CN104124347A - Flexible organic electroluminescent device and preparation method thereof - Google Patents
Flexible organic electroluminescent device and preparation method thereof Download PDFInfo
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- CN104124347A CN104124347A CN201310157825.XA CN201310157825A CN104124347A CN 104124347 A CN104124347 A CN 104124347A CN 201310157825 A CN201310157825 A CN 201310157825A CN 104124347 A CN104124347 A CN 104124347A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/841—Self-supporting sealing arrangements
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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
- H10K71/80—Manufacture or treatment specially adapted for the organic devices covered by this subclass using temporary substrates
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
- H10K77/111—Flexible substrates
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/311—Flexible OLED
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a flexible organic electroluminescent device. The flexible organic electroluminescent device comprises a polyimide film, a barrier layer, an anode, a luminescent layer and a cathode, all of which are orderly stacked on each other; the barrier layer comprises a first barrier film and a second barrier film formed on the surface of the first barrier film; the first barrier film is made of silicon dioxide, while the second barrier film is made of silicon nitride; the organic electroluminescent device further comprises an encapsulation cover for encapsulating the anode, the luminescent layer and the cathode on the barrier layer; the encapsulation cover comprises a silicon dioxide film and a silicon nitride film stacked on the surface of the silicon dioxide film. The flexible organic electroluminescent device is excellent in stability. The invention also provides a preparation method of the flexible organic electroluminescent device.
Description
Technical field
The present invention relates to a kind of flexible organic electroluminescent device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) is used ultra-thin glass conventionally, thin polymer film, sheet metal etc. are as flexible polyimide film, than more frivolous, the more impact-resistant advantage of having of glass polyimide film, and the preparation of flexible device can adopt volume to volume mode to produce, thereby reduces manufacturing cost significantly.
Flexible substrate mainly contains ultra-thin glass, sheet metal etc. at present.For flexible light and demonstration, for curling property, curling such as small curve, is wound around, and requires backing material thinner, and has extraordinary crimp property.But when substrate, cross when thin, its mechanical strength is lower, and in the technical process of preparation OLED, because the mechanical strength of substrate is lower, under higher temperature, it easily deforms, and makes surface irregularity, makes the life-span of organic electroluminescence device shorter.
Summary of the invention
Based on this, be necessary to provide longer flexible organic electroluminescent device of a kind of life-span and preparation method thereof.
A kind of flexible organic electroluminescent device, comprise the polyimide film, barrier layer, anode, luminescent layer and the negative electrode that stack gradually, described barrier layer comprises the first block film and is formed at second block film on the first block film surface, the material of described the first block film is silicon dioxide, and the material of described the second block film is silicon nitride;
Described organic electroluminescence device also comprises cap, and described cap is packaged in described anode, luminescent layer and negative electrode on described barrier layer, and described cap comprises silica membrane and is laminated in the silicon nitride film on described silica membrane surface.
In an embodiment, the thickness of described the first block film is 50nm～100nm therein, and the thickness of described the second block film is 50nm～100nm.
Therein in an embodiment, the material of described anode is at least two kinds of formation in silver, gold and aluminium closes gold, silver, gold or aluminium.
In an embodiment, the thickness of described polyimide film is 20 μ m～100 μ m therein.
In an embodiment, the number of plies of the first block film described in described barrier layer and described the second block film is 1～3 therein, and described the first block film and described the second block film are alternately laminated.
In an embodiment, described in described cap, the number of plies of silica membrane and described silicon nitride film is 1～3 therein, and described silica membrane and described silicon nitride film are alternately laminated.
A preparation method for flexible organic electroluminescent device, comprises the following steps:
At rigid substrates surface spin coating polyamic acid solution, form Polyamic Acid Film;
Under vacuum environment, the Polyamic Acid Film on described stiff base and described rigid substrates surface is heated to 200 ℃～350 ℃ and carries out processed, make described Polyamic Acid Film dehydration form polyimide film;
At described polyimide film surface sputtering, prepare barrier layer, described barrier layer comprises the first block film and is formed at second block film on the first block film surface, the material of described the first block film is silicon dioxide, and the material of described the second block film is silicon nitride;
Surface on described barrier layer is prepared anode, luminescent layer and negative electrode successively;
At described cathode surface, prepare cap, described cap is packaged in described anode, luminescent layer and negative electrode on described barrier layer, and described cap comprises silica membrane and is laminated in the silicon nitride film on described silica membrane surface; And
By described polyimide film from described rigid substrates sur-face peeling.
Therein in an embodiment, described polyamic acid solution is prepared by following steps: by 4,4 ' diaminodiphenyl ether adds in organic solvent and is mixed with 4,4 ' diaminodiphenyl ether solution, described organic solvent is selected from N, N '-dimethyl formamide, N, at least one in N '-dimethylacetylamide, 1-METHYLPYRROLIDONE and oxolane; Pyromellitic acid anhydride is added to 4,4, and ' diaminodiphenyl ether solution, stirs and within 1 hour～2 hours, forms polyamic acid solution, and wherein 4,4 ' mol ratio of diaminodiphenyl ether and pyromellitic acid anhydride is 1:0.8～1.2.
Therein in an embodiment, described 4,4 ' in diaminodiphenyl ether solution, 4,4 ' mass concentration of diaminodiphenyl ether is 5%～15%; The preparation of described polyamic acid solution also comprises step: to adding described organic solvent to regulate the mass concentration of polyamic acid in described polyamic acid solution in described polyamic acid solution, be 5%～20%.
In an embodiment, the time of described processed is 5 hours～10 hours therein.
Above-mentioned flexible organic electroluminescent device and preparation method thereof, polyimide film has good pliability as substrate, and crimp property is very excellent; Polyimide film resistance to elevated temperatures is good simultaneously, not yielding under high temperature; Between polyimide film and anode, barrier layer is set, barrier layer comprises the first block film and is formed at second block film on the first block film surface, the first block film and the second block film can play the effect of block water oxygen infiltration, improve life-span and the stability of flexible organic electroluminescent device; Cap can play the effect that intercepts water oxygen, further increases life-span and the stability of flexible organic electroluminescent device; By preparing polyimide film as substrate on stiff base surface, in preparation process, there is stiff base to support, in preparation process, the surface smoothness of organic electroluminescence device is good, is difficult for deforming.
Accompanying drawing explanation
Fig. 1 is the structural representation of the flexible organic electroluminescent device of an execution mode;
Fig. 2 is preparation method's the flow chart of the flexible organic electroluminescent device of an execution mode.
Embodiment
Below in conjunction with the drawings and specific embodiments, flexible organic electroluminescent device and preparation method thereof is further illustrated.
Refer to Fig. 1, the flexible organic electroluminescent device 100 of an execution mode comprises polyimide film 10, barrier layer 20, anode 30, hole injection layer 40, hole transmission layer 50, luminescent layer 60, electron transfer layer 70, electron injecting layer 80, negative electrode 85 and the cap 90 stacking gradually.
The thickness 20 μ m～100 μ m of the material of polyimide film 10.。
Barrier layer 20 comprises the first block film 22 and is formed at second block film 24 on the first block film 22 surfaces.The material of the first block film 22 is silicon dioxide (SiO
2).The thickness of the first block film is 50nm～100nm.The material of the second block film 24 is silicon nitride (Si
3n
4).The thickness of the second block film 24 is 50nm～100nm.
Further, in barrier layer 20, the number of plies of the first block film 22 and the second block film 24 is 1～3, the first block film 22 and the second block film 24 are alternately laminated, form the structure as the first block film 22/ second block film 24/ first block film 22/ second block film 24/ first block film 22/ second block film 24....The thickness on barrier layer 20 is 150nm～300nm.
Anode 30 is formed at 20 surfaces, barrier layer.The material of anode 30 is at least two kinds of formation in silver (Ag), gold (Au) and aluminium (Al) closes gold, silver (Ag), gold (Au) or aluminium (Al).The thickness of anode 30 is 70nm～200nm.
Hole injection layer 40 is formed at anode 30 surfaces.The material of hole injection layer 40 is selected from least one in CuPc (CuPc), Phthalocyanine Zinc (ZnPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc) and phthalocyanine platinum (PtPc).The thickness of hole injection layer 40 is 20nm～40nm.
Hole transmission layer 50 is formed at hole injection layer 40 surfaces.The material of hole transmission layer 50 is selected from 4,4', 4''-tri-(2-naphthyl phenyl amino) triphenylamine (2-TNATA), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines (TPD), 4,4', a kind of in 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of hole transmission layer 50 is 20nm～40nm.
Luminescent layer 60 is formed at the surface of hole transmission layer 50.The material of luminescent layer 60 is that guest materials is entrained in mixture or the fluorescent material forming in material of main part.Guest materials is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic), two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ) 2 (acac)), three (1-phenyl-isoquinolin) close iridium (Ir (piq) 3) and three (2-phenylpyridines) close at least one in iridium (Ir (ppy) 3).Material of main part is selected from 4,4'-bis-(9-carbazole) biphenyl (CBP), oxine aluminium (Alq
3), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, at least one in 4'-diamines (NPB).The mass ratio of guest materials and material of main part is 1:100～10:100.Fluorescent material is selected from 4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl (DPVBi), 4,4'-two [4-(di-p-tolyl is amino) styryl] biphenyl (DPAVBi) and 5,6, at least one in 11,12-tetraphenyl naphthonaphthalene (Rubrene).The thickness of luminescent layer 60 is 1nm～20nm.
Electron transfer layer 70 is formed at the surface of luminescent layer 60.The material of electron transfer layer 70 is selected from 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP) and 1, at least one in 2,4-triazole derivative (TAZ).The thickness of electron transfer layer 70 is 20nm～40nm.
Electron injecting layer 80 is formed at the surface of electron transfer layer 70.The material of electron injecting layer 80 is selected from least one in lithium fluoride (LiF) and cesium fluoride (CsF).The thickness of electron injecting layer 80 is 0.5nm～1nm.
Negative electrode 85 is formed at electron injecting layer 80 surfaces.The material of negative electrode 85 is silver (Ag), aluminium (Al), samarium (Sm) or ytterbium (Yb).The thickness of negative electrode 85 is 15nm～35nm.
Cap 90 is covered on negative electrode 85, and anode 30, hole injection layer 40, hole transmission layer 50, luminescent layer 60, electron transfer layer 70, electron injecting layer 80 and negative electrode 85 are packaged in to 20 surfaces, barrier layer.Cap 90 is formed with host cavity 95.Cap 90 is covered on negative electrode 85 surfaces and anode 30, hole injection layer 40, hole transmission layer 50, luminescent layer 60, electron transfer layer 70, electron injecting layer 80 and negative electrode 85 is contained in to host cavity 95.Cap 90 comprises silicon dioxide (SiO
2) film 97 and be laminated in the silicon nitride (Si on silica membrane 97 surfaces
3n
4) film 98.Further, cap 90 comprises 1～3 silica membrane 97 and 1～3 silicon nitride film 98, silica membrane 97 is alternately laminated with silicon nitride film 98, forms silica membrane 97/ silicon nitride film 98/ silica membrane 97/ silicon nitride film 98 ... structure.The thickness of silica membrane 97 is 50nm～100nm, and the thickness of silicon nitride film 98 is 50nm～100nm.The thickness of cap 90 is 150nm～300nm.
Above-mentioned flexible organic electroluminescent device 100, polyimide film 10 has good pliability as substrate, and crimp property is very excellent; Polyimide film 10 resistances to elevated temperatures are good simultaneously, not yielding under high temperature; Between polyimide film 10 and anode 30, barrier layer 20 is set, barrier layer 20 comprises the first block film 22 and is formed at second block film 24 on the first block film 22 surfaces, the first block film 22 and the second block film 24 can play the effect of block water oxygen infiltration, improve life-span and the stability of flexible organic electroluminescent device; Cap 90 can play the effect that intercepts water oxygen, further increases life-span and the stability of flexible organic electroluminescent device.
It should be noted that, one or more in hole injection layer 40, hole transmission layer 50, electron transfer layer 70, electron injecting layer 80 can omit, and other functional layers can certainly be set as required in flexible organic electroluminescent device 100.
Please refer to Fig. 2, the preparation method of the flexible organic electroluminescent device 100 of an execution mode, comprises the following steps:
Step S110, at rigid substrates surface spin coating polyamic acid solution, form Polyamic Acid Film.
The material of rigid substrates can be glass, metal or polymer, only otherwise possess flexibility or flexibility is poor.
In present embodiment, rigid substrates first carries out pre-treatment before use, and pre-treatment comprises: rigid substrates is placed in the deionized water that contains washing agent and carries out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen.
Polyamic acid solution is prepared by following steps:
Step S111, ' diaminodiphenyl ether (ODA) adds and in organic solvent, is mixed with 4,4 ' diaminodiphenyl ether solution by 4,4.Organic solvent is selected from N, N '-dimethyl formamide (DMF), N, at least one in N '-dimethylacetylamide (DMAc), 1-METHYLPYRROLIDONE (NMP) and oxolane (THF).
Preferably, 4,4 ' in diaminodiphenyl ether solution, 4,4 ' mass concentration of diaminodiphenyl ether is 5%～15%.
Preferably, in reactor, prepare 4,4 ' diaminodiphenyl ether solution.
Step S112, pyromellitic acid anhydride (PMDA) is added to 4,4, and ' diaminodiphenyl ether solution, stirs and within 1 hour～2 hours, forms polyamic acid solution, and wherein 4,4 ' mol ratio of diaminodiphenyl ether and pyromellitic acid anhydride is 1:0.8～1.2.
Step S113, to adding in polyamic acid solution organic solvent to regulate the mass concentration of polyamic acid in polyamic acid solution, be 5%～20%.
The organic solvent adding in this step is in step S111, to prepare 4, the 4 ' organic solvents that diaminodiphenyl ether solution is used.
Step S120, under vacuum environment, the Polyamic Acid Film on stiff base and rigid substrates surface is heated to 200 ℃～350 ℃ and carries out processed, make Polyamic Acid Film dehydration form polyimide film.
Preferably, the time of processed is 5 hours～10 hours.
Step S130, on preparation barrier layers 20, polyimide film 10 surface.
Barrier layer 20 comprises the first block film 22 and is formed at second block film 24 on the first block film 22 surfaces.The material of the first block film 22 is silicon dioxide (SiO
2).The thickness of the first block film is 50nm～100nm.The material of the second block film 24 is silicon nitride (Si
3n
4).The thickness of the second block film 24 is 50nm～100nm.
The first block film 22 and the second block film 24 are prepared by magnetron sputtering.
Further, in barrier layer 20, the number of plies of the first block film 22 and the second block film 24 is 1～3, the first block film 22 and the second block film 24 are alternately laminated, form as the first block film 22/ second block film 24/ first block film 22/ second block film 24/ first block film 22/ second block film 24 ... structure.The thickness on barrier layer 20 is 150nm～300nm.
In present embodiment, magnetic control sputtering plating prepares the first block film 22 and the second block film 24 carries out in vacuum coating system, and vacuum degree is 1 * 10
-3pa～1 * 10
-5pa.
Further, in barrier layer 20, the number of plies of the first block film 22 and the second block film 24 is 3～6 layers, the first block film 22 and the second block film 24 are alternately laminated, form as the first block film 22/ second block film 24/ first block film 22/ second block film 24/ first block film 22/ second block film 24 ... structure.Thereby the first block film 22 between two the second block films 24 can absorb the stress of the second block film 24 generations avoids the second block film 24 crackings.
Step S140, on barrier layer, 20 surface is prepared anode 30, hole injection layer 40, hole transmission layer 50, luminescent layer 60, electron transfer layer 70, electron injecting layer 80 and negative electrode 85 successively.
Anode 30 is formed at 20 surfaces, barrier layer.The material of anode 30 is at least two kinds of formation in silver (Ag), gold (Au) and aluminium (Al) closes gold, silver (Ag), gold (Au) or aluminium (Al).The thickness of anode 30 is 70nm～200nm.Anode 30 is prepared by evaporation, and evaporation is 1 * 10 at vacuum pressure
-3pa～1 * 10
-5under Pa, carry out, evaporation speed is 0.2nm/s～2nm/s.In present embodiment, anode 30 is positioned at middle part and covering barrier layer 20 part surfaces on barrier layer 20.
Hole injection layer 40 is formed at anode 30 surfaces.The material of hole injection layer 40 is selected from least one in CuPc (CuPc), Phthalocyanine Zinc (ZnPc), ranadylic phthalocyanine (VOPc), TiOPc (TiOPc) and phthalocyanine platinum (PtPc).The thickness of hole injection layer 40 is 20nm～40nm.Hole injection layer 40 is prepared by evaporation, and evaporation is 1 * 10 at vacuum pressure
-3pa～1 * 10
-5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
Hole transmission layer 50 is formed at hole injection layer 40 surfaces.The material of hole transmission layer 50 is selected from 4,4', 4''-tri-(2-naphthyl phenyl amino) triphenylamine (2-TNATA), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines (TPD), 4,4', a kind of in 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of hole transmission layer 50 is 20nm～40nm.Hole transmission layer 50 is prepared by evaporation, and evaporation is 1 * 10 at vacuum pressure
-3pa～1 * 10
-5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
Luminescent layer 60 is formed at the surface of hole transmission layer 50.The material of luminescent layer 60 is that guest materials is entrained in mixture or the fluorescent material forming in material of main part.Guest materials is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic), two (4,6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ) 2 (acac)), three (1-phenyl-isoquinolin) close iridium (Ir (piq) 3) and three (2-phenylpyridines) close at least one in iridium (Ir (ppy) 3).Material of main part is selected from 4,4'-bis-(9-carbazole) biphenyl (CBP), oxine aluminium (Alq
3), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, at least one in 4'-diamines (NPB).The mass ratio of guest materials and material of main part is 1:100～10:100.Fluorescent material is selected from 4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl (DPVBi), 4,4'-two [4-(di-p-tolyl is amino) styryl] biphenyl (DPAVBi) and 5,6, at least one in 11,12-tetraphenyl naphthonaphthalene (Rubrene).The thickness of luminescent layer 60 is 1nm～20nm.Luminescent layer 60 is prepared by evaporation, and evaporation is 1 * 10 at vacuum pressure
-3pa～1 * 10
-5under Pa, carry out, evaporation speed is 0.01nm/s～1nm/s.
Electron transfer layer 70 is formed at the surface of luminescent layer 60.The material of electron transfer layer 70 is selected from 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole (PBD), 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP) and 1, at least one in 2,4-triazole derivative (TAZ).The thickness of electron transfer layer 70 is 20nm～40nm.Electron transfer layer 70 is prepared by evaporation, and evaporation is 1 * 10 at vacuum pressure
-3pa～1 * 10
-5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
Electron injecting layer 80 is formed at the surface of electron transfer layer 70.The material of electron injecting layer 80 is selected from least one in lithium fluoride (LiF) and cesium fluoride (CsF).The thickness of electron injecting layer 80 is 0.5nm～1nm.Electron injecting layer 80 is prepared by evaporation, and evaporation is 1 * 10 at vacuum pressure
-3pa～1 * 10
-5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
Negative electrode 85 is formed at electron injecting layer 80 surfaces.The material of negative electrode 85 is silver (Ag), aluminium (Al), samarium (Sm) or ytterbium (Yb).The thickness of negative electrode 85 is 15nm～35nm.Negative electrode 85 is prepared by evaporation, and evaporation is 1 * 10 at vacuum pressure
-3pa～1 * 10
-5under Pa, carry out, evaporation speed is 0.2nm/s～2nm/s.
Step S150, on negative electrode 85 surfaces, prepare cap 90, cap 90 is packaged in anode 30, hole injection layer 40, hole transmission layer 50, luminescent layer 60, electron transfer layer 70, electron injecting layer 80 and negative electrode 85 on barrier layer 20, and cap 90 comprises silica membrane 97 and is laminated in the silicon nitride film 98 on silica membrane 97 surfaces.
Cap 90 is formed with host cavity 95.Cap 90 is covered on negative electrode 85 surfaces and anode 30, hole injection layer 40, hole transmission layer 50, luminescent layer 60, electron transfer layer 70, electron injecting layer 80 and negative electrode 85 is contained in to host cavity 95.Cap 90 comprises silicon dioxide (SiO
2) film 97 and be laminated in the silicon nitride (Si on silica membrane 97 surfaces
3n
4) film 98.Further, cap 90 comprises 1～3 silica membrane 97 and 1～3 silicon nitride film 98, silica membrane 97 is alternately laminated with silicon nitride film 98, forms silica membrane 97/ silicon nitride film 98/ silica membrane 97/ silicon nitride film 98 ... structure.The thickness of silica membrane 97 is 50nm～100nm, and the thickness of silicon nitride film 98 is 50nm～100nm.The thickness of cap 90 is 150nm～300nm.
In present embodiment, silica membrane 97 and silicon nitride film 98 be magnetic control sputtering plating preparation in vacuum coating system, and vacuum degree is 1 * 10
-3pa～1 * 10
-5pa.
Step S150, by polyimide film 10 from rigid substrates sur-face peeling.
Polyimide film 10, from rigid substrates sur-face peeling, is formed to curling organic electroluminescence device.In present embodiment, strip operation is mechanical stripping.
The preparation method of above-mentioned flexible organic electroluminescent device, operates comparatively simple.
Below in conjunction with specific embodiment, the preparation method of flexible organic electroluminescent device provided by the invention is elaborated.
The preparation used of the embodiment of the present invention and comparative example and tester are: test is high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd) with Preparation equipment, the USB4000 fiber spectrometer testing electroluminescent spectrum of U.S. marine optics Ocean Optics, the Keithley2400 test electric property of U.S. Keithley company, CS-100A colorimeter test brightness and the colourity of Japanese Konica Minolta company.
Embodiment 1
Flexible organic electroluminescent device structure is polyimide film/barrier layer/Ag (100nm)/ZnPc (20nm)/NPB (30nm)/(Ir (ppy)
3: CBP (10%, 10nm)/Bphen (30nm)/LiF (1nm)/Ag (25nm), its making step comprises following:
Step 1, provide rigid substrates, be placed in the deionized water that contains washing agent and carry out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen.
Step 2, in the reactor with heater, add solvent and 4,4 ' diaminodiphenyl ether (ODA), solvent for use is N, N '-dimethyl formamide (DMF), the mass percent that makes ODA is 5%; After treating ODA agitating solution, add pyromellitic acid anhydride (PMDA), the mol ratio that makes ODA and PMDA is 1:1, then stirs 2 hours, forms polyamic acid solution; After completion of the reaction, by polyamic acid solution N, N '-dimethyl formamide (DMF) dilutes, and the mass percent that makes polyamic acid is 5%; The solution of polyamic acid is covered to rigid substrates surface by spin coating, and the rotating speed of spin coating is 2500 revs/min; After spin coating, substrate is transferred in vacuum drying chamber, is heated to 200 ℃, react processed 5 hours, make polyamic acid dehydration form polyimide film, the thickness of final film forming is 20 μ m.
Step 3, in vacuum degree, be 1 * 10
-4in Pa vacuum coating system, barrier layer is prepared in sputter, and the structure on the barrier layer of formation is SiO
2(50nm)/Si
3n
4(50nm)/SiO
2(50nm)/Si
3n
4(50nm)/SiO
2(50nm)/Si
3n
4(50nm), gross thickness is 300nm.
Step 4, in vacuum degree, be 1 * 10
-4in the vacuum coating system of Pa, on the surface on barrier layer, evaporation is prepared anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, and the material of anode is Ag, and thickness is 100nm, and evaporation speed is 0.2nm/s; The material of hole injection layer is ZnPc, and thickness is 20nm, and evaporation speed is 0.1nm/s; The material of hole transmission layer is NPB, and thickness is 30nm, and evaporation speed is 0.1nm/s; The material of luminescent layer comprises CBP and is entrained in the Ir (ppy) in CBP
3, Ir (ppy)
3with the mass ratio of CBP be 10:100, thickness is 10nm, the evaporation speed of CBP is 1nm/s, Ir (ppy)
3evaporation speed be 0.1nm/s; The material of electron transfer layer is Bphen, and thickness is 30nm, and evaporation speed is 0.1nm/s; The material of electron injecting layer is LiF, and thickness is 1nm, and evaporation speed is 1nm/s; The material of negative electrode is Ag, and thickness is 25nm, and evaporation speed is 0.2nm/s.
Step 5, utilize thin-film package technique, in cathode surface sputter, prepare cap, cap is packaged in anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode on barrier layer, cap comprises silica membrane and is laminated in the silicon nitride film on silica membrane surface, and sputtering at vacuum degree is 1 * 10
-4in the vacuum coating system of Pa, carry out, the structure of cap is SiO
2(50nm)/Si
3n
4(50nm)/SiO
2(50nm)/Si
3n
4(50nm)/SiO
2(50nm)/Si
3n
4(50nm), gross thickness is 300nm.
Step 6, flexible OLED is carried out to mechanical stripping from rigid substrates, form curling OLED.
Embodiment 2
Flexible organic electroluminescent device structure is polyimide film/barrier layer/Al (200nm)/CuPc (40nm)/2-TNATA (40nm) //Ir (piq)
3: NPB (8%, 20nm)/TPBi (40nm)/CsF (1nm)/Al (18nm)/cap, its making step comprises following:
Step 1, provide rigid substrates, be placed in the deionized water that contains washing agent and carry out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen.
Step 2, in the reactor with heater, add solvent and 4,4 ' diaminodiphenyl ether (ODA), solvent for use is N, N '-dimethyl formamide (DMF), the mass percent that makes ODA is 10%; After treating ODA agitating solution, add pyromellitic acid anhydride (PMDA), the mol ratio that makes ODA and PMDA is 1:0.8, then stirs 2 hours, forms polyamic acid solution; After completion of the reaction, by polyamic acid solution N, N '-dimethyl formamide (DMF) dilutes, and the mass percent that makes polyamic acid is 10%; The solution of polyamic acid is covered to rigid substrates surface by spin coating, and the rotating speed of spin coating is 3000 revs/min; After spin coating, substrate is transferred in vacuum drying chamber, is heated to 350 ℃, react processed 5 hours, make polyamic acid dehydration form polyimide film, the thickness of final film forming is 100 μ m.
Step 3, in vacuum degree, be 1 * 10
-3in Pa vacuum coating system, barrier layer is prepared in sputter, and the structure on the barrier layer of formation is SiO
2(50nm)/Si
3n
4(100nm) gross thickness is 150nm.
Step 4, in vacuum degree, be 1 * 10
-3in the vacuum coating system of Pa, on the surface on barrier layer, evaporation is prepared anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, and the material of anode is Al, and thickness is 200nm, and evaporation speed is 2nm/s; The material of hole injection layer is CuPc, and thickness is 40nm, and evaporation speed is 1nm/s; The material of hole transmission layer is 2-TNATA, and thickness is 40nm, and evaporation speed is 1nm/s; The material of luminescent layer comprises NPB and is entrained in the Ir (piq) in NPB
3, Ir (piq)
3with the mass ratio of NPB be 8:100, thickness is 20nm, the evaporation speed of NPB is 1nm/s, Ir (piq)
3evaporation speed be 0.08nm/s; The material of electron transfer layer is TPBi, and thickness is 40nm, and evaporation speed is 1nm/s; The material of electron injecting layer is CsF, and thickness is 1nm, and evaporation speed is 0.1nm/s; The material of negative electrode is Al, and thickness is 180nm, and evaporation speed is 2nm/s.
Step 5, utilize thin-film package technique, in cathode surface sputter, prepare cap, cap is packaged in anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode on barrier layer, cap comprises silica membrane and is laminated in the silicon nitride film on silica membrane surface, and sputtering at vacuum degree is 1 * 10
-3vacuum coating system in carry out, the structure of cap is SiO
2(50nm)/Si
3n
4(50nm)/SiO
2(100nm)/Si
3n
4(100nm), gross thickness is 300nm.
Step 6, flexible OLED is carried out to mechanical stripping from rigid substrates, form curling OLED.
Embodiment 3
Flexible organic electroluminescent device structure is polyimide film/barrier layer/Au (70nm)/TiOPc (20nm)/m-MTDATA (20nm)/DCJTB:Alq
3(1%, 1nm)/PBD (20nm)/CsF/Sm(35nm)/cap, its making step comprises following:
Step 1, provide rigid substrates, be placed in the deionized water that contains washing agent and carry out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen.
Step 2, in the reactor with heater, add solvent and 4,4 ' diaminodiphenyl ether (ODA), solvent for use is N, N '-dimethyl formamide (DMF), the mass percent that makes ODA is 15%; After treating ODA agitating solution, add pyromellitic acid anhydride (PMDA), the mol ratio that makes ODA and PMDA is 1:1.2, then stirs 2 hours, forms polyamic acid solution; After completion of the reaction, by polyamic acid solution N, N '-dimethyl formamide (DMF) dilutes, and the mass percent that makes polyamic acid is 20%; The solution of polyamic acid is covered to rigid substrates surface by spin coating, and the rotating speed of spin coating is 2000 revs/min; After spin coating, substrate is transferred in vacuum drying chamber, is heated to 250 ℃, react processed 10 hours, make polyamic acid dehydration form polyimide film, the thickness of final film forming is 80 μ m.
Step 3, in vacuum degree, be 1 * 10
-5in Pa vacuum coating system, barrier layer is prepared in sputter, and the structure on the barrier layer of formation is SiO
2(50nm)/Si
3n
4(50nm), gross thickness is 100nm.
Step 4, in vacuum degree, be 1 * 10
-5in the vacuum coating system of Pa, on the surface on barrier layer, evaporation is prepared anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively, and the material of anode is Au, and thickness is 70nm, and evaporation speed is 0.5nm/s; The material of hole injection layer is TiOPc, and thickness is 20nm, and evaporation speed is 0.5nm/s; The material of hole transmission layer is m-MTDATA, and thickness is 20nm, and evaporation speed is 0.5nm/s; The material of luminescent layer comprises Alq
3and be entrained in Alq
3in DCJTB, DCJTB and Alq
3mass ratio be 1:100, thickness is 1nm, Alq
3evaporation speed be 1nm/s, the evaporation speed of DCJTB is 0.01nm/s; The material of electron transfer layer is PBD, and thickness is 20nm, and evaporation speed is 0.5nm/s; The material of electron injecting layer is CsF, and thickness is 0.5nm, and evaporation speed is 0.5nm/s; The material of negative electrode is Sm, and thickness is 35nm, and evaporation speed is 0.5nm/s.
Step 5, utilize thin-film package technique, in cathode surface sputter, prepare cap, cap is packaged in anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode on barrier layer, cap comprises silica membrane and is laminated in the silicon nitride film on silica membrane surface, and sputtering at vacuum degree is 1 * 10
-5in the vacuum coating system of Pa, carry out, the structure of cap is SiO
2(50nm)/Si
3n
4(50nm) gross thickness is 100nm.
Step 6, flexible OLED is carried out to mechanical stripping from rigid substrates, form curling OLED.
Embodiment 4
Flexible organic electroluminescent device structure is polyimide film/barrier layer/Ag-Al (100nm)/VOPc (20nm)/TPD (40nm)/Rubrene (10nm)/BCP (40nm)/LiF (1nm)/Yb(20nm)/cap, its making step comprises following:
Step 1, provide rigid substrates, be placed in the deionized water that contains washing agent and carry out ultrasonic cleaning, use successively isopropyl alcohol after cleaning up, acetone is processed 20 minutes in ultrasonic wave, and then dries up with nitrogen.
Step 2, in the reactor with heater, add solvent and 4,4 ' diaminodiphenyl ether (ODA), solvent for use is N, N '-dimethyl formamide (DMF), the mass percent that makes ODA is 10%; After treating ODA agitating solution, add pyromellitic acid anhydride (PMDA), the mol ratio that makes ODA and PMDA is 1:1, then stirs 2 hours, forms polyamic acid solution; After completion of the reaction, by polyamic acid solution N, N '-dimethyl formamide (DMF) dilutes, and the mass percent that makes polyamic acid is 8%; The solution of polyamic acid is covered to rigid substrates surface by spin coating, and the rotating speed of spin coating is 2500 revs/min; After spin coating, substrate is transferred in vacuum drying chamber, is heated to 300 ℃, react processed 6 hours, make polyamic acid dehydration form polyimide film, the thickness of final film forming is 100 μ m.
Step 3, in vacuum degree, be 1 * 10
-4in Pa vacuum coating system, barrier layer is prepared in sputter, and the structure on the barrier layer of formation is SiO
2(60nm)/Si
3n
4(60nm)/SiO
2(60nm)/Si
3n
4(60nm), gross thickness is 240nm.
Step 4, in vacuum degree, be 1 * 10
-4in the vacuum coating system of Pa, evaporation anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively on the surface on barrier layer, the material of anode is Ag-Al, and thickness is 100nm, and evaporation speed is 0.5nm/s; The material of hole injection layer is VOPc, and thickness is 20nm, and evaporation speed is 0.2nm/s; The material of hole transmission layer is TPD, and thickness is 40nm, and evaporation speed is 0.5nm/s; The material of luminescent layer is Rubrene, and thickness is 10nm, and evaporation speed is 0.1nm/s; The material of electron transfer layer is BCP, and thickness is 40nm, and evaporation speed is 0.5nm/s; The material of electron injecting layer is LiF, and thickness is 1nm, and evaporation speed is 0.1nm/s; The material of negative electrode is Yb, and thickness is 20nm, and evaporation speed is 0.2nm/s.
Step 5, utilize thin-film package technique, in cathode surface sputter, prepare cap, cap is packaged in anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode on barrier layer, cap comprises silica membrane and is laminated in the silicon nitride film on silica membrane surface, and sputtering at vacuum degree is 1 * 10
-4vacuum coating system in carry out, the structure of cap is SiO
2(60nm)/Si
3n
4(60nm)/SiO
2(60nm)/Si
3n
4(60nm), gross thickness is 240nm.
Step 6, flexible OLED is carried out to mechanical stripping from rigid substrates, form curling OLED.
Comparative example
The structure of comparative example is identical with the structure of embodiment 1, and its difference is that the preparation of OLED ray structure is to prepare on the direct polyimide film that is 0.1mm at thickness, does not adopt rigid substrates as support.
Its making step comprises following:
Step 1, thickness is provided is the polyimide film substrate of 0.1mm, and cleans up, and nitrogen dries up.
Step 2, in vacuum degree, be 1 * 10
-4in Pa vacuum coating system, barrier layer is prepared in sputter, the SiO that the structure on the barrier layer of formation is single layer structure
2at the surface of film substrate, SiO
2thickness be 200nm.
Step 3, in vacuum degree, be 1 * 10
-4in the vacuum coating system of Pa, at the barrier layer surface of film substrate successively evaporation, prepare anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, the material of anode is Ag, and thickness is 100nm, and evaporation speed is 0.2nm/s; The material of hole injection layer is ZnPc, and thickness is 20nm, and evaporation speed is 0.1nm/s; The material of hole transmission layer is NPB, and thickness is 30nm, and evaporation speed is 0.1nm/s; The material of luminescent layer comprises CBP and is entrained in the Ir (ppy) in CBP
3, Ir (ppy)
3with the mass ratio of CBP be 10:100, thickness is 10nm, the evaporation speed of CBP is 1nm/s, Ir (ppy)
3evaporation speed be 0.1nm/s; The material of electron transfer layer is Bphen, and thickness is 30nm, and evaporation speed is 0.1nm/s; The material of electron injecting layer is LiF, and thickness is 1nm, and evaporation speed is 1nm/s; The material of negative electrode is Ag, and thickness is 25nm, and evaporation speed is 0.2nm/s.
Step 4, utilize thin-film package technique, in cathode surface sputter, prepare cap, cap is packaged in anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode on barrier layer, cap comprises silica membrane and is laminated in the silicon nitride film on silica membrane surface, and sputtering at vacuum degree is 1 * 10
-4in the vacuum coating system of Pa, carry out, the structure of cap is SiO
2(50nm)/Si
3n
4(50nm)/SiO
2(50nm)/Si
3n
4(50nm)/SiO
2(50nm)/Si
3n
4(50nm), gross thickness is 300nm.
Table 1
Refer to table 1, table 1 is embodiment 1,2, the luminescent properties data of the flexible organic electroluminescent device of 3,4 preparations, and the data of surveying are to be 1000cd/m in initial brightness
2time, service time when initial brightness 70% is arrived in brightness decay.As can be seen from Table 1, embodiment 1,2, and the flexible organic electroluminescent device luminous efficiency of 3,4 preparations is all higher, and all reached more than 2300 hours useful life.Compare with comparative example, comparative example is in the process of preparation, because substrate is thinner, support strength is poor, causes substrate itself in preparation process that partial deformation occurs, and causes various materials uneven thickness when film forming, easily produce pin hole and defect, thereby the OLED device luminous efficiency obtaining is on the low side.Comparative example has only adopted the barrier layer of individual layer on substrate simultaneously, and it is obviously worse than the stacked barrier layer of bilayer provided by the invention to the blocking effect of water oxygen, so only have 1750 hours its useful life.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a flexible organic electroluminescent device, it is characterized in that, comprise the polyimide film, barrier layer, anode, luminescent layer and the negative electrode that stack gradually, described barrier layer comprises the first block film and is formed at second block film on the first block film surface, the material of described the first block film is silicon dioxide, and the material of described the second block film is silicon nitride;
Described organic electroluminescence device also comprises cap, and described cap is packaged in described anode, luminescent layer and negative electrode on described barrier layer, and described cap comprises silica membrane and is laminated in the silicon nitride film on described silica membrane surface.
2. flexible organic electroluminescent device according to claim 1, is characterized in that, the thickness of described the first block film is 50nm～100nm, and the thickness of described the second block film is 50nm～100nm.
3. flexible organic electroluminescent device according to claim 1, is characterized in that, the material of described anode is at least two kinds of formation in silver, gold and aluminium closes gold, silver, gold or aluminium.
4. flexible organic electroluminescent device according to claim 1, is characterized in that, the thickness of described polyimide film is 20 μ m～100 μ m.
5. flexible organic electroluminescent device according to claim 1, is characterized in that, the number of plies of the first block film described in described barrier layer and described the second block film is 1～3, and described the first block film and described the second block film are alternately laminated.
6. flexible organic electroluminescent device according to claim 1, is characterized in that, described in described cap, the number of plies of silica membrane and described silicon nitride film is 1～3, and described silica membrane and described silicon nitride film are alternately laminated.
7. a preparation method for flexible organic electroluminescent device, is characterized in that, comprises the following steps:
At rigid substrates surface spin coating polyamic acid solution, form Polyamic Acid Film;
Under vacuum environment, the Polyamic Acid Film on described stiff base and described rigid substrates surface is heated to 200 ℃～350 ℃ and carries out processed, make described Polyamic Acid Film dehydration form polyimide film;
At described polyimide film surface sputtering, prepare barrier layer, described barrier layer comprises the first block film and is formed at second block film on the first block film surface, the material of described the first block film is silicon dioxide, and the material of described the second block film is silicon nitride;
Surface on described barrier layer is prepared anode, luminescent layer and negative electrode successively;
At described cathode surface, prepare cap, described cap is packaged in described anode, luminescent layer and negative electrode on described barrier layer, and described cap comprises silica membrane and is laminated in the silicon nitride film on described silica membrane surface; And
By described polyimide film from described rigid substrates sur-face peeling.
8. the preparation method of flexible organic electroluminescent device according to claim 7, it is characterized in that, described polyamic acid solution is prepared by following steps: by 4,4 ' diaminodiphenyl ether adds in organic solvent and is mixed with 4,4 ' diaminodiphenyl ether solution, described organic solvent is selected from N, N '-dimethyl formamide, N, at least one in N '-dimethylacetylamide, 1-METHYLPYRROLIDONE and oxolane; Pyromellitic acid anhydride is added to 4,4, and ' diaminodiphenyl ether solution, stirs and within 1 hour～2 hours, forms polyamic acid solution, and wherein 4,4 ' mol ratio of diaminodiphenyl ether and pyromellitic acid anhydride is 1:0.8～1.2.
9. the preparation method of flexible organic electroluminescent device according to claim 8, is characterized in that, described 4,4, and ' in diaminodiphenyl ether solution, 4,4 ' mass concentration of diaminodiphenyl ether is 5%～15%; The preparation of described polyamic acid solution also comprises step: to adding described organic solvent to regulate the mass concentration of polyamic acid in described polyamic acid solution in described polyamic acid solution, be 5%～20%.
10. the preparation method of flexible organic electroluminescent device according to claim 7, is characterized in that, the time of described processed is 5 hours～10 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020124864A1 (en) * | 2018-12-18 | 2020-06-25 | 武汉华星光电半导体显示技术有限公司 | Display panel and manufacturing method therefor, and display device |
| CN111584744A (en) * | 2020-05-13 | 2020-08-25 | 深圳市华星光电半导体显示技术有限公司 | Display panel and preparation method thereof |
| CN111766727A (en) * | 2020-06-16 | 2020-10-13 | 浙江中科玖源新材料有限公司 | Polyimide substrate for flexible liquid crystal display and preparation method thereof |
| CN114302527A (en) * | 2021-12-23 | 2022-04-08 | 固安翌光科技有限公司 | OLED light-emitting device and control method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1871722A (en) * | 2003-10-21 | 2006-11-29 | 康宁股份有限公司 | OLED structures with barrier layer and strain relief |
| CN1957485A (en) * | 2004-04-02 | 2007-05-02 | 通用电气公司 | Organic electronic packages having sealed edges and methods of manufacturing such packages |
| WO2011023397A1 (en) * | 2009-08-29 | 2011-03-03 | Bundesdruckrei Gmbh | Device comprising an organic light emitting display |
| CN102210035A (en) * | 2008-12-30 | 2011-10-05 | 三星移动显示器株式会社 | Method for encapsulating environmentally sensitive devices |
-
2013
- 2013-04-28 CN CN201310157825.XA patent/CN104124347A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1871722A (en) * | 2003-10-21 | 2006-11-29 | 康宁股份有限公司 | OLED structures with barrier layer and strain relief |
| CN1957485A (en) * | 2004-04-02 | 2007-05-02 | 通用电气公司 | Organic electronic packages having sealed edges and methods of manufacturing such packages |
| CN102210035A (en) * | 2008-12-30 | 2011-10-05 | 三星移动显示器株式会社 | Method for encapsulating environmentally sensitive devices |
| WO2011023397A1 (en) * | 2009-08-29 | 2011-03-03 | Bundesdruckrei Gmbh | Device comprising an organic light emitting display |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020124864A1 (en) * | 2018-12-18 | 2020-06-25 | 武汉华星光电半导体显示技术有限公司 | Display panel and manufacturing method therefor, and display device |
| CN111584744A (en) * | 2020-05-13 | 2020-08-25 | 深圳市华星光电半导体显示技术有限公司 | Display panel and preparation method thereof |
| CN111766727A (en) * | 2020-06-16 | 2020-10-13 | 浙江中科玖源新材料有限公司 | Polyimide substrate for flexible liquid crystal display and preparation method thereof |
| CN114302527A (en) * | 2021-12-23 | 2022-04-08 | 固安翌光科技有限公司 | OLED light-emitting device and control method thereof |
| CN114302527B (en) * | 2021-12-23 | 2023-09-01 | 固安翌光科技有限公司 | OLED light-emitting device and control method thereof |
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