation material NPB, thick
Degree is 10nm；
Experimental result: experimental subjects and the photoelectric efficiency of reference object maintain an equal level；Other performance comparisons are as shown in table 1 below:
Analysis of experimental results: the definition in above-mentioned service life is time when decaying to original brightness half from original brightness；
After having used technical scheme, the high-temperature operation life-span upgrading of OLED device 50%, OLED device under ultraviolet irradiation
2 times of part life-span upgrading, hole mobility improves 1 order of magnitude；It is effectively improved high temperature and irradiates lower device stability；This reality
Testing object can effectively stop wavelength in the ultra-violet bands of 380nm-450nm up to 40% or more；.
Experiment two:
Reference object: red phosphorescent system OLED device, structure are as shown in Figure 5；
Experimental subjects: its structure is as shown in Figure 1, doping concentration is 2% in the hole transport functional layer 30 of reference object
Tungsten oxide (WO3) form carrier transport ability and promote layer, carrier transport ability promoted layer with a thickness of 50nm, hole passes
The material of main part of transmission function layer is cavitation material NPB, and optical energy gap is 3.4 electron-volts, and protective layer also uses cavitation material
NPB, with a thickness of 15nm；
Experimental result: experimental subjects and the photoelectric efficiency of reference object maintain an equal level；Other performance comparisons are as shown in table 1 below:
Analysis of experimental results: after having used technical scheme, the high-temperature operation life-span upgrading of OLED device
50%, 3.8 times of OLED device life-span upgrading under ultraviolet irradiation, hole mobility improves about 10 times.
Experiment three:
Reference object: red phosphorescent system OLED device, structure are as shown in Figure 5；
Experimental subjects: its structure is as shown in Figure 1, doping concentration is 50% in the hole transport functional layer 30 of reference object
High electron affinity organic material F4-TCNQ form carrier transport ability and promote layer, carrier transport ability promotes layer
With a thickness of 42nm, the material of main part of hole transport functional layer is cavitation material NPB, and optical energy gap is 3.0 electron-volts, protection
Layer also uses cavitation material NPB, with a thickness of 12nm；This experimental subjects effectively can stop wavelength in the ultraviolet of 380nm-450nm
Line wave band is up to 45% or more；
Experimental result: experimental subjects and the photoelectric efficiency of reference object maintain an equal level；Other performance comparisons are as shown in table 1 below:
Analysis of experimental results: after having used technical scheme, the high-temperature operation life-span upgrading of OLED device
45%, 8 times of OLED device life-span upgrading under ultraviolet irradiation, hole mobility improves 2 orders of magnitude or more；This reality simultaneously
, it was also found that having used the OLED device of technical scheme in testing, the blue light wave that red shift to wavelength is about 470nm can be absorbed
Section, and wavelength can effectively be stopped, up to 50% or more, to effectively reduce ultraviolet in environment in the ultra-violet bands of 370nm-420nm
Light causes the influence of deterioration to device.
In above-mentioned experiment, it was also found that when the doped semiconductor materials in hole transport functional layer, hole transport functional layer
The optical energy gap of material is doped between 2.6-3.4 electron-volts, alternatively, the electronics doped with the semiconductor material passes
The optical energy gap of material is doped in transmission function layer between 2.6-3.4 electron-volts.This corresponding wavelength of range energy is about fallen
In 360-470 nanometer, that is, black light is fallen in the wave band of dark blue light, can so be further ensured that the electronics being doped passes
Transmission function layer or hole transport functional layer have the ability for absorbing 360-470nm or so wave band, namely further such that OLED device
Part itself has the optical ability of anti-high-energy.
It is found in the comparative experiments of thickness, with the increase of thickness, carrier transport ability promotes layer to ultraviolet light wave
The blocking rate of section is also being promoted.The overall thickness of OLED device functional layer will coincide optical design principle, that is, thickness is necessary
In particular range, dopant material is provided simultaneously with the function of absorbing light and promote transmission characteristic, according to basic law, doping half
The hole transport functional layer of conductor material and the more thick effective uptake of the thickness of electron-transport functional layer just will increase, while because
Also rise for the transmission characteristic of this layer, indicates that the relatively poor material thickness of other transmittabilities must continue reduction, therefore the layer is got over
It is more that thickness represents extinction amount, and transmittability improves, and the thickness for the electron-transport functional layer or hole transport functional layer being doped
When greater than 40nm, absorbing ability and transmittability have all obtained very big improvement.
Above-mentioned experimental result all illustrates that the technical solution of the application effectively improves service life and the stabilization of OLED device
Property.
Above description is only the preferred embodiment of the application and the explanation to institute's application technology principle.Those skilled in the art
Member is it should be appreciated that invention scope involved in the application, however it is not limited to technology made of the specific combination of above-mentioned technical characteristic
Scheme, while should also cover in the case where not departing from the inventive concept, it is carried out by above-mentioned technical characteristic or its equivalent feature
Any combination and the other technical solutions formed.Such as features described above has similar function with (but being not limited to) disclosed herein
Can technical characteristic replaced mutually and the technical solution that is formed.
Claims (9)
1. a kind of organic electroluminescence device, including luminescent layer and positioned at the hole transport functional layer and electricity of the luminescent layer two sides
Sub- transfer function layer, which is characterized in that
In the hole transport functional layer or the electron-transport functional layer of electroluminescent device light-emitting surface side
Doped with semiconductor material.
2. organic electroluminescence device according to claim 1, which is characterized in that the semiconductor material of the doping is to wave
Long range is that the blocking rate of the light in 350nm-450nm is more than or equal to 40%.
3. organic electroluminescence device according to claim 1, which is characterized in that the semiconductor material include metal,
Metal oxide, carbon materials, the organic material of high electron affinity or low free ability, high electron affinity or low free ability
At least one of organic metal misfit object.
4. organic electroluminescence device according to claim 1 or 2, which is characterized in that
It is more than or equal to 40nm doped with the thickness of the hole transport functional layer of the semiconductor material, alternatively,
It is more than or equal to 40nm doped with the thickness of the electron-transport functional layer of the semiconductor material.
5. according to claim 1 to organic electroluminescence device described in 3 any one, which is characterized in that the half of the doping
The volume percent range of conductor material is 2%-50%.
6. according to claim 1 to organic electroluminescence device described in 3 any one, which is characterized in that
Doped with being doped the optical energy gap of material in the hole transport functional layer of the semiconductor material between 2.6-3.4 electronics
Volt,
Alternatively,
Doped with being doped the optical energy gap of material between 2.6-3.4 in the electron-transport functional layer of the semiconductor material
Electron-volt.
7. according to claim 1 to organic electroluminescence device described in 3 any one, which is characterized in that
Doped between the hole transport functional layer and the luminescent layer of the semiconductor material be equipped with protective layer,
Alternatively,
Doped between the electron-transport functional layer and luminescent layer of the semiconductor material be equipped with protective layer.
8. organic electroluminescence device according to claim 7, which is characterized in that the carrier of material in the protective layer
Transmission characteristic,
With in the hole transport functional layer doped with the semiconductor material to be doped material consistent；
Or
With in the electron-transport functional layer doped with the semiconductor material to be doped material consistent.
9. organic electroluminescence device according to claim 8, which is characterized in that the thickness of the protective layer is more than or equal to
10nm。
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811398407.9A CN109473562A (en) | 2018-11-22 | 2018-11-22 | A kind of organic electroluminescence device |
| EP19834725.4A EP3751630A4 (en) | 2018-07-12 | 2019-07-10 | Organic electroluminescent device |
| PCT/CN2019/095436 WO2020011202A1 (en) | 2018-07-12 | 2019-07-10 | Organic electroluminescent device |
| US16/976,533 US11444267B2 (en) | 2018-07-12 | 2019-07-10 | Organic light emitting device |
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| CN201811398407.9A CN109473562A (en) | 2018-11-22 | 2018-11-22 | A kind of organic electroluminescence device |
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| WO2020011202A1 (en) * | 2018-07-12 | 2020-01-16 | 固安翌光科技有限公司 | Organic electroluminescent device |
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| CN1578561A (en) * | 2003-07-29 | 2005-02-09 | 三星Sdi株式会社 | Organic electroluminescent display device comprising ultraviolet light stabilizer |
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