CN112467056A - Green light OLED device with waveguide mode light coupling enhancement and preparation method thereof - Google Patents
Green light OLED device with waveguide mode light coupling enhancement and preparation method thereof Download PDFInfo
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- CN112467056A CN112467056A CN202011539446.3A CN202011539446A CN112467056A CN 112467056 A CN112467056 A CN 112467056A CN 202011539446 A CN202011539446 A CN 202011539446A CN 112467056 A CN112467056 A CN 112467056A
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- 230000008878 coupling Effects 0.000 title claims abstract description 43
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- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000002347 injection Methods 0.000 claims abstract description 103
- 239000007924 injection Substances 0.000 claims abstract description 103
- 238000005530 etching Methods 0.000 claims abstract description 29
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- 239000000758 substrate Substances 0.000 claims abstract description 25
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- 239000010410 layer Substances 0.000 claims description 171
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 38
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- -1 (4-phenyl) (2,4, 6-trifluoromethylphenyl) amine Chemical class 0.000 claims description 23
- 239000012298 atmosphere Substances 0.000 claims description 16
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- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 15
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- GMYCTLAMROUHJF-UHFFFAOYSA-N 10-[4-[5-(4-phenoxazin-10-ylphenyl)-1,3,4-oxadiazol-2-yl]phenyl]phenoxazine Chemical compound O1C(=NN=C1C1=CC=C(C=C1)N1C2=C(OC3=C1C=CC=C3)C=CC=C2)C1=CC=C(C=C1)N1C2=C(OC3=C1C=CC=C3)C=CC=C2 GMYCTLAMROUHJF-UHFFFAOYSA-N 0.000 claims description 3
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 claims description 3
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 claims description 3
- PYZPSMJBEZBFOM-UHFFFAOYSA-N 2,4,5,6-tetra(carbazol-9-yl)benzene-1,3-dicarbonitrile Chemical compound N#Cc1c(c(C#N)c(c(c1-n1c2ccccc2c2ccccc12)-n1c2ccccc2c2ccccc12)-n1c2ccccc2c2ccccc12)-n1c2ccccc2c2ccccc12.N#Cc1c(c(C#N)c(c(c1-n1c2ccccc2c2ccccc12)-n1c2ccccc2c2ccccc12)-n1c2ccccc2c2ccccc12)-n1c2ccccc2c2ccccc12 PYZPSMJBEZBFOM-UHFFFAOYSA-N 0.000 claims description 3
- FQJQNLKWTRGIEB-UHFFFAOYSA-N 2-(4-tert-butylphenyl)-5-[3-[5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]phenyl]-1,3,4-oxadiazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=NN=C(C=2C=C(C=CC=2)C=2OC(=NN=2)C=2C=CC(=CC=2)C(C)(C)C)O1 FQJQNLKWTRGIEB-UHFFFAOYSA-N 0.000 claims description 3
- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 claims description 3
- HONWGFNQCPRRFM-UHFFFAOYSA-N 2-n-(3-methylphenyl)-1-n,1-n,2-n-triphenylbenzene-1,2-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C(=CC=CC=2)N(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 HONWGFNQCPRRFM-UHFFFAOYSA-N 0.000 claims description 3
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 claims description 3
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 claims description 3
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- LGDCSNDMFFFSHY-UHFFFAOYSA-N 4-butyl-n,n-diphenylaniline Polymers C1=CC(CCCC)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 LGDCSNDMFFFSHY-UHFFFAOYSA-N 0.000 claims description 3
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 claims description 3
- AOQKGYRILLEVJV-UHFFFAOYSA-N 4-naphthalen-1-yl-3,5-diphenyl-1,2,4-triazole Chemical compound C1=CC=CC=C1C(N1C=2C3=CC=CC=C3C=CC=2)=NN=C1C1=CC=CC=C1 AOQKGYRILLEVJV-UHFFFAOYSA-N 0.000 claims description 3
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- FWXNJWAXBVMBGL-UHFFFAOYSA-N 9-n,9-n,10-n,10-n-tetrakis(4-methylphenyl)anthracene-9,10-diamine Chemical compound C1=CC(C)=CC=C1N(C=1C2=CC=CC=C2C(N(C=2C=CC(C)=CC=2)C=2C=CC(C)=CC=2)=C2C=CC=CC2=1)C1=CC=C(C)C=C1 FWXNJWAXBVMBGL-UHFFFAOYSA-N 0.000 claims description 3
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- CDEASXIPDPAOGW-UHFFFAOYSA-N bis[4-(9,9-dimethylacridin-10-yl)phenyl]methanone Chemical compound C12=CC=CC=C2N(C2=C(C1(C)C)C=CC=C2)C1=CC=C(C(=O)C2=CC=C(N3C4=CC=CC=C4C(C4=C3C=CC=C4)(C)C)C=C2)C=C1 CDEASXIPDPAOGW-UHFFFAOYSA-N 0.000 claims description 3
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- VVOLVFOSOPJKED-UHFFFAOYSA-N copper phthalocyanine Chemical compound [Cu].N=1C2=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC=1C1=CC=CC=C12 VVOLVFOSOPJKED-UHFFFAOYSA-N 0.000 claims description 3
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- LUJALESCMWZZQD-UHFFFAOYSA-M sodium;quinolin-8-olate Chemical compound [Na+].C1=CN=C2C([O-])=CC=CC2=C1 LUJALESCMWZZQD-UHFFFAOYSA-M 0.000 claims description 3
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 claims description 3
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Images
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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
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/854—Arrangements for extracting light from the devices comprising scattering means
-
- 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
Abstract
The invention discloses a green light OLED device with waveguide mode light coupling enhancement and a preparation method thereof, and relates to the field of organic light emitting diodes. The device comprises a substrate, an anode, a hole injection layer, a hole transport layer, a green light emitting layer, an electron transport layer, an electron injection layer and a cathode. The device is characterized by an organic or inorganic hole injection layer, the hole injection layer film being vapor phase microetched by means of preferably an organic solvent or acid. The etching time and the film thickness of the hole injection layer are accurately adjusted to control the etching depth of gas molecules, so that an effective surface light scattering structure is formed. Therefore, light emitted from the interior of the green OLED device is refracted and diffused when passing through the scattering structure, photons in a waveguide mode can be effectively emitted, the luminous flux is increased, the light coupling efficiency is improved, and the external quantum efficiency is finally improved. The problem that the optical coupling of the OLED device is limited at present is solved.
Description
Technical Field
The invention relates to the technical field of organic light emitting diodes, in particular to a green light OLED device with waveguide mode light coupling enhancement.
Background
Organic light-emitting diodes (OLEDs) have great application potential in the fields of full-color flat panel display, solid-state lighting, and the like by virtue of their advantages of self-luminescence, wide viewing angle, rich colors, low-voltage direct-current drive, and the like. In addition, flexible OLEDs are highlighting their importance in the field of wearable displays and lighting. OLEDs are currently being commercialized in small-sized displays.
However, it has been found that two important factors that limit the final External Quantum Efficiency (EQE) of an OLED are the carrier transport balance and the optical coupling efficiency, in addition to the absolute quantum efficiency of the material itself. The excitons recombine radiatively in the light emitting layer to generate photons, and when the photons pass through the organic layer, the transparent electrode and the substrate, most of the photons are absorbed, scattered and reflected to be lost, so that the final light coupling efficiency is only about 20%, and the final EQE and the practical application of the OLED are limited to a great extent. With the gradual development and improvement of luminescent materials and device preparation processes, the key technology for improving the EQE is to improve the optical coupling efficiency and improve the carrier transport balance.
Existing optical coupling techniques include introducing diffraction gratings, photonic crystals, light scattering media, anode surface patterns, micro-cavities, micro-lenses, folds, scattering films, antireflection films, sandblasting, etc. at the appropriate interface of the device, most of these techniques involve complicated fabrication processes such as multiple pattern transfers, or require expensive equipment, harsh reaction conditions, high cost, or are not conducive to large-area device light extraction, etc. In view of the foregoing, there is a need for an OLED with waveguide mode optical coupling enhancement and a method for making the same that is relatively low cost and simple in process.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects in the prior art and provide a green OLED device with waveguide mode light coupling enhancement and a preparation method thereof. From the aspects of low cost, repeatability and safety, the method is different from the conventional liquid phase solvent treatment process, but adopts a gas phase solvent to carry out micro-etching on a hole injection layer in the green OLED, and controls the penetration depth of solvent gas molecules by accurately adjusting the etching time of the gas phase solvent and the film thickness of the hole injection layer, thereby controlling the film surface micro-morphology and phase separation. The defect of serious leakage current caused by a liquid phase solvent treatment process is overcome. The formed light scattering structure enables light emitted from the interior of the green OLED to be refracted and scattered in a diffuse mode when passing through the scattering structure, so that the limitation of a waveguide mode of the device is reduced, optical coupling is enhanced, the external quantum efficiency is finally improved, and the color stability of the device is not influenced.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a green light OLED device with waveguide mode optical coupling enhancement comprises a substrate, an anode, a hole injection layer, a hole transport layer, a green light emitting layer, an electron transport layer, an electron injection layer and a conductive cathode which are sequentially stacked from bottom to top; the light-emitting object material of the green light-emitting layer adopts a fluorescent, phosphorescent and thermally activated delayed fluorescent material which emits green light; the hole injection layer is treated by a solvent, and the etching depth of solvent gas molecules is controlled by adjusting the solvent treatment time and the film thickness of the hole injection layer.
Preferably, the hole injection layer is made of a polymer material, and comprises at least one of the following materials:
poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate)、poly[N,N'-bis(4-butylphenyl)-N,N'-bis(phenyl)-benzidine]、poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine](PTAA)、poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylam ine)]；
preferably, or, the hole injection layer is made of a small molecule material, including at least one of the following materials: 4,4',4"-tris (N-3-methylphenyl-N-phenyl-amino) triphenylamine, 4',4" -tris (N- (naphtalen-2-yl) -N-phenyl-amino) triphenylamine, copper (II) phthalocyanine (CuPC), titanium (IV) oxydiphatic yanine, pyraz ino [2,3-f ] [1,10] phenanthrone-2, 3-dicarbonitrile, N, N, N ', N ' -tetrapropyl (4-methoxyphenylamino) benzidine, N, N ' -diphenyl-N, N ' -di- [4- (N, N-di-p-tolylamino) phenylphenylphenylphenylbenzidine, N, N ' -di- [ 4' - (4-tolyl-p-tolyll-amino) phenylphenylbenzidine, N, N ' -dithiophenyl ] benzidine, N, N ' -dithiophenyl ] triphenylamine, N, 4' -dithiophenyl-N-4 ' -dithiophenyl-aminothiophene [4, N ' -dithiophenyl-4 ' - (3-thienyl-2, 4' -dithiophenyl-3-diyl) triphenylamine, N, N ' -dithiophenyl-4 ' -dithiophene-4, N, N ' -dithiophenyl-4 ' -dithiophene-4, N, N, 4' -dithiophene-4, 4' -dithiophene-3, 4' -dithiophene-3632, 4' -dithiophene-4, 4' -dithiophene-3, 4' -dithiophene-, 3'-h ] quinoxaline-2,3,6,7,10,11-hexa carbonitrile, diquinoxaline [2,3-a:2',3'-c ] phenazine, 7,8,8-tetracyano quinodimethane, 2,3,5,6-tetrafluoro-7,7,8, 8-tetracyano-quinodimethane, 2' - (naphthalene-2, 6-diyl) dimethanol;
preferably, or, the hole injection layer is made of an oxide material, including at least one of the following materials: MoO3、CuO、V2O5、NiO2、WO3。
Preferably, the material of the substrate layer is at least one of a rigid glass material, a transparent polymer flexible material and a biodegradable flexible material. Further preferably, the transparent polymer flexible material is any one or more of polyethylene, polymethyl methacrylate, polycarbonate, polyurethane, polyimide resin and polyacrylic acid.
Preferably, the anode is made of at least one of ITO, FTO, AZO, IZO, graphene, carbon nanotubes, elemental metal nanowires, metal alloy nanowires, and metal heterojunction nanowires; the thickness of the anode is 80-200 nm.
Preferably, the hole transport layer is made of N, N '-bis (naphthalene-1-yl) -N, N' -bis (phenyl) -benzidine, N '-bis (3-methylphenyl) -N, N' -bis (phenyl) -benzidine, 4 '-tris (carbozol-9-yl) triphenylamine, N' -bis (3-methylphenyl) -N, N '-bis (phenyl) -2, 7-diamido-9, 9-spirobifluorene, N' -bis (naphthalene-1-yl) -N, N '-bis (phenyl) -2, 7-diamido-9, 9-diamido-fluoroene, 9-bis [4- (N, N-phenyl-1-yl) -N, N' -bis (phenyl) -2, 7-diamido-9, 9-diamido-9-fluoronaphthalene, 9-bis [4- (N, N-hydroxyphenyl) -2-butyl-9-hydroxyphenyl ] -HfHfyl-9-benzyl-2, 7-diamido-9-fluoronaphthalene, At least one material selected from di- [4- (N, N-di-p-tolyl-amino) -phenyl ] cyclohexane, N1, N4-diphenyl-N1, N4-di-m-tolyilbenzene-1, 4-diamine, N4, N4' -bis (4- (6- ((3-ethylhexylan-3-yl) methoxy) phenyl) -N4, N4' -diphenylylphenyl-4, 4' -diamine, 4' - (diphenylsilylediyl) bis (N, N-diphenyleneine), 4' - (diphenylmethyene) bis (N, N-diphenyleneine).
Preferably, the light-emitting guest material of the green light-emitting layer is fac-tris (2-phenylpyridine) iridium (iii), bis (2-phenylpyridine) (acetylacetate) iridium (iii), 9,10-bis [ N, N-di- (p-tol yl) -amino [ ]]anthracene、N10,N10,N10',N10'-tetraphenyl-9,9'-bianthrac ene-10,10'-diamine、9,9',9”-(5-(4,6-diphenyl-1,3,5–triazin-2-yl)benzene-1,2,3-triyl)tris(3,6-dimethyl-9H-carbazole)、9,10-bis[N,N-di-(p-tolyl)-amino]anthracene、(4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile、2,5-bis(4-(10H-phenoxa zin-10-yl)phenyl)-1,3,4-oxadiazole、10,10'-(4,4'-sulfonlybis(4,1-phenylene))bis(10H-phenoxazine)、1,4-bis(9,9-dimethylacridan-10-yl-pphenyl)-2,5-bis(p-tolyl-metha noyl)benzene、bis(4-(9,9-dimethylacridin-10(9H)-yl)phenyl)methanone、5-chloro-2,4,6-tris(3,6-di-tert-butyl-9H-carbazol-9-yl)isophthalonitrile、4,4”-di-10H-phenoxazin-10-yl[1,1':2',1”-terphenyl]-at least one of 4',5' -dicarbonitrile;
preferably, the luminescent host material of the green light emitting layer is 1,3-bis (carbozol-9-yl) benzene, 2,8-bis (phenyleophoryl) bis [ b, d ] thiophene (PPT), 4' -tris (carbozol-9-yl) triphenylamine, 4' -bis (carbozol-9-yl) phenyl, bis [2- (phenyletho) phenyl ] ether, 2,6-di (9H-carbozol-9-yl) pyridine, 2,4,6-tris (3- (9H-carbozol-9-yl) phenyl) -1,3,5-triazine, 4' - (9H-carbozol-9-yl) phenyl, 5-phenylene-3, 5-phenyl, 4- (9H-carbozol-9-yl) phenyl, 3, 5-phenylene-4 [ (3-4-carbozol-9-yl) phenyl ] ether, 4-carbozol-9-yl ] phenyl, 4-phenyl ] phenyl, 4- (9H-carbozol-9-yl) phenyl ] phenyl, 4-carbozin-4- (3-4-phenyl) phenyl ] phenyl-4, 4- (9-phenyl) phenyl-4, 4-phenyl ] phenyl-4, 4-phenyl-4, 4-phenyl-4, 4-phenyl-3, 4-phenyl- At least one of-9, 9-dimethyl-9, 10-dihydroacridine.
Preferably, the material of the electron transport layer adopts 4,7-diphenyl-1,10-phenanthroline, 2'- (1,3, 5-benzinetryl) -tris (1-phenyl-1-H-benzimidazole), thiocuproline, tris- (8-hydroxyquinolinato) aluminum, 2- (4-biphenol) -5- (4-tert-butyl-phenyl) -1,3, 4-oxadiazine, bis (2-methyl-8-quinonolate) -4- (phenyl-linolato) aluminum, 1,3-bis [2- (2,2' -biphenol-6-yl) -1,3, 4-oxadiazine-5-yl ] -5-oxadiazine]benzene、4-(naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-triazole、tris(2,4,6-trimethyl-3-(pyridin-3-yl)phenyl)borane、phenyl-dipyrenylphosphineoxide、1,3-bis[2-(4-tert-butylphenyl)-1,3,4-oxadiazo-5-yl]benzene、1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene, graphene, carbon nano tube, ZnO and Cs2CO3At least one of (1).
Preferably, the material of the electron injection layer adopts at least one of lithium fluoride, 8-hydroxyquinoline to lithium, magnesium fluoride, 8-hydroxyquinoline sodium salt and magnesium fluoride; preferably, the material of the cathode is at least one of Al, Ag, Au, IZO, Ca, magnesium silver alloy, and lithium aluminum alloy.
The invention relates to a preparation method of a green OLED device with waveguide mode light coupling enhancement, which comprises the following steps:
1) cleaning the substrate and the anode, and drying by nitrogen;
2) preparing a hole injection layer on the surface of the anode by adopting a spin coating, printing, spraying or evaporation mode and adopting a hole injection layer material;
3) heating a preferred solvent in a closed container to generate a high-concentration steam atmosphere, adjusting the flow rate of solvent gas, putting the hole injection layer film into the container, standing for a set time, taking out, and annealing and drying the film at different annealing temperatures according to the used solvent;
4) preparing a hole transport layer, a green light emitting layer, an electron transport layer and an electron injection layer in sequence by adopting a spin coating, printing, spraying or evaporation mode on the surface of the hole injection layer treated in the step 3);
5) replacing a mask plate, and evaporating a cathode material on the surface of the electron injection layer prepared in the step 4) to form an electrode cathode layer, so that each functional layer of the OLED is manufactured.
Preferably, in the step 3), the following steps are adopted:
a. preparing hole injection layers with different thicknesses on the substrate layer/the anode, wherein the thickness is 10-50 nm; the hole injection layer is made of at least one of a polymer, a small molecule or an oxide which is mainly used for transmitting holes, has an energy level matched with that of the anode and the hole transmission layer and can be dissolved by a volatile solvent and an acid;
b. creating a high-concentration organic solvent or acid vapor atmosphere in a closed container, enabling gas to continuously flow, and placing a hole injection layer film for standing for different times to control the penetration depth of gas molecules; adjusting the steam flow rate to be 3-10L/min, and keeping the film standing for 30-60 min;
c. and taking out the hole injection layer film, annealing and drying to obtain the processed hole injection layer. And then sequentially laminating a hole transport layer, a green light emitting layer, an electron transport layer, an electron injection layer and a cathode on the green light emitting layer to form the complete green OLED device.
Preferably, the solvent for gas phase treatment is an organic solvent or an acid, and the solvent for gas phase treatment is at least one of methanol, ethanol, n-butanol, isopropanol, acetone, DMA, DMSO, DMF, tetrahydrofuran, toluene, chlorobenzene, dichloromethane, trichloromethane, carbon disulfide, triethylamine, m-cresol, hydrochloric acid, nitric acid, acetic acid, and formic acid.
Preferably, the flow rate of the solvent vapor in the closed container is adjusted to be 3-10L/min, and the standing time of the film in the atmosphere is preferably 30-60 min; as a further preferable mode of the above mode, the thin film after the gas phase treatment is to form an effective phase separation, and a certain ordered structure is observed in XRD diffraction, or an AFM image shows a distinct condensed phase.
Preferably, the evaporation rate of the functional layer materials is controlled as follows: the electron injection layer has a material evaporation rate of
The cathode material has an evaporation rate of
Other organic substances have an evaporation rate of
On the basis of preparing a hole injection layer film, the invention constructs a high-concentration solvent gas-phase atmosphere in a closed environment, places the film in the atmosphere for standing for a certain time, and utilizes the strong permeability of solvent gas molecules and the solubility of hole injection layer materials to carry out micro-etching on the surface of the film. The penetration or etching depth of solvent gas molecules is accurately controlled through the etching time of the gas-phase solvent and the film thickness of the hole injection layer, so that effective phase separation occurs on the surface of the film within the depth range of nanometer level and a light scattering microstructure is formed. Photons emitted by the green OLED light emitting layer are refracted and scattered when passing through the scattering microstructure and then are effectively emitted, so that the optical coupling of a waveguide mode is enhanced, and the optical coupling efficiency of the device is finally improved.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. compared with the traditional hole injection layer with single function, the invention adopts high-concentration steam of proper solvent to carry out micro-etching on the surface of the hole injection layer film of the green OLED so as to cause the hole injection layer film to be separated and patterned, the etching effect of the gas-phase solvent is milder than that of the liquid-phase solvent, and the leakage current of devices is avoided;
2. the penetration or etching depth of solvent gas molecules is accurately controlled through the processing time of the gas-phase solvent and the film thickness of the hole injection layer, and the etching precision is controllable, so that the surface micro-morphology and the phase separation of the film are controlled;
3. the device disclosed by the invention has the advantages that under the condition of no other additional optical design and no complex process, the limitation of the waveguide mode of the device is reduced by a simple method, and the optical coupling and external quantum efficiency are enhanced;
4. the invention has simple process, stable performance of the processed film and suitability for batch production of flexible green light emitting devices with different areas and rigidity;
5. the method is simple and easy to implement, low in cost and suitable for popularization and application.
Drawings
Fig. 1 is a schematic structural diagram of an organic light emitting diode according to the present invention.
Fig. 2 is a flow chart of the preparation of organic light emitting diodes according to third to sixth embodiments of the present invention.
FIG. 3 is an AFM image of PEDOT: PSS films of the same thickness and PEDOT: PSS films of different thicknesses in the same DMF vapor treatment time for example five.
Fig. 4 shows the current efficiency and power efficiency of devices in example five, example six and the reference example.
FIG. 5 shows the external quantum efficiency and the electroluminescence spectra of the devices of example five, example six and the reference example.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
the first embodiment is as follows:
in the present embodiment, referring to fig. 1, a green OLED device with waveguide mode optical coupling enhancement comprises a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a green light emitting layer 5, an electron transport layer 6, an electron injection layer 7 and a conductive cathode 8, which are sequentially stacked from bottom to top; the light-emitting object material of the green light-emitting layer 5 adopts a fluorescent, phosphorescent and heat-activated delayed fluorescent material which emits green light; the hole injection layer 3 is treated by a solvent, and the etching depth of solvent gas molecules is controlled by adjusting the solvent treatment time and the film thickness of the hole injection layer 3.
The light scattering structure formed by the green OLED device with enhanced waveguide mode light coupling in the embodiment enables light emitted inside the green OLED to be refracted and scattered in a diffuse mode when passing through the scattering structure, so that the limitation of the waveguide mode of the device is reduced, the light coupling is enhanced, the external quantum efficiency is finally improved, and the color stability of the device is not affected.
Example two:
this embodiment is substantially the same as the first embodiment, and is characterized in that:
in the present embodiment, referring to fig. 1, the hole injection layer 3 is made of a polymer material including at least one of the following materials: poly (3,4-ethylenedioxythiophene) -poly (phenylenesulfonate), poly [ N, N ' -bis (4-butylphenyl) -N, N ' -bis (phenyl) -benzidine ], poly [ bis (4-phenyl) (2,4, 6-trifluoromethylphenyl) amine ] (PTAA), poly [ (9, 9-dimethoxyphenyl-2, 7-diyl) -co- (4,4' - (N- (4-sec-butylphenyl) diphenylamine) ];
in this embodiment, alternatively, the hole injection layer 3 is made of a small molecule material, including at least one of the following materials: 4,4',4"-tris (N-3-methylphenyl-N-phenyl-amino) triphenylamine, 4',4" -tris (N- (naphtalen-2-yl) -N-phenyl-amino) triphenylamine, copper (II) phthalocyanine (CuPC), titanium (IV) oxydiphatic yanine, pyraz ino [2,3-f ] [1,10] phenanthrone-2, 3-dicarbonitrile, N, N, N ', N ' -tetrapropyl (4-methoxyphenylamino) benzidine, N, N ' -diphenyl-N, N ' -di- [4- (N, N-di-p-tolylamino) phenylphenylphenylphenylbenzidine, N, N ' -di- [ 4' - (4-tolyl-p-tolyll-amino) phenylphenylbenzidine, N, N ' -dithiophenyl ] benzidine, N, N ' -dithiophenyl ] triphenylamine, N, 4' -dithiophenyl-N-4 ' -dithiophenyl-aminothiophene [4, N ' -dithiophenyl-4 ' - (3-thienyl-2, 4' -dithiophenyl-3-diyl) triphenylamine, N, N ' -dithiophenyl-4 ' -dithiophene-4, N, N ' -dithiophenyl-4 ' -dithiophene-4, N, N, 4' -dithiophene-4, 4' -dithiophene-3, 4' -dithiophene-3632, 4' -dithiophene-4, 4' -dithiophene-3, 4' -dithiophene-, 3'-h ] quinoxaline-2,3,6,7,10,11-hexa carbonitrile, diquinoxaline [2,3-a:2',3'-c ] phenazine, 7,8,8-tetracyano quinodimethane, 2,3,5,6-tetrafluoro-7,7,8, 8-tetracyano-quinodimethane, 2' - (naphthalene-2, 6-diyl) dimethanol;
in this embodiment, alternatively, the hole injection layer 3 is made of an oxide material including at least one of the following materials: MoO3、CuO、V2O5、NiO2、WO3。
In this embodiment, the material of the substrate layer 1 is at least one of a rigid glass material, a transparent polymer flexible material and a biodegradable flexible material.
In this embodiment, the anode 2 is made of at least one of ITO, FTO, AZO, IZO, graphene, a carbon nanotube, a simple metal nanowire, a metal alloy nanowire, and a metal heterojunction nanowire; the thickness of the anode is 80-200 nm.
In this embodiment, the hole transport layer 4 is made of N, N ' -bis (phenyl-1-yl) -N, N ' -bis (phenyl) -benzidine, N ' -bis (3-methylphenyl) -N, N ' -bis (phenyl) -benzidine, 4',4 ″ -tris (carbozol-9-yl) triphenylamine, N ' -bis (3-methylphenyl) -N, N ' -bis (phenyl) -2, 7-diamido-9, 9-spirobifluorene, N ' -bis (phenyl-1-yl) -N, N ' -bis (phenyl) -2, 7-diamido-9, 9-diamido-2, 9-diamido-9, 9-bis [4- (N-phenyl-1-yl) -N, N ' -bis (phenyl) -2, 7-diamido-9, 9-diamido-9-dimethyl-2, 9-4- (N-phenyl-2-hydroxyphenyl) -N, N ' -bis [ 4-butyl-9-2, N-hydroxyphenyl ] -phenyl-bis, At least one material selected from di- [4- (N, N-di-p-tolyl-amino) -phenyl ] cyclohexane, N1, N4-diphenyl-N1, N4-di-m-tolyilbenzene-1, 4-diamine, N4, N4' -bis (4- (6- ((3-ethylhexylan-3-yl) methoxy) phenyl) -N4, N4' -diphenylylphenyl-4, 4' -diamine, 4' - (diphenylsilylediyl) bis (N, N-diphenyleneine), 4' - (diphenylmethyene) bis (N, N-diphenyleneine).
In this embodiment, the light-emitting guest material of the green light-emitting layer 5 is fac-tris (2-phenylpyridine) iridium (iii), bis (2-phenylpyridine) (acetylacetate) iridium (iii), 9,10-bis [ N, N-di- (p-tol yl) -amino [ ]]anthracene、N10,N10,N10',N10'-tetraphenyl-9,9'-bianthrac ene-10,10'-diamine、9,9',9”-(5-(4,6-diphenyl-1,3,5–triazin-2-yl)benzene-1,2,3-triyl)tris(3,6-dimethyl-9H-carbazole)、9,10-bis[N,N-di-(p-tolyl)-amino]anthracene、(4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile、2,5-bis(4-(10H-phenoxa zin-10-yl)phenyl)-1,3,4-oxadiazole、10,10'-(4,4'-sulfonlybis(4,1-phenylene))bis(10H-phenoxazine)、1,4-bis(9,9-dimethylacridan-10-yl-pphenyl)-2,5-bis(p-tolyl-metha noyl)benzene、bis(4-(9,9-dimethylacridin-10(9H)-yl)phenyl)methanone、5-chloro-2,4,6-tris(3,6-di-tert-butyl-9H-carbazol-9-yl)isophthalonitrile、4,4”-di-10H-phenoxazin-10-yl[1,1':2',1”-terphenyl]-at least one of 4',5' -dicarbonitrile;
in this embodiment, the light-emitting host material of the green light-emitting layer 5 is 1,3-bis (carbozol-9-yl) benzene, 2,8-bis (diphenylophoryl) diphenylene [ b, d ] thiophene (ppt), 4',4 ″ -tris (carbozol-9-yl) triphenylamine, 4' -bis (carbozol-9-yl) diphenylene, bis [2- (diphenylophono) phenyl ] ether, 2,6-di (9H-carbozol-9-yl) pyridine, 2,4,6-tris (3- (9H-carbozol-9-yl) phenyl) -1,3,5-triazine, 4'- (9H-carbozol-9-yl) phenyl) -3, 5-triazine, 3-carbozine, 3-5-triazine, 3-5-phenyl ] phenyl, 3,5-triazine, 3-bis (3-carbozol-9-yl) phenyl ] phenyl, 3-5-triazine, 3-triazine, 5-triazine, 3-benzyl, 3-phenyl, 3-triazine, 3-benzyl-3, 3-triazine, 3-benzyl-phenyl, 3-triazine, 3-benzyl-4' - (9, 10- (4- (9H-carbazol-9-yl) phenylsulfonyl) phenyl) -9,9-dimethyl-9, 10-dihydroacridinine.
In this embodiment, the electron transport layer 6 is made of 4,7-diphenyl-1,10-phenanthroline, 2' - (1,3, 5-benzinetryl) -tris (1-phenyl-1-H-benzimidazole), bathiouproine, tris- (8-hydroxyquinolinato) aluminum, 2- (4-biphenyl) -5- (4-tert-butyl-phenyl) -1,3, 4-oxadiazine, bis (2-methyl-8-quinolinolate)-4-(pheny lphenolato)aluminium、1,3-bis[2-(2,2'-bipyridine-6-yl)-1,3,4–oxadiazo-5-yl]benzene、4-(naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-triazole、tris(2,4,6-trimethyl-3-(pyridin-3-yl)phenyl)borane、phenyl-dipyrenylphosphineoxide、1,3-bis[2-(4-tert-butylphenyl)-1,3,4-oxadiazo-5-yl]benzene、1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene, graphene, carbon nano tube, ZnO and Cs2CO3At least one of (1).
In the present embodiment, the material of the electron injection layer 7 is at least one of lithium fluoride, 8-hydroxyquinoline to-lithium, magnesium fluoride, 8-hydroxyquinoline sodium salt, and magnesium fluoride; the cathode 8 is made of at least one of Al, Ag, Au, IZO, Ca, Mg-Ag alloy and Li-Al alloy.
The design of the green OLED device with waveguide mode light coupling enhancement is realized through selection and matching of materials of the energy-enhancing layer. The device comprises a substrate, an anode, a hole injection layer, a hole transport layer, a green light emitting layer, an electron transport layer, an electron injection layer and a cathode. The device is characterized by an organic or inorganic hole injection layer, the hole injection layer film being vapor phase microetched by means of preferably an organic solvent or acid. The etching time and the film thickness of the hole injection layer are accurately adjusted to control the etching depth of gas molecules, so that an effective surface light scattering structure is formed.
Example three:
this embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a method for manufacturing a green OLED device with waveguide mode light coupling enhancement includes the following steps:
1) cleaning the substrate and the anode, and drying by nitrogen;
2) preparing a hole injection layer on the surface of the anode by adopting a spin coating, printing, spraying or evaporation mode and adopting a hole injection layer material;
3) heating a preferred solvent in a closed container to generate a high-concentration steam atmosphere, adjusting the flow rate of solvent gas, putting the hole injection layer film into the container, standing for a set time, taking out, and annealing and drying the film at different annealing temperatures according to the used solvent;
4) preparing a hole transport layer, a green light emitting layer, an electron transport layer and an electron injection layer in sequence by adopting a spin coating, printing, spraying or evaporation mode on the surface of the hole injection layer treated in the step 3);
5) replacing a mask plate, and evaporating a cathode material on the surface of the electron injection layer prepared in the step 4) to form an electrode cathode layer, so that each functional layer of the OLED is manufactured.
In this embodiment, on the basis of preparing a hole injection layer thin film, a high-concentration solvent gas phase atmosphere is constructed in a closed environment, the thin film is placed therein and left standing for a certain time, and the surface of the thin film is subjected to micro-etching by utilizing the strong permeability of solvent gas molecules and the solubility of a material of the hole injection layer. The penetration or etching depth of solvent gas molecules is accurately controlled through the etching time of the gas-phase solvent and the film thickness of the hole injection layer, so that effective phase separation occurs on the surface of the film within the depth range of nanometer level and a light scattering microstructure is formed. Photons emitted by the green OLED light emitting layer are refracted and scattered when passing through the scattering microstructure and then are effectively emitted, so that the optical coupling of a waveguide mode is enhanced, and the optical coupling efficiency of the device is finally improved.
Example four:
this embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, in the step 3), the following steps are adopted:
a. preparing hole injection layers with different thicknesses on the substrate layer/the anode, wherein the thickness is 10-50 nm; the hole injection layer is made of at least one of a polymer, a small molecule or an oxide which is mainly used for transmitting holes, has an energy level matched with that of the anode and the hole transmission layer and can be dissolved by a volatile solvent and an acid;
b. creating a high-concentration organic solvent or acid vapor atmosphere in a closed container, enabling gas to continuously flow, and placing a hole injection layer film for standing for different times to control the penetration depth of gas molecules; adjusting the steam flow rate to be 3-10L/min, and keeping the film standing for 30-60 min;
c. and taking out the hole injection layer film, annealing and drying to obtain the processed hole injection layer.
In this embodiment, the solvent for vapor phase treatment is an organic solvent or an acid, and the solvent for vapor phase treatment is at least one of methanol, ethanol, n-butanol, isopropanol, acetone, DMA, DMSO, DMF, tetrahydrofuran, toluene, chlorobenzene, dichloromethane, trichloromethane, carbon disulfide, triethylamine, m-cresol, hydrochloric acid, nitric acid, acetic acid, and formic acid.
In this embodiment, the flow rate of the solvent vapor in the closed container is adjusted to 3 to 10L/min, and the standing time of the film in the atmosphere is 30 to 60 min.
Compared with the traditional hole injection layer with a single function, the method provided by the embodiment of the invention adopts high-concentration steam of a proper solvent to carry out micro-etching on the surface of the hole injection layer film of the green OLED so as to cause phase separation and patterning, the etching effect of a gas-phase solvent is milder than that of a liquid-phase solvent, and the leakage current of a device is avoided. In the embodiment, the penetration or etching depth of solvent gas molecules is accurately controlled through the processing time of the gas-phase solvent and the film thickness of the hole injection layer, and the etching precision is controllable, so that the surface micro-morphology and the phase separation of the film are controlled. The device prepared by the embodiment reduces the limitation of the waveguide mode of the device by a simple method and enhances the optical coupling and external quantum efficiency under the condition of no other additional optical design and no complex process. The method has simple process, and the processed film has stable performance and can be suitable for batch production of green light emitting devices with different areas and rigidity and flexibility.
Example five:
this embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a green OLED device with waveguide mode light coupling enhancement includes the steps of:
(1) an ITO glass substrate consisting of a substrate layer and an anode layer is adopted,the thickness of the ITO is 150nm, namely a transparent IT0 glass substrate etched into a certain template is selected as an anode, ultrasonic cleaning is sequentially carried out for 20-30 minutes by using a cleaning agent, acetone, deionized water and isopropanol, nitrogen is blown to dry, and UV/O is carried out3Treating for 15-30 minutes for later use;
(2) ultrasonically treating a solution of PEDOT and PSS to be used for 5-10 s to uniformly mix the PEDOT and the PSS, and transferring 30-50 ul of the mixed solution to be dripped on an ITO glass substrate; coating PEDOT at 3000-5000rmp/60s by a spin coating method, wherein PSS is used for preparing a hole injection layer with the thickness of 30-15 nm; annealing the film on a hot plate at 130 ℃ for 10-20 minutes, and quickly placing the film in a closed container after cooling; continuously heating liquid phase DMF in a closed container at 100-120 ℃ to generate high-concentration steam, wherein the gas phase flow rate is 5-10L/min; treating the film in a solvent gas phase atmosphere for 30-60 min; then taking the processed film out of the closed environment, and annealing at 150-170 ℃ for 10-20 min to dry;
(3) placing the hole injection layer treated in the step (2) in a vacuum degree of less than 3 multiplied by 10-4And (2) sequentially depositing an NPB hole transport layer of 25-45 nm, a 4CZIPN CBP green light emitting layer of 10-25 nm in mass ratio of 1: 100-1: 25, a TPBi electron transport layer of 30-50 nm and a LiF electron injection layer of 0.5-0.8 nm in a vacuum evaporation chamber of Pa, and finally replacing a mask plate to evaporate cathode metal Al to prepare an electrode cathode layer of 80-100 nm in thickness. The OLED device with the light-emitting area not less than 2mm multiplied by 2mm is prepared by the method. The evaporation rate was: organic matter
LiF is
AL is
d. The fabrication process of the reference device was substantially the same as that of example 1, except that PEDOT: PSS was used directly as the hole injection layer in the reference device, and the film was not solvent vapor treated.
The flow chart for constructing the green OLED in this embodiment is shown in fig. 2. For the same thickness in DMF gas phase atmosphereThe PEDOT PSS film is processed for 30-60min, and the PEDOT PSS films with different thicknesses prepared at different rotating speeds are processed for 45min in a DMF gas phase atmosphere, and AFM images of the films are shown in figure 3. It was found that the longer the vapor treatment time or the thinner the PEDOT: PSS film, the deeper the film surface etching, and the increased roughness. Therefore, the penetration depth of gas molecules can be controlled by accurately adjusting the etching time and the film thickness of the hole injection layer. The etching time can be adjusted to 30-60 min. The adjustable speed is 3000-5000rmp/60 s. And preparing a green OLED by using the PEDOT/PSS film subjected to DMF gas phase treatment as a hole injection layer and carrying out a luminescence test to obtain the graphs of FIG. 4 and FIG. 5. As can be seen from fig. 4, the green OLED device prepared in example five has good light emitting properties. Compared with the reference device, the current efficiency of the DMF-containing PEDOT/PSS layer gas-phase processed device is improved from 23.09cd/A to 25.56 cd/A. Maximum luminance of device 7008cd/m from reference example2Increased to 7538cd/m2. The external quantum efficiency and the electroluminescence spectrum of the device are shown in fig. 5, the EQE of the device is improved under different brightness, and the maximum EQE is improved from 7.91% of the reference example to 8.50% and is improved by 7.4%. The electroluminescence spectrum of the device is shown in fig. 5, and it can be seen from the graph that the CIE color coordinate offset of the green OLED device prepared by the hole injection layer after the gas phase treatment is less than 0.01 compared with that of the reference device, which shows that the color stability is good.
Example six:
this embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a green OLED device with waveguide mode light coupling enhancement includes the steps of:
(1) an ITO glass substrate consisting of a substrate layer and an anode layer is adopted, the thickness of the ITO is 150nm, namely, a transparent IT0 glass substrate etched into a certain template is selected as the anode, ultrasonic cleaning is sequentially carried out for 20-30 minutes by using a detergent, acetone, deionized water and isopropanol, nitrogen is dried, and UV/O (ultraviolet/oxygen) is carried out3Treating for 15-30 minutes for later use;
(2) ultrasonically treating a solution of PEDOT and PSS to be used for 5-10 s to uniformly mix the PEDOT and the PSS, and transferring 30-50 ul of the mixed solution to be dripped on an ITO glass substrate; coating PEDOT at 3000-5000rmp/60s by a spin coating method, wherein PSS is used for preparing a hole injection layer with the thickness of 30-15 nm; annealing the film on a hot plate at 130 ℃ for 10-20 minutes, and quickly placing the film in a closed container after cooling; continuously heating liquid phase DMSO in a closed container at 130-145 ℃ to generate high-concentration steam, wherein the flow rate of a gas phase is 3-10L/min; treating the film in a solvent gas phase atmosphere for 30-60 min; then taking the processed film out of the closed environment, and annealing at 190-210 ℃ for 10-20 min to dry;
(3) placing the hole injection layer treated in the step (2) in a vacuum degree of less than 3 multiplied by 10-4And (2) sequentially depositing an NPB hole transport layer of 25-45 nm, a 4CZIPN CBP green light emitting layer of 10-25 nm in mass ratio of 1: 100-1: 25, a TPBi electron transport layer of 30-50 nm and a LiF electron injection layer of 0.5-0.8 nm in a vacuum evaporation chamber of Pa, and finally replacing a mask plate to evaporate cathode metal Al to prepare an electrode cathode layer of 80-100 nm in thickness. The OLED device with the light-emitting area not less than 2mm multiplied by 2mm is prepared by the method. The evaporation rate was: organic matter
LiF is
AL is
d. The fabrication process of the reference device was substantially the same as that of example 2, except that PEDOT: PSS was used directly as the hole injection layer in the reference device, and the film was not solvent vapor treated.
The flow chart for constructing the green OLED in this embodiment is shown in fig. 2. And preparing a green OLED by using the PEDOT/PSS film subjected to DMSO gas phase treatment as a hole injection layer and performing a light emitting test to obtain figures 4 and 5. As can be seen from fig. 4, the green OLED device obtained in example six has good emission performance. Compared with the reference device, the current efficiency of the DMSO-contained PEDOT/PSS layer vapor-treated device is improved from 23.09cd/A to 25.55 cd/A. Maximum luminance of device 7008cd/m from reference example2Increased to 8146cd/m2. The external quantum efficiency and the electroluminescence spectrum of the device are shown in figure 5, the EQE of the device is improved under different brightness, and the maximum EQE is improved from 7.91% of the reference example to 8.5%6%, improved by 8.2%. The electroluminescence spectrum of the device is shown in fig. 5, and it can be seen from the graph that the CIE color coordinate offset of the green OLED device prepared by the hole injection layer after the gas phase treatment is less than 0.01 compared with that of the reference device, which shows that the color stability is good.
In the fifth embodiment and the sixth embodiment, by optimizing a strong polar solvent, a high-concentration gas-phase atmosphere is constructed to carry out micro-etching on a hole injection layer film widely applied to an organic optoelectronic device, so that a scattering microstructure beneficial to light emission is formed, the hole mobility is properly reduced, and meanwhile, the OLED carrier transmission balance and the light coupling improvement are realized. The method has the characteristics of low cost, simple process, large-area processing, capability of processing a film on a flexible substrate and the like. Can be widely applied to the aspects of organic light emitting diode display and illumination.
The embodiment of the green OLED device with the waveguide mode light coupling enhancement relates to the field of organic light emitting diodes. The device comprises a substrate, an anode, a hole injection layer, a hole transport layer, a green light emitting layer, an electron transport layer, an electron injection layer and a cathode. The device is characterized by an organic or inorganic hole injection layer, the hole injection layer film being vapor phase microetched by means of preferably an organic solvent or acid. The embodiment accurately adjusts the etching time and the film thickness of the hole injection layer to control the etching depth of gas molecules and form an effective surface light scattering structure. Therefore, light emitted from the interior of the green OLED device is refracted and diffused when passing through the scattering structure, photons in a waveguide mode can be effectively emitted, the luminous flux is increased, the light coupling efficiency is improved, and the external quantum efficiency is finally improved. The above-described embodiments solve the problem of limited optical coupling of current OLED devices.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitutions, as long as the purpose of the present invention is met, and the present invention shall fall within the protection scope of the present invention without departing from the technical principle and inventive concept of the present invention.
Claims (12)
1. The green OLED device with waveguide mode optical coupling enhancement is characterized by comprising a substrate (1), an anode (2), a hole injection layer (3), a hole transport layer (4), a green light emitting layer (5), an electron transport layer (6), an electron injection layer (7) and a conductive cathode (8) which are sequentially stacked from bottom to top; the light-emitting guest material of the green light-emitting layer (5) adopts fluorescent, phosphorescent and heat-activated delayed fluorescent material which emits green light; the hole injection layer (3) is treated by a solvent, and the etching depth of solvent gas molecules is controlled by adjusting the solvent treatment time and the film thickness of the hole injection layer (3).
2. The green OLED device with waveguide-mode optical coupling enhancement of claim 1, wherein: the hole injection layer (3) is made of polymer materials and comprises at least one of the following materials: poly (3,4-ethylenedioxythiophene) -poly (phenylenesulfonate), poly [ N, N ' -bis (4-butylphenyl) -N, N ' -bis (phenyl) -benzidine ], poly [ bis (4-phenyl) (2,4, 6-trifluoromethylphenyl) amine ] (PTAA), poly [ (9, 9-dimethoxyphenyl-2, 7-diyl) -co- (4,4' - (N- (4-sec-butylphenyl) diphenylamine) ];
or, the hole injection layer (3) adopts a small molecule material, and comprises at least one of the following materials: 4,4',4"-tris (N-3-methylphenyl-N-phenyl-amino) triphenylamine, 4',4" -tris (N- (naphtalen-2-yl) -N-phenyl-amino) triphenylamine, copper (II) phthalocyanine (CuPC), titanium (IV) oxydiphatic yanine, pyraz ino [2,3-f ] [1,10] phenanthrone-2, 3-dicarbonitrile, N, N, N ', N ' -tetrapropyl (4-methoxyphenylamino) benzidine, N, N ' -diphenyl-N, N ' -di- [4- (N, N-di-p-tolylamino) phenylphenylphenylphenylbenzidine, N, N ' -di- [ 4' - (4-tolyl-p-tolyll-amino) phenylphenylbenzidine, N, N ' -dithiophenyl ] benzidine, N, N ' -dithiophenyl ] triphenylamine, N, 4' -dithiophenyl-N-4 ' -dithiophenyl-aminothiophene [4, N ' -dithiophenyl-4 ' - (3-thienyl-2, 4' -dithiophenyl-3-diyl) triphenylamine, N, N ' -dithiophenyl-4 ' -dithiophene-4, N, N ' -dithiophenyl-4 ' -dithiophene-4, N, N, 4' -dithiophene-4, 4' -dithiophene-3, 4' -dithiophene-3632, 4' -dithiophene-4, 4' -dithiophene-3, 4' -dithiophene-, 3'-h ] quinoxaline-2,3,6,7,10,11-hexa carbonitrile, diquinoxaline [2,3-a:2',3'-c ] phenazine, 7,8,8-tetracyano quinodimethane, 2,3,5,6-tetrafluoro-7,7,8, 8-tetracyano-quinodimethane, 2' - (naphthalene-2, 6-diyl) dimethanol;
alternatively, the hole injection layer (3) is made of an oxide materialComprising at least one of the following materials: MoO3、CuO、V2O5、NiO2、WO3。
3. The green OLED device with waveguide-mode optical coupling enhancement of claim 1, wherein: the substrate layer (1) is made of at least one of rigid glass materials, transparent polymer flexible materials and biodegradable flexible materials.
4. The green OLED device with waveguide-mode optical coupling enhancement of claim 1, wherein: the anode (2) is made of at least one of ITO, FTO, AZO, IZO, graphene, carbon nano tubes, elementary metal nano wires, metal alloy nano wires and metal heterojunction nano wires; the thickness of the anode is 80-200 nm.
5. The green OLED device with waveguide-mode optical coupling enhancement of claim 1, wherein: the hole transport layer (4) is made of N, N ' -bis (naphthalene-1-yl) -N, N ' -bis (phenyl) -benzidine, N ' -bis (3-methylphenyl) -N, N ' -bis (phenyl) -benzidine, 4' -tris (carbozol-9-yl) triphenylamine, N ' -bis (3-methylphenyl) -N, N ' -bis (phenyl) -2, 7-diamido-9, 9-spirobifluorene, N ' -bis (naphthalene-1-yl) -N, N ' -bis (phenyl) -2, 7-diamido-9, 9-diamido-fluoroene, 9-bis [4- (N, N-hydroxyphenyl) -2-phenyl ] -9-diamido-9, 9-diamido-9-fluoronaphthalene, At least one material selected from di- [4- (N, N-di-p-tolyl-amino) -phenyl ] cyclohexane, N1, N4-diphenyl-N1, N4-di-m-tolyilbenzene-1, 4-diamine, N4, N4' -bis (4- (6- ((3-ethylhexylan-3-yl) methoxy) phenyl) -N4, N4' -diphenylylphenyl-4, 4' -diamine, 4' - (diphenylsilylediyl) bis (N, N-diphenyleneine), 4' - (diphenylmethyene) bis (N, N-diphenyleneine).
6. The green OLED device with waveguide-mode optical coupling enhancement of claim 1, wherein: the light-emitting guest material of the green light-emitting layer (5) is fac-tris (2-phenylpyridine) iridium (III),bis(2-phenylpy ridine)(acetylacetonate)iridium(III)、9,10-bis[N,N-di-(p-tol yl)-amino]anthracene、N10,N10,N10',N10'-tetraphenyl-9,9'-bianthrac ene-10,10'-diamine、9,9',9”-(5-(4,6-diphenyl-1,3,5–triazin-2-yl)benzene-1,2,3-triyl)tris(3,6-dimethyl-9H-carbazole)、9,10-bis[N,N-di-(p-tolyl)-amino]anthracene、(4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile、2,5-bis(4-(10H-phenoxa zin-10-yl)phenyl)-1,3,4-oxadiazole、10,10'-(4,4'-sulfonlybis(4,1-phenylene))bis(10H-phenoxazine)、1,4-bis(9,9-dimethylacridan-10-yl-pphenyl)-2,5-bis(p-tolyl-metha noyl)benzene、bis(4-(9,9-dimethylacridin-10(9H)-yl)phenyl)methanone、5-chloro-2,4,6-tris(3,6-di-tert-butyl-9H-carbazol-9-yl)isophthalonitrile、4,4”-di-10H-phenoxazin-10-yl[1,1':2',1”-terphenyl]-at least one of 4',5' -dicarbonitrile;
the main luminescent material of the green luminescent layer (5) is 1,3-bis (carbozol-9-yl) benzene, 2,8-bis (phenyleophoryl) bis [ b, d ] thiophene (PPT), 4 '-tris (carbozol-9-yl) triphenylamine, 4' -bis (carbozol-9-yl) phenyl, bis [2- (phenyletho) phenyl ] ether, 2,6-di (9H-carbozol-9-yl) pyridine, 2,4,6-tris (3- (9H-carbozol-9-yl) phenyl) -1,3,5-triazine, 4'- (9H-carbozol-9-yl) phenyl, 5-bis (3- (9H-carbozol-9-yl) phenyl) -1,3,5-triazine, 4' - (9H-carbozol-9-phenyl) phenyl, 5-phenyl, 3- (4-carbozol-9-yl) phenyl, 4- (3-4-carbozol-10-yl) phenyl ] phenyl, 4- (9H-carbozol-9-yl) phenyl) At least one of-9, 9-dimethyl-9, 10-dihydroacridine.
7. The green OLED device with waveguide-mode optical coupling enhancement of claim 1, wherein: the electron transport layer (6) is made of 4,7-diphenyl-1,10-phenanthroline, 2'- (1,3, 5-phenanetryl) -tris (1-phenyl-1-H-phenantzolide), thiocuproline, tris- (8-hydroxyquinolato) aluminum, 2- (4-biphenyl) -5- (4-tert-butyl-phenyl) -1,3, 4-oxadiazine, bis (2-methyl-8-quinolate) -4- (phenanolato) aluminum, 1,3-bis [2- (2,2' -biphenyl-6-yl) -1,3, 4-oxadiazine-5-yl ] aluminum]benzene、4-(naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-triazole、tris(2,4,6-trimethyl-3-(pyridin-3-yl)phenyl)borane、phenyl-dipyrenylphosphine oxide、1,3-bis[2-(4-tert-butylphenyl)-1,3,4-oxadiazo-5-yl]benzene、1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene, graphene, carbon nano tube, ZnO and Cs2CO3At least one of (1).
8. The green OLED device with waveguide-mode optical coupling enhancement of claim 1, wherein: the electron injection layer (7) is made of at least one of lithium fluoride, 8-hydroxyquinoline to-lithium, magnesium fluoride, 8-hydroxyquinoline sodium salt and magnesium fluoride; the cathode (8) is made of at least one of Al, Ag, Au, IZO, Ca, magnesium-silver alloy and lithium-aluminum alloy.
9. A method of making a green OLED device with waveguide-mode optical coupling enhancement of claim 1, comprising the steps of:
1) cleaning the substrate and the anode, and drying by nitrogen;
2) preparing a hole injection layer on the surface of the anode by adopting a spin coating, printing, spraying or evaporation mode and adopting a hole injection layer material;
3) heating a preferred solvent in a closed container to generate a high-concentration steam atmosphere, adjusting the flow rate of solvent gas, putting the hole injection layer film into the container, standing for a set time, taking out, and annealing and drying the film at different annealing temperatures according to the used solvent;
4) preparing a hole transport layer, a green light emitting layer, an electron transport layer and an electron injection layer in sequence by adopting a spin coating, printing, spraying or evaporation mode on the surface of the hole injection layer treated in the step 3);
5) replacing a mask plate, and evaporating a cathode material on the surface of the electron injection layer prepared in the step 4) to form an electrode cathode layer, so that each functional layer of the OLED is manufactured.
10. The method of making a green OLED device with waveguide-mode optical coupling enhancement of claim 9, wherein: in the step 3), the following steps are adopted:
a. preparing hole injection layers with different thicknesses on the substrate layer/the anode, wherein the thickness is 10-50 nm; the hole injection layer is made of at least one of a polymer, a small molecule or an oxide which is mainly used for transmitting holes, has an energy level matched with that of the anode and the hole transmission layer and can be dissolved by a volatile solvent and an acid;
b. creating a high-concentration organic solvent or acid vapor atmosphere in a closed container, enabling gas to continuously flow, and placing a hole injection layer film for standing for different times to control the penetration depth of gas molecules; adjusting the steam flow rate to be 3-10L/min, and keeping the film standing for 30-60 min;
c. and taking out the hole injection layer film, annealing and drying to obtain the processed hole injection layer.
11. The method of making a green OLED device with waveguide-mode optical coupling enhancement of claim 9, wherein: the solvent for gas phase treatment adopts an organic solvent or acid, and the solvent for gas phase treatment adopts at least one of methanol, ethanol, n-butanol, isopropanol, acetone, DMA, DMSO, DMF, tetrahydrofuran, toluene, chlorobenzene, dichloromethane, trichloromethane, carbon disulfide, triethylamine, m-cresol, hydrochloric acid, nitric acid, acetic acid and formic acid.
12. The method of making a green OLED device with waveguide-mode optical coupling enhancement of claim 9, wherein: the flow rate of the solvent vapor in the closed container is adjusted to be 3-10L/min, and the standing time of the film in the atmosphere is 30-60 min.
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