CN106910843A - Blue-light-emitting OLED and preparation method thereof - Google Patents
Blue-light-emitting OLED and preparation method thereof Download PDFInfo
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- CN106910843A CN106910843A CN201710229697.3A CN201710229697A CN106910843A CN 106910843 A CN106910843 A CN 106910843A CN 201710229697 A CN201710229697 A CN 201710229697A CN 106910843 A CN106910843 A CN 106910843A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
Abstract
The invention discloses it is a kind of based on FIrpic as decorative layer blue light organic emissive device and preparation method, include substrate, anode, hole injection layer, hole transmission layer, luminescent layer, decorative layer, electron injecting layer and negative electrode successively, decorative layer is undoped FIrpic superthin layers.Phosphor material FIrpic is modified CBP by the present invention for functional layer first:The blue doping luminescent layers of FIrpic, greatly improve brightness, current density, power efficiency, the EQE of Nan dian Yao device, and preparation process is simple, low cost, luminescent material is applied into great novelty as functionalized modification layer, the device performance of gained is good, is with a wide range of applications.
Description
Technical field
The invention belongs to semiconductor display technology field, it is related to a kind of blue light of the ultra-thin decorative layer based on FIrpic organic
Light emitting diode and preparation method thereof.
Background technology
All the time, it is exactly vision that the mankind are used for obtaining most important in the perception of information.Into after the information age,
Increase with digital information explosion type, requirement of the people to display device is also stepped up.Put down for current of greatest concern
For panel display device, the black-and-white crystal electronic watch of limited numeral is only able to display from the beginning, gorgeous complexity can be showed till now
The large-scale curved high-definition display screen of picture, the continuous progress of human sciences's technology will be continued to develop with display is scientific and technological, and
Can be reflected in everywhere in people's life.
The characteristics of organic electroluminescence device (OrganicLight-EmittingDevice, OLED), is very distinct.With work as
Lower conventional liquid crystal display mode is different, and OLED is spontaneous luminous, and after plus appropriate voltage, carrier can directly exist device
Recombination luminescence in the luminescent layer of device, such spontaneous light characteristic not only solves that liquid crystal display is perishable, visible angle is small
Hard nut to crack, more causes that the display screen made using OLED technology no longer needs the photoswitch and backlight of complexity, allows lighter
The appearance of more thin display becomes possibility.Due to these advantages and characteristic, so display industry unanimously assert that OLED technology is worked as
To have nothing to be ashamed of be the bellwether for opening Display Technique of future generation.
It is fluorescent material that can be divided into the classes of two class mono- for the luminescent material in OLED, and a class is phosphor material.According to spin
Quantum statistics is theoretical, and the formation probability ratio of singlet excitons and triplet exciton is 1: 3 after electronics and hole-recombination, i.e. substance
State exciton only accounts for the 25% of " electron-hole pair ", and 75% " electron-hole pair " swashs due to foring the triplet of spin forbidden
Son is to " electroluminescent " without contribution.Therefore, the simple fluorescence luminescent material luminous by singlet excitons attenuation, its electricity
The maximum internal quantum efficiency of photoluminescence is 25%.Phosphor material can be realized being mixed with singlet state and triple by intersystem crossing
The luminous phosphorescent emissions of state.In theory, using the OLED internal quantum efficiencies of phosphor material making up to 100%, its luminous effect
Rate improves three times than fluorescent material.Late 1990s, the Forrest professors of Princeton university and University of Southern California
The cooperation of Thompson professors Liang Ge research groups, successfully using platinum-metalloporphyrin complex, Cyclometalated iridium-phenylpyridine
Complex is as phosphorescent coloring and charge transporting host material by the common method making organic electroluminescence device being deposited with
Luminescent layer, the external quantum efficiency of device respectively reaches 4% and 8%, is greatly improved relative to electrochromic fluorescent devices.Closely
Several years, the research based on heavy metal complex, particularly iridium complex electroluminescent phosphor material and device turned into current Organic Electricity
The focus of photoluminescence area research.Wherein, the multilayer OLED for being made as phosphor material by the use of complex of iridium, it is maximum
External quantum efficiency has reached 19.2%, and energy conversion efficiency is 72lm/W (65cd/m2).
The selection of modification layer material and thickness and concentration are one of principal elements of influence Organic Light Emitting Diode performance,
The selection of material, preparation method have vital influence on Organic Light Emitting Diode.FIrpic has high triplet energy level,
The advantages of low lumo energy, and easily cause triplet to be buried in oblivion in host-guest system, because appointing the right preparation technology that exists to answer
Miscellaneous, step is complicated, the problem that PE (power efficiency) and CE (current efficiency) and brightness cannot take into account simultaneously.
The content of the invention
It is an object of the invention to by the use of FIrpic as decorative layer, improve the CE (current efficiency) and PE (work(of device
Rate efficiency), realize high performance blue light organic emissive diode.For this provides a kind of ultra-thin decorative layer based on FIrpic
Blue light organic emissive diode preparation method.
The technical scheme is that:It is a kind of based on FIrpic as the blue light organic emissive device of decorative layer, wrap successively
Include substrate, anode, hole injection layer, hole transmission layer, luminescent layer, decorative layer, electron injecting layer and negative electrode, it is characterised in that
Modification layer material is Firpic, and luminescent layer is that material is CBP ︰ FIrpic.
Further, the thickness of Firpic material layers is 0.5nm.
Further, in luminescent layer, the doping of Firpic is 12%.
Further, hole injection layer material is MoO3。
Further, hole transmission layer is made up of NPB material layers and TCTA material layers.
Further, electron injecting layer material is TPBi.
Further, device architecture is:
Glass substrate/ITO/MoO3/NPB/TCTA/CBP:FIrpic/FIrpic/TPBi/Mg:Ag;Wherein, MoO3Thickness
It is 5nm to spend, and NPB thickness degree is 40nm, and TCTA thickness degree is 15nm, CBP:Firpic layers of thickness is 20nm, Firpic thickness
It is 0.5nm to spend, and TPBi thickness degree is 35nm.
It is a kind of based on FIrpic as the blue light organic emissive device of decorative layer preparation method, step is as follows:
(1) ito glass substrate is cleaned;
(2) method by vacuum evaporation on ito glass substrate prepares hole injection layer;
(3) method by vacuum evaporation on hole injection layer prepares hole transmission layer;
(4) device after step (3) treatment is put into organic vacuum cavity, room air pressure to be deposited is less than 3 × 10-4Pa,
WithEvaporation rate, with CBP as material of main part, FIrpic carries out mixing evaporation as guest emitting material, prepares luminous
Layer, after light emitting layer thickness reach it is predetermined after, then withEvaporation rate carry out the evaporation of FIrpic materials, prepare decorative layer,
Thickness degree to be finished reaches after making a reservation for and terminates evaporation;
(5) method by vacuum evaporation on decorative layer prepares electron injecting layer;
(6) method by vacuum evaporation on electron injecting layer prepares negative electrode.
Further, step is as follows:
(1) ito glass substrate is cleaned:A () sets ultrasonic instrument parameter:30 DEG C of temperature, time 15min, power 70w;(b)
Acetone is stained with non-dust cloth and wipes ito glass substrate surface, untill being observed visually without granule foreign;C () will clean dry
Net ito glass substrate is placed on teflon substrate frame, is carried out in the beaker of the deionized water for placing into dress detergent
The first step is cleaned by ultrasonic;D () takes out substrate frame, with to be placed into after acetone rinsing, carry out second step in the beaker equipped with acetone clear
Wash;E () carries out the ultrasonic cleaning of the 3rd step with deionized water to ito glass substrate, (f) takes out substrate frame, after being rinsed with isopropanol
Being put into the beaker equipped with isopropanol carries out the cleaning of the 4th step, and (g) is put into 20 minutes in baking box, the ito glass lining that (h) will be dried
Bottom is taken out, and is put into glass dish, is placed into and carry out in UV devices UV and irradiate 15 minutes;
(2) hole injection layer is prepared:Ito glass substrate after step (1) treatment is put into vacuum chamber, with MoO3As
Hole injection layer material;Room air pressure to be deposited is less than 1.8 × 10-3Pa, starts to rise to 20A to itself plus electric current, withEvaporation
Speed obtains the film that thickness is 5nm;
(3) hole transmission layer is prepared:Ito glass substrate after step (2) treatment is put into vacuum chamber, with NPB and
Used as hole transport layer material, room air pressure to be deposited is less than 3 × 10 to TCTA-4Pa, withEvaporation rate, treat that thickness reaches respectively
Reach after 40nm and 15nm, terminate evaporation;
(4) luminescent layer and decorative layer are prepared:Ito glass substrate after step (3) treatment is put into organic vacuum cavity,
Mixing evaporation is carried out as emitting layer material using CBP and FIrpic, room air pressure to be deposited is less than 3 × 10-4Pa, withEvaporation
Speed, after thickness reaches 20nm again withEvaporation rate carry out the evaporation of FIrpic materials, treat that thickness reaches
Terminate evaporation after 0.5nm;
(5) electron injecting layer is prepared:Ito glass substrate after step (4) treatment is put into organic vacuum cavity, with
Used as electron injecting layer, room air pressure to be deposited is less than 3 × 10 to TPBi materials-4Pa, withEvaporation rate, treat that thickness reaches
35nm terminates evaporation;
(6) metallic cathode is prepared:Ito glass substrate after step (5) treatment is put into metal vacuum deposition chamber, with Mg and
As metallic cathode, room air pressure to be deposited is less than 1.8 × 10 to Ag-3Pa, withEvaporation rate obtain thickness for 200nm
Metallic film.
In the present invention:
FIrpic refers to:Double (4,6- difluorophenyl pyridinatos-N, C2) pyridinecarboxylics close iridium;
CBP refers to:4,4- bis- (9- carbazoles) biphenyl 4,4';
TPBi refers to:1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene;
NPB refers to:N, N'- diphenyl-N, N'- (1- naphthyls) -1,1'- biphenyl -4,4'- diamines N, N';
TCTA refers to:(carbazole -9- bases) triphenylamines of 4,4', 4 "-three 4,4', 4 ";
The present invention has the following advantages that compared with prior art:
The present invention is individually first extremely of practical meaning as one layer of undoped decorative layer using phosphor material FIrpic
, phosphorescent light-emitting materials are greatly improved as decorative layer device electricity Liu Mi Du ﹑ current efficiency and power efficiency and
Brightness, significantly reduces experimental procedure and cost of manufacture.
Brief description of the drawings
Fig. 1 is the structural representation of blue light organic emissive device of the invention.
Fig. 2 is device architecture:Glass substrate/ITO/MoO3 (5nm)/NPB (40nm)/TCTA (15nm)/CBP:FIrpic
(25nm)/FIrpic(0.5nm)/TPBi(35nm)/Mg:The normalization light spectrogram of Ag.
Fig. 3 is device architecture:Glass substrate/ITO/MoO3 (5nm)/NPB (40nm)/TCTA (15nm)/CBP:FIrpic
(20nm)/FIrpic(0.5nm)/TPBi(35nm)/Mg:The voltage-current density curve map of Ag.
Fig. 4 is device architecture:Glass substrate/ITO/MoO3 (5nm)/NPB (40nm)/TCTA (15nm)/CBP:FIrpic
(20nm)/FIrpic(0.5nm)/TPBi(35nm)/Mg:The current density of Ag-current efficiency figure.
Specific embodiment
It is a kind of based on FIrpic as decorative layer blue light organic emissive device, successively including substrate, anode, hole injection
Layer, hole transmission layer, luminescent layer, decorative layer, electron injecting layer and negative electrode, decorative layer are Firpic material layers, and luminescent layer is material
Expect to be CBP ︰ FIrpic.Device of the invention is by the ultra-thin blue phosphorescent rhetorical function layer of one layer of the addition after the luminescent layer that adulterates
Greatly improve device efficiency.Preferably, the thickness of Firpic material layers is 0.5nm.In luminescent layer, the doping of Firpic
It is 12% (mass percent).Preferably, hole injection layer material is MoO3.Hole transmission layer is by NPB material layers and TCTA materials
The bed of material is constituted.Electron injecting layer material is TPBi.
Most preferably, device architecture is:
Glass substrate/ITO/MoO3/NPB/TCTA/CBP:FIrpic/FIrpic/TPBi/Mg:Ag;Wherein, MoO3Thickness
It is 5nm to spend, and NPB thickness degree is 40nm, and TCTA thickness degree is 15nm, CBP:Firpic layers of thickness is 20nm, Firpic thickness
It is 0.5nm to spend, and TPBi thickness degree is 35nm.
It is a kind of based on FIrpic as the blue light organic emissive device of decorative layer preparation method, step is as follows:
(1) ito glass substrate is cleaned;
(2) method by vacuum evaporation on ito glass substrate prepares hole injection layer;
(3) method by vacuum evaporation on hole injection layer prepares hole transmission layer;
(4) device after step (3) treatment is put into organic vacuum cavity, room air pressure to be deposited is less than 3 × 10-4Pa,
WithEvaporation rate, with CBP as material of main part, FIrpic carries out mixing evaporation as guest emitting material, prepares luminous
Layer, after light emitting layer thickness reach it is predetermined after, then withEvaporation rate carry out the evaporation of FIrpic materials, prepare decorative layer,
Thickness degree to be finished reaches after making a reservation for and terminates evaporation;
(5) method by vacuum evaporation on decorative layer prepares electron injecting layer;
(6) method by vacuum evaporation on electron injecting layer prepares negative electrode.
Embodiment 1
As shown in figure 1, it is a kind of based on FIrpic as decorative layer blue light organic emissive device, successively including substrate, sun
Pole, hole injection layer, hole transmission layer, luminescent layer, decorative layer, electron injecting layer and negative electrode, the luminescent layer is by material of main part
Formed with guest materials doping, decorative layer is FIrpic.
Concrete structure is:Glass substrate/ITO/MoO3 (5nm)/NPB (40nm)/TCTA (15nm)/CBP:FIrpic
(20nm)/FIrpic(0.5nm)/TPBi(35nm)/Mg:Ag。
Preparation method is:
(1) ito glass substrate is cleaned:A () sets ultrasonic instrument parameter:30 DEG C of temperature, time 15min, power 70w;(b)
Acetone is stained with non-dust cloth and wipes ito glass substrate surface, untill being observed visually without granule foreign;C () will clean dry
Net ito glass substrate is placed on teflon substrate frame, is carried out in the beaker of the deionized water for placing into dress detergent
The first step is cleaned by ultrasonic;D () takes out substrate frame, with to be placed into after acetone rinsing, carry out second step in the beaker equipped with acetone clear
Wash;E () carries out the ultrasonic cleaning of the 3rd step with deionized water to ito glass substrate, (f) takes out substrate frame, after being rinsed with isopropanol
Being put into the beaker equipped with isopropanol carries out the cleaning of the 4th step, and (g) is put into 20 minutes in baking box, the ito glass lining that (h) will be dried
Bottom is taken out, and is put into glass dish, is placed into and carry out in UV devices UV and irradiate 15 minutes;
(2) hole injection layer is prepared:Ito glass substrate after step (1) treatment is put into vacuum chamber, with MoO3As
Hole injection layer material;Room air pressure to be deposited is less than 1.8 × 10-3Pa, starts to rise to 20A to itself plus electric current, withEvaporation
Speed obtains the film that thickness is 5nm;
(3) hole transmission layer is prepared:Ito glass substrate after step (2) treatment is put into vacuum chamber, with NPB and
Used as hole transport layer material, room air pressure to be deposited is less than 3 × 10 to TCTA-4Pa, withEvaporation rate, treat that thickness reaches respectively
Reach after 40nm and 15nm, terminate evaporation;
(4) luminescent layer and decorative layer are prepared:Ito glass substrate after step (3) treatment is put into organic vacuum cavity,
Mixing evaporation is carried out as emitting layer material using CBP and FIrpic, room air pressure to be deposited is less than 3 × 10-4Pa, withEvaporation
Speed, after thickness reaches 20nm again withEvaporation rate carry out the evaporation of FIrpic materials, treat that thickness reaches
Terminate evaporation after 0.5nm;
(5) electron injecting layer is prepared:Ito glass substrate after step (4) treatment is put into organic vacuum cavity, with
Used as electron injecting layer, room air pressure to be deposited is less than 3 × 10 to TPBi materials-4Pa, withEvaporation rate, treat that thickness reaches
35nm terminates evaporation.
(6) metallic cathode is prepared:Ito glass substrate after step (5) treatment is put into metal vacuum deposition chamber, with Mg and
As metallic cathode, room air pressure to be deposited is less than 1.8 × 10 to Ag-3Pa, withEvaporation rate obtain thickness for 200nm
Metallic film.
Embodiment described above only expresses the specific embodiment of the application, and its description is more specific and detailed, but simultaneously
Therefore the limitation to the application protection domain can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, on the premise of technical scheme design is not departed from, various modifications and improvements can be made, these belong to this
The protection domain of application.
Claims (9)
1. it is a kind of based on FIrpic as decorative layer blue light organic emissive device, successively including substrate, anode, hole injection
Layer, hole transmission layer, luminescent layer, decorative layer, electron injecting layer and negative electrode, it is characterised in that modification layer material is Firpic, hair
Photosphere is that material is CBP ︰ FIrpic.
2. it is according to claim 1 it is a kind of based on FIrpic as decorative layer blue light organic emissive device, its feature exists
In the thickness of Firpic material layers is 0.5nm.
3. it is according to claim 1 it is a kind of based on FIrpic as decorative layer blue light organic emissive device, its feature exists
In in luminescent layer, the doping of Firpic is 12%.
4. it is according to claim 1 it is a kind of based on FIrpic as decorative layer blue light organic emissive device, its feature exists
In hole injection layer material is MoO3。
5. it is according to claim 1 it is a kind of based on FIrpic as decorative layer blue light organic emissive device, its feature exists
In hole transmission layer is made up of NPB material layers and TCTA material layers.
6. it is according to claim 1 it is a kind of based on FIrpic as decorative layer blue light organic emissive device, its feature exists
In electron injecting layer material is TPBi.
7. according to claim any one of 1-6 it is a kind of based on FIrpic as decorative layer blue light organic emissive device,
Characterized in that, device architecture is:Glass substrate/ITO/MoO3/NPB/TCTA/CBP:FIrpic/FIrpic/TPBi/Mg:
Ag;Wherein, MoO3Thickness degree is 5nm, and NPB thickness degree is 40nm, and TCTA thickness degree is 15nm, CBP:Firpic layers of thickness is
20nm, Firpic thickness degree are 0.5nm, and TPBi thickness degree is 35nm.
8. a kind of according to claim any one of 1-6 based on FIrpic as the blue light organic emissive device of decorative layer
Preparation method, it is characterised in that step is as follows:
(1) ito glass substrate is cleaned;
(2) method by vacuum evaporation on ito glass substrate prepares hole injection layer;
(3) method by vacuum evaporation on hole injection layer prepares hole transmission layer;
(4) device after step (3) treatment is put into organic vacuum cavity, room air pressure to be deposited is less than 3 × 10-4Pa, withEvaporation rate, with CBP as material of main part, FIrpic carries out mixing evaporation as guest emitting material, prepares luminous
Layer, after light emitting layer thickness reach it is predetermined after, then withEvaporation rate carry out the evaporation of FIrpic materials, prepare decorative layer,
Thickness degree to be finished reaches after making a reservation for and terminates evaporation;
(5) method by vacuum evaporation on decorative layer prepares electron injecting layer;
(6) method by vacuum evaporation on electron injecting layer prepares negative electrode.
9. it is according to claim 8 it is a kind of based on FIrpic as the blue light organic emissive device of decorative layer preparation side
Method, it is characterised in that step is as follows:
(1) ito glass substrate is cleaned:A () sets ultrasonic instrument parameter:30 DEG C of temperature, time 15min, power 70w;B () uses nothing
Dirt cloth is stained with acetone and wipes ito glass substrate surface, untill being observed visually without granule foreign;C () will scrub
Ito glass substrate is placed on teflon substrate frame, and first is carried out in the beaker of the deionized water for placing into dress detergent
Step is cleaned by ultrasonic;D () takes out substrate frame, carry out second step in the beaker equipped with acetone and cleaned with being placed into after acetone rinsing;(e)
The ultrasonic cleaning of the 3rd step is carried out to ito glass substrate with deionized water, (f) takes out substrate frame, dress is put into after being rinsed with isopropanol
The beaker for having isopropanol carries out the cleaning of the 4th step, and (g) is put into 20 minutes in baking box, and (h) takes the ito glass substrate of drying
Go out, be put into glass dish, place into and carry out in UV devices UV and irradiate 15 minutes;
(2) hole injection layer is prepared:Ito glass substrate after step (1) treatment is put into vacuum chamber, with MoO3As hole
Injection layer material;Room air pressure to be deposited is less than 1.8 × 10-3Pa, starts to rise to 20A to itself plus electric current, withEvaporation rate
Obtain the film that thickness is 5nm;
(3) hole transmission layer is prepared:Ito glass substrate after step (2) treatment is put into vacuum chamber, is made with NPB and TCTA
It is hole transport layer material, room air pressure to be deposited is less than 3 × 10-4Pa, withEvaporation rate, treat that thickness is respectively reached and reach
After 40nm and 15nm, terminate evaporation;
(4) luminescent layer and decorative layer are prepared:Ito glass substrate after step (3) treatment is put into organic vacuum cavity, with
CBP and FIrpic carries out mixing evaporation as emitting layer material, and room air pressure to be deposited is less than 3 × 10-4Pa, withEvaporation speed
Rate, after thickness reaches 20nm again withEvaporation rate carry out the evaporation of FIrpic materials, treat that thickness reaches 0.5nm
After terminate evaporation;
(5) electron injecting layer is prepared:Ito glass substrate after step (4) treatment is put into organic vacuum cavity, with TPBi materials
Used as electron injecting layer, room air pressure to be deposited is less than 3 × 10 to material-4Pa, withEvaporation rate, treat that thickness reaches 35nm and terminates
Evaporation;
(6) metallic cathode is prepared:Ito glass substrate after step (5) treatment is put into metal vacuum deposition chamber, is done with Mg and Ag
It is metallic cathode, room air pressure to be deposited is less than 1.8 × 10-3Pa, withEvaporation rate obtain thickness be 200nm metal
Film.
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CN110085765A (en) * | 2019-04-28 | 2019-08-02 | 深圳市华星光电半导体显示技术有限公司 | Display panel and preparation method thereof |
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CN110085765A (en) * | 2019-04-28 | 2019-08-02 | 深圳市华星光电半导体显示技术有限公司 | Display panel and preparation method thereof |
CN110085765B (en) * | 2019-04-28 | 2021-08-24 | 深圳市华星光电半导体显示技术有限公司 | Display panel and manufacturing method thereof |
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