CN104466008A - Organic light-emitting diode device and preparation method thereof - Google Patents
Organic light-emitting diode device and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H10K50/85—Arrangements for extracting light from the devices
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- H—ELECTRICITY
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- H10K50/00—Organic light-emitting devices
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- H10K50/854—Arrangements for extracting light from the devices comprising scattering means
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Abstract
The invention provides an organic light-emitting diode device comprising a substrate, a conductive anode, a light-emitting function layer and a conductive cathode. The substrate, the conductive anode, the light-emitting function layer and the conductive cathode are successively laminated. In addition, the organic light-emitting diode device also includes a light extraction layer arranged at one or two surfaces of the substrate; and the light extraction layer and a light-emitting function layer are arranged in an opposite or face-to-face mode. The materials employed by the light extraction layer contain at least three kinds of different-diameter-based nanoparticle materials doped in a polymer material. According to the organic light-emitting diode device provided by the invention, because of the light scattering effect of the nanoparticles, the nanoparticles with different dimensions can scatter various light with different wavelengths, thereby changing the reflection direction of the incident light at the surface and changing the total-reflection critical angle of the integrated light emitting. Therefore, the light emitting efficiency can be increased.
Description
Technical field
The present invention relates to field of organic electroluminescence, particularly relate to a kind of Organnic electroluminescent device and preparation method thereof.
Background technology
Organic electroluminescent, also known as OLED, has the characteristics such as brightness is high, material selection range is wide, driving voltage is low, all solidstate active illuminating, has high definition, wide viewing angle simultaneously, and the advantage such as fast response time.Be a kind of Display Technique and light source of great potential, meet the development trend of information age mobile communication and information displaying, and the requirement of green lighting technique, be the focal point of current lot of domestic and foreign researcher.
The OLED light-emitting device of usual preparation, due to electrode material, the refractive index between glass substrate and air is not mated.The light that OLED luminescence unit is launched transmits from electrode to glass substrate, and when then entering in air, under the restriction of the cirtical angle of total reflection, generally only have the light of about 17% can outgoing, most light be then limited in OLED structure.
Summary of the invention
The object of the present invention is to provide a kind ofly increases the Organnic electroluminescent device of luminous efficiency and the preparation method of this Organnic electroluminescent device.
In order to solve the problems of the technologies described above, the invention provides a kind of Organnic electroluminescent device, described Organnic electroluminescent device comprises the substrate stacked gradually, conductive anode, light emitting functional layer and conductive cathode, wherein, described Organnic electroluminescent device also comprises the light-extraction layer be arranged on one or two surface of described substrate, and this light-extraction layer and described light emitting functional layer opposing or arrange in opposite directions, described light emitting functional layer is luminous through described light-extraction layer, described light-extraction layer thickness range is 10 μm ~ 100 μm, the Nano microsphere that described light-extraction layer material comprises at least three kinds of different-diameters adulterates the mixture formed in the polymer, the mass ratio of described Nano microsphere and polymer is 10:100 ~ 50:100, the material of described Nano microsphere is the material of silicon dioxide or titanium dioxide or macromolecule polysterol, and the material of described polymer is the material of the amide resin of the epoxy resin of hot curing or the acrylic resin of photocuring or hot curing, the Nano microsphere of described at least three kinds of different-diameters comprises first group of Nano microsphere, second group of Nano microsphere and the 3rd group of Nano microsphere, described first group of Nano microsphere diameter range is 50nm ~ 199nm, described second group of Nano microsphere diameter range is 200nm ~ 599nm, described 3rd group of Nano microsphere diameter range is 600nm ~ 1500nm, described first group of Nano microsphere accounts for 5% ~ 40% of Nano microsphere total amount in described light-extraction layer, described second group of Nano microsphere accounts for 40% ~ 90% of Nano microsphere total amount in described light-extraction layer, described 3rd group of Nano microsphere accounts for 5% ~ 20% of Nano microsphere total amount in described light-extraction layer.
Wherein, described conductive anode is indium and tin oxide film or indium-zinc oxide or aluminium zinc oxide or gallium zinc oxide; Described conductive cathode material is gold or silver or aluminium or magnesium or metal alloy.
Wherein, described conductive cathode thickness range is 70nm ~ 200nm; Described conductive anode thickness range is 70nm ~ 200nm.
Wherein, described light emitting functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually.
Wherein, described hole injection layer material is Phthalocyanine Zinc, CuPc or phthalocyanine platinum;
The layer material of described cave transport layer is 4,4', 4''-tri-(2-naphthylphenyl is amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, (4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines) or 4,4', 4''-tri-(carbazole-9-base) triphenylamine;
The material of luminescent layer comprises the composite material of material of main part doping guest materials composition, the mass ratio of material of main part and guest materials is 1:100 ~ 20:100, described guest materials is 4-(dintrile methyl)-2-butyl-6-(1, 1, 7, 7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, two (4, 6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes iridium, two (4, 6-difluorophenyl pyridinato)-four (1-pyrazolyl) boric acid conjunction iridium (FIr6), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium, three (1-phenyl-isoquinolin) close iridium or three (2-phenylpyridines) close iridium, described material of main part is 4, 4'-bis-(9-carbazole) biphenyl, oxine aluminium, 1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines,
Or the material of described luminescent layer is (4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl, 4,4'-two [4-(di-p-tolyl is amino) styryl] biphenyl, 5,6,11,12-tetraphenyl naphthonaphthalene or dimethylquinacridone;
The material of described electron transfer layer is 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole, 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene or 1,2,4-triazole derivative;
The material of described electron injecting layer is LiF.
A preparation method for Organnic electroluminescent device, it comprises step:
One substrate is provided;
Silk screen printing order number light-extraction layer described in one or two deposited on silicon of described substrate is preset with first, through photocuring or hot curing film forming, wherein,
The Nano microsphere that described light-extraction layer material comprises at least three kinds of different-diameters adulterates the mixture formed in the polymer, and the mass ratio of described Nano microsphere and polymer is 10:100 ~ 50:100, the material of described Nano microsphere is the material of silicon dioxide or titanium dioxide or macromolecule polysterol, and the material of described polymer is the material of the amide resin of the epoxy resin of hot curing or the acrylic resin of photocuring or hot curing, the Nano microsphere of described at least three kinds of different-diameters comprises first group of Nano microsphere, second group of Nano microsphere and the 3rd group of Nano microsphere, described first group of Nano microsphere diameter range is 50nm ~ 199nm, described second group of Nano microsphere diameter range is 200nm ~ 599nm, described 3rd group of Nano microsphere diameter range is 600nm ~ 1500nm, described first group of Nano microsphere accounts for 5% ~ 40% of Nano microsphere total amount in described light-extraction layer, described second group of Nano microsphere accounts for 40% ~ 90% of Nano microsphere total amount in described light-extraction layer, described 3rd group of Nano microsphere accounts for 5% ~ 20% of Nano microsphere total amount in described light-extraction layer,
Vacuum sputtering conductive anode on the substrate, described conductive anode is conductive oxide film;
At described conductive anode away from described substrate side vacuum evaporation light emitting functional layer, described light emitting functional layer is luminous through substrate under the first predeterminated voltage;
In described light emitting functional layer away from described conductive anode one side vacuum evaporation conductive cathode, described conductive cathode is metallic film.
Wherein, silk screen printing order number is being preset in the step of light-extraction layer described in one or two deposited on silicon of described substrate with first, described light-extraction layer material comprises the Nano microsphere of at least three kinds of different-diameters, in photocuring or hot curing film forming, described first silk screen printing order number scope is 200 ~ 600.
Wherein, at described conductive anode away from described substrate side vacuum evaporation light emitting functional layer, described light emitting functional layer is through in the step of substrate luminescence under the first predeterminated voltage, and described first predeterminated voltage is 6V.
The preparation method of Organnic electroluminescent device provided by the invention and this Organnic electroluminescent device, because Nano microsphere has light scattering effect, the Nano microsphere of sizes can produce scattering to the light of multiple different wave length, change the reflection direction of incident light on its surface, thus change the cirtical angle of total reflection of overall light outgoing, thus increase light extraction efficiency.It is relative to the Nano microsphere of single size, effectively can solve the shortcoming that it strengthens narrower part wavelength dispersion effect, also can improve the problem that luminescent spectrum narrows simultaneously.
Accompanying drawing explanation
In order to be illustrated more clearly in technical scheme of the present invention, be briefly described to the accompanying drawing used required in execution mode below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the Organnic electroluminescent device schematic diagram that the invention provides the first execution mode;
Fig. 2 is the Organnic electroluminescent device schematic diagram that the invention provides the second execution mode;
Fig. 3 is the Organnic electroluminescent device schematic diagram that the invention provides the 3rd execution mode.
Embodiment
Below in conjunction with the accompanying drawing in embodiment of the present invention, the technical scheme in embodiment of the present invention is clearly and completely described.
Refer to Fig. 1, a kind of Organnic electroluminescent device 100 that first embodiment of the invention provides, it comprises the substrate 10, light-extraction layer 11, conductive anode 12, light emitting functional layer 13 and the conductive cathode 14 that stack gradually.Described substrate 10 is positioned at described conductive anode 12 away from described light emitting functional layer 13 side, and described light-extraction layer 11 is arranged between described substrate 10 and described conductive anode 12.Described light emitting functional layer 13 is luminous through described substrate 10 under the voltage driven of described conductive anode 12 and conductive cathode 14.Light-extraction layer 11 described in the light therethrough that described light emitting functional layer 13 sends.
Concrete, described substrate 10 is clear glass, and described substrate 10 comprises the first plane 10a and the second plane 10b that are oppositely arranged.Described light emitting functional layer 13 can be arranged near described first plane 10a, also can be arranged near described second plane 10b.When described light emitting functional layer 13 is arranged near described first plane 10a, described first plane 10a is plane of light incidence, and described second plane 10b is light outgoing plane; When described light emitting functional layer 13 is arranged near described second plane 10b, described second plane 10b is plane of light incidence, and described first plane 10a is light outgoing plane.
For improving the luminous efficiency of described Organnic electroluminescent device, increase light-extraction layer at the plane of light incidence of described substrate or beam projecting face, or plane of light incidence and beam projecting face all increase light extract layer.In present embodiment, described light-extraction layer 11 is arranged at described substrate 10 on a surface of described light emitting functional layer 13, and described light-extraction layer 11 is arranged in opposite directions with described light emitting functional layer 13.Certainly, described substrate can also be arranged at away from described light emitting functional layer surface in light-extraction layer described in other embodiments, described light-extraction layer and described light emitting functional layer support or oppose and arrange, or described light-extraction layer is arranged at substrate near described light emitting functional layer with away from two surfaces of described light emitting functional layer.
Described light-extraction layer 11 is arranged at described first plane 10a.Described light-extraction layer 11 forms light transmission film at described first plane 10a.Concrete, described light-extraction layer 11 material comprises nanospheres and the polymeric material of at least three kinds of different-diameters.In order to make described light-extraction layer 11 form film, described light-extraction layer 11 material comprises polymer, and the Nano microsphere of described at least three kinds of different-diameters is mixed in described polymer.The Nano microsphere material of described at least three kinds of different-diameters is silicon dioxide or titanium dioxide or any one ceramic material of macromolecule polysterol or macromolecular material.Described polymerizable material is any one heat reactive resin of amide resin or the light-cured resin of the epoxy resin of hot curing or the acrylic resin of photocuring or hot curing.More specifically, in present embodiment, described light-extraction layer 11 comprises first group of Nano microsphere, second group of Nano microsphere and the 3rd group of Nano microsphere, and described three groups of Nano microsphere diameters are all in different scopes.Described Nano microsphere material selection titanium dioxide.Described polymerizable material selects the acrylic resin of photocuring.Certainly, in other embodiments, described light-extraction layer can also comprise the 4th group of Nano microsphere.Described Nano microsphere material can also select silicon dioxide or macromolecule polysterol etc.Described polymer can also select the epoxy resin of hot curing or the amide resin etc. of hot curing.
Because described Nano microsphere mixes mutually with the component of different-diameter, so the diameter range of described Nano microsphere and described first group of Nano microsphere, between second group of Nano microsphere and the 3rd group of Nano microsphere, mass ratio produces Different Effects to the luminous efficiency of described Organnic electroluminescent device 100.Described first group of Nano microsphere diameter range is 50nm ~ 199nm, described second group of Nano microsphere diameter range is 200nm ~ 599nm, described 3rd group of Nano microsphere diameter range is 600nm ~ 1500nm, described first group of Nano microsphere accounts for 5% ~ 40% of Nano microsphere total amount in described light-extraction layer 11, described second group of Nano microsphere accounts for 40% ~ 90% of Nano microsphere total amount in described light-extraction layer 11, and described 3rd group of Nano microsphere accounts for 5% ~ 20% of Nano microsphere total amount in described light-extraction layer 11.In present embodiment, described first group of Nano microsphere diameter is 50nm, and described second group of Nano microsphere diameter is 250nm, and described 3rd group of Nano microsphere diameter is 800nm.Certainly, in other embodiments, can also Nano microsphere all containing different-diameter in described first group of Nano microsphere, second group of Nano microsphere and the 3rd Nano microsphere.Such as, in second group of Nano microsphere, being 300nm and diameter containing diameter is two kinds of Nano microspheres of 500nm and mixes with the ratio of 40:60.But the Nano microsphere of these two kinds of different-diameters to account in described light-extraction layer 11 Nano microsphere total amount all the time between scope 40% ~ 90%.Certainly, in other embodiments, if described light-extraction layer also comprises the 4th group of Nano microsphere, then the diameter range of described 4th group of Nano microsphere can also for being greater than 1500nm, and it can also be less than 5% that described 4th group of Nano microsphere accounts for Nano microsphere total amount in light-extraction layer 11.
Because described Nano microsphere mixes mutually with described polymer, so the quality of Nano microsphere total amount and described polymer is 10:100 ~ 50:100 than scope in described light-extraction layer 11.Due to described first group of Nano microsphere, between second group of Nano microsphere and the 3rd group of Nano microsphere, mass ratio is different, and Nano microsphere total amount is different from the ratio of described polymer in described light-extraction layer 11, different results is all produced to the luminous efficiency of described Organnic electroluminescent device 100.In present embodiment, provide three kinds of concrete described first group of Nano microspheres, the mass ratio of Nano microsphere total amount and described polymer in mass ratio and described light-extraction layer 11 between second group of Nano microsphere and the 3rd group of Nano microsphere, detailed data refers to table 1.Certainly, in other embodiments, described first group of Nano microsphere, between second group of Nano microsphere and the 3rd group of Nano microsphere, in mass ratio and described light-extraction layer 11, the mass ratio of Nano microsphere total amount and described polymer can also be other multi-form combinations in preferable range.
In addition, the luminous efficiency of thickness to described Organnic electroluminescent device 100 of described light-extraction layer 11 has an impact equally.As a kind of preferred version, described light-extraction layer 11 thickness range is 10 μm ~ 100 μm.In present embodiment, corresponding three kinds of described first group of Nano microspheres, between second group of Nano microsphere and the 3rd group of Nano microsphere, ratio provides the light-extraction layer of three kinds of different-thickness, and concrete data are see table 1.
In present embodiment, described conductive anode 12 is indium and tin oxide film, and thickness is 100nm.Certainly, in other embodiments, described conductive anode can also be indium-zinc oxide or aluminium zinc oxide or any one transparent conductive oxide film of gallium zinc oxide, and described conductive anode thickness can also be other thickness in scope 70nm ~ 200nm.
For increasing the luminous efficiency of described Organnic electroluminescent device 100, in present embodiment, light emitting functional layer 13 comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually.Certainly, in other embodiments, between described conductive anode and conductive cathode, hole transmission layer, luminescent layer, electron transfer layer can also be set gradually, but between described conductive anode and conductive cathode, luminescent layer is necessary.In present embodiment, the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and and the electron injecting layer that stack gradually are set between described conductive anode 12 and described conductive cathode 14.Certainly, in other embodiments, in order to improve luminous efficiency, between described conductive anode and described conductive cathode, hole blocking layer and electronic barrier layer can also be comprised.Described hole blocking layer is between described luminescent layer and described electron transfer layer, and described electronic barrier layer is between described luminescent layer and described hole transmission layer.
Concrete, described electron injecting layer material is LiF, thickness 1nm.
The material of described electron transfer layer is 2-(4-xenyl)-5-(4-the tert-butyl group) phenyl-1,3,4-oxadiazole, 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene or 1,2,4-triazole derivative.In present embodiment, described electron transfer layer selects 4,7-diphenyl-o-phenanthroline, and thickness is 3nm.
The material of luminescent layer comprises the composite material of material of main part doping guest materials composition, and the mass ratio of material of main part and guest materials is 1:100 ~ 20:100.Described guest materials is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic closes iridium, two (4,6-difluorophenyl pyridinato)-four (1-pyrazolyl) boric acid closes iridium (FIr6), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium, three (1-phenyl-isoquinolin) close iridium or three (2-phenylpyridines) close iridium; Described material of main part is 4,4'-bis-(9-carbazole) biphenyl, oxine aluminium, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene, N, N'-diphenyl-N, N'-bis-(1-naphthyls)-1,1'-biphenyl-4,4'-diamines.Or the material of described luminescent layer is (4,4'-bis-(2,2-diphenylethyllene)-1,1'-biphenyl, 4,4'-two [4-(di-p-tolyl is amino) styryl] biphenyl, 5,6,11,12-tetraphenyl naphthonaphthalene or dimethylquinacridone.In present embodiment, described luminescent layer adopts oxine aluminium, and thickness is 20nm.
The layer material of described cave transport layer is 4,4', 4''-tri-(2-naphthylphenyl is amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, (4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines) or 4,4', 4''-tri-(carbazole-9-base) triphenylamine.In present embodiment, described hole transmission layer adopts N, N'-diphenyl-N, and N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, thickness is 30nm.
Described hole injection layer material is Phthalocyanine Zinc, CuPc or phthalocyanine platinum.In present embodiment, described hole injection layer adopts CuPc, and thickness is 20nm.
Described conductive cathode 14 material is any one metallic film of gold or silver or aluminium or magnesium or metal alloy, and described conductive cathode 14 thickness range is 70nm ~ 200nm.In present embodiment, described conductive cathode 14 material is silver, and thickness is 100nm.
For more described light-extraction layer 11 affects the luminous efficiency of described Organnic electroluminescent device with the Nano microsphere containing single diameter containing there being the Nano microsphere of multiple diameter.The invention provides the Organnic electroluminescent device of the first contrast execution mode.Described first contrast execution mode and described first execution mode difference are that described light-extraction layer adopts single diameter to be the Nano microsphere of 200nm, and the mass ratio of described Nano microsphere and polymer is 20:100.Correction data refers to table 1.
For more described light-extraction layer is on the impact of described Organnic electroluminescent device, the invention provides the Organnic electroluminescent device of the second contrast execution mode.Described second contrast execution mode is from the first different dwelling of execution mode, and described Organnic electroluminescent device cancels light-extraction layer.Correction data refers to table 1.
This first execution mode also provides a kind of preparation method of Organnic electroluminescent device, and it comprises step:
101: a substrate is provided.
102: preset silk screen printing order number light-extraction layer described in one or two deposited on silicon of described substrate with first, through photocuring or hot curing film forming, wherein,
The Nano microsphere material that described light-extraction layer material comprises at least three kinds of different-diameters is silicon dioxide, or titanium dioxide, or the material of macromolecule polysterol and polymerizable material are the epoxy resin of hot curing, or the acrylic resin of photocuring, or the material of the amide resin of hot curing, the nanospheres of described at least three kinds of different-diameters is doped in described polymeric material, the Nano microsphere of described at least three kinds of different-diameters comprises first group of Nano microsphere, second group of Nano microsphere and the 3rd group of Nano microsphere, described first group of Nano microsphere diameter range is 50nm ~ 199nm, described second group of Nano microsphere diameter range is 200nm ~ 599nm, described 3rd group of Nano microsphere diameter range is 600nm ~ 1500nm, described first group of Nano microsphere accounts for 5% ~ 40% of Nano microsphere total amount in described light-extraction layer, described second group of Nano microsphere accounts for 40% ~ 90% of Nano microsphere total amount in described light-extraction layer, described 3rd group of Nano microsphere accounts for 5% ~ 20% of Nano microsphere total amount in described light-extraction layer.
In present embodiment, preset silk screen printing order number in the step of light-extraction layer described in one or two deposited on silicon of described substrate with first, described silk screen printing order number scope is 200 ~ 600.More specifically, utilize screen printing apparatus that the mixed solution of Nano microsphere and polymer is deposited equably on the substrate by mesh under the effect of scraper plate.In the present embodiment, described light-extraction layer material comprises the Nano microsphere of three groups of different-diameters and the mixing of polymer, concrete, and first group of Nano microsphere diameter is 50nm, and second group of Nano microsphere diameter is 250nm, and the 3rd group of Nano microsphere diameter is 800nm.Certainly, in other embodiments, described first Nano microsphere diameter can also be within the scope of 50 ~ 199nm, also has diameter 60nm and 80nm two kinds mixing.In addition, in present embodiment, provide the ratio of described three groups of Nano microsphere content, detailed data is see table 1.Described Nano microsphere material is titanium dioxide, and described polymerizable material is acrylic resin.Certainly, in other embodiments, described light-extraction layer can also arrange the 4th group of Nano microsphere, and the Nano microsphere mass ratio of described four groups of different-diameters can also be other forms of combination.In present embodiment, for different silk screen printing order number, the luminous efficiency of described Organnic electroluminescent device is affected, concrete corresponding three kinds described first group Nano microspheres, between second group of Nano microsphere and the 3rd group of Nano microsphere, ratio provides three kinds of different silk screen printing order numbers, and detailed data is see table 1.
103: vacuum sputtering conductive anode on the substrate, described conductive anode is conductive oxide film.
In present embodiment, vacuum sputtering conductive anode on the substrate, described conductive anode is in conductive oxide film, using described substrate as bombardment target.In present embodiment, described conductive anode 12 is formed near described first plane 10a side, in vacuum degree 10
-4avacuum coating equipment in, using described substrate 10 as negative potential, described conductive oxide, as the bombardment of positive potential by lotus energy particle, is sputtered onto in the light-extraction layer 11 on the first plane 10a of described substrate 10 by described conductive oxide raw material, forms conductive oxide film.Certainly, in other embodiments, if described conductive anode 12 can also be formed on described second plane 10b.
104: at described conductive anode away from described substrate side vacuum evaporation light emitting functional layer successively, described light emitting functional layer is luminous through substrate under the first predeterminated voltage.
In present embodiment, at described conductive anode away from described substrate side vacuum evaporation light emitting functional layer successively, described light emitting functional layer under the first predeterminated voltage through in substrate luminescence, vapour pressure is provided to the raw material of light emitting functional layer, raw material are gasified, and condensation, nucleation form film then on described conductive anode.In present embodiment, on conductive anode, film forming order is followed successively by hole injection layer, hole transmission layer, organic luminous layer, electron transfer layer, electron injecting layer.Certainly, in other embodiments, if also comprise hole blocking layer and electronic barrier layer between conductive anode and conductive cathode, then after described hole transmission layer is formed, form electronic barrier layer, after described luminescent layer is formed, form hole blocking layer.
105: in described light emitting functional layer away from described conductive anode one side vacuum evaporation conductive cathode, described conductive cathode is metallic film.
In present embodiment, in described light emitting functional layer away from described conductive anode one side vacuum evaporation conductive cathode, described conductive cathode is in metallic film, in vacuum degree 10
-4avacuum coating equipment in, provide vapour pressure to the raw material of conductive cathode, raw material gasified, and condense on described electron injecting layer, nucleation forms film then.In present embodiment, the raw material of described conductive cathode are silver, and described conductive cathode is formed at described electron injecting layer away from described electron transfer layer side.Certainly, in other embodiments, described conductive cathode raw material can also be gold, aluminium or magnesium etc.
For the luminous efficiency of more described Organnic electroluminescent device, in present embodiment, corresponding described three kinds described first group Nano microspheres, the light-extraction layer that between second group of Nano microsphere and the 3rd group of Nano microsphere, mass ratio is different provide three kinds of different silk screen printing order numbers.And the light-extraction layer in corresponding described first contrast execution mode, different silk screen printing order numbers is provided.Concrete data refer to table 1.
First execution mode and the first contrast execution mode and second are contrasted execution mode and carries out test and comparison, described test luminous efficiency presets driving voltage at first of 6V to carry out, and described luminescent layer is luminous through described substrate 10 under presetting driving voltage first.
Table 1 is the contrast test result obtained in present embodiment, as can be seen from the table, after adopting light-extraction layer, the luminous efficiency of Organnic electroluminescent device can be significantly improved, bring up to more than 17.8lm/W from initial 10.3lm/W, the luminous efficiency that embodiment provided by the invention improves is higher, contrast compared with execution mode with first, its highest luminous efficiency has brought up to 23.6lm/W, improves more than 40%, and relative second contrast execution mode, its efficiency improves 129%.
The luminous efficiency of Organnic electroluminescent device tested by table 1
Refer to Fig. 2, the Organnic electroluminescent device 200 that second embodiment of the invention provides, described second execution mode and the first execution mode difference are that the light-extraction layer 21 of described Organnic electroluminescent device 200 is arranged at described substrate 20 away from described light emitting functional layer 23 one side.Described light-extraction layer 21 adopts Properties of Polystyrene Nano Particles, and described first group of Nano microsphere diameter is 180nm, and described second group of Nano microsphere diameter is 400nm, and described 3rd group of Nano microsphere diameter is 1500nm.Described polymeric material is light-cured acrylic resin, and the quality of the Nano microsphere total amount in described light-extraction layer 21 and polymer is 10:100 ~ 50:100 than scope.
Same, in present embodiment, there is provided three kinds different described in state first group of Nano microsphere, mass ratio between second group of Nano microsphere and the 3rd group of Nano microsphere, and the thickness of the mass ratio of the Nano microsphere of correspondence and polymer, the meshcount of light-extraction layer and light-extraction layer.Detailed data refers to table 2.
For the Nano microsphere of more described light-extraction layer 21 containing three kinds of diameters affects the luminous efficiency of described Organnic electroluminescent device with the Nano microsphere containing single diameter.The invention provides the Organnic electroluminescent device of the 3rd contrast execution mode.Described 3rd contrast execution mode and described second execution mode difference are that described light-extraction layer adopts single diameter to be the Nano microsphere of 400nm, and the mass ratio of described Nano microsphere and polymer is 20:100.Correction data refers to table 2.
For more described light-extraction layer is on the impact of described Organnic electroluminescent device, the invention provides the Organnic electroluminescent device of the 4th contrast execution mode.Described 4th contrast execution mode is from the second different dwelling of execution mode, and described Organnic electroluminescent device cancels light-extraction layer.Correction data refers to table 2.
Second execution mode and the 3rd contrast execution mode and the 4th are contrasted execution mode and carries out test and comparison, described test luminous efficiency presets driving voltage at first of 6V to carry out.
Table 2 is the contrast test results obtained in present embodiment, as can be seen from the table, after adopting light to extract, the luminous efficiency of Organnic electroluminescent device can be significantly improved, bring up to more than 16.1lm/W from initial 10.3lm/W, the efficiency that embodiment provided by the invention improves is higher, contrast compared with execution mode with the 3rd, its highest luminous efficiency has brought up to 30.2lm/W, improves more than 60%, and relative 4th contrast execution mode, its efficiency improves 144%.
The luminous efficiency of Organnic electroluminescent device tested by table 2
Refer to Fig. 3, the Organnic electroluminescent device 300 that third embodiment of the invention provides, described 3rd execution mode and the first execution mode difference are that the light-extraction layer 31 of described Organnic electroluminescent device 300 is arranged at the surface of described substrate 30 away from described light emitting functional layer 33 and the surface near described light emitting functional layer 33.Described light-extraction layer 31 adopts silicon dioxide nanosphere, and it be 50nm and diameter is 100nm two kinds of Nano microspheres that described first group of Nano microsphere contains diameter, and the ratio of the Nano microsphere content of two kinds of different-diameters is 1:1.It is 200nm and diameter is 500nm two kinds of Nano microspheres that described second group of Nano microsphere contains diameter, and the ratio of the Nano microsphere content of two kinds of different-diameters is 1:1.It is 800nm that described 3rd group of Nano microsphere contains single diameter.Described polymeric material is light-cured acrylic resin, and the quality of the Nano microsphere total amount in described light-extraction layer 21 and polymer is 10:100 ~ 50:100 than scope.
Same, in present embodiment, there is provided three kinds different described in state first group of Nano microsphere, mass ratio between second group of Nano microsphere and the 3rd group of Nano microsphere, and the thickness of the mass ratio of the Nano microsphere of correspondence and polymer, the meshcount of light-extraction layer and light-extraction layer.Detailed data refers to table 3.
For the Nano microsphere of more described light-extraction layer 31 containing three kinds of diameters affects the luminous efficiency of described Organnic electroluminescent device with the Nano microsphere containing single diameter.The invention provides the Organnic electroluminescent device of the 5th contrast execution mode.Described 5th contrast execution mode and described 3rd execution mode difference are that described light-extraction layer adopts single diameter to be the Nano microsphere of 400nm, and the mass ratio of described Nano microsphere and polymer is 15:100.Correction data refers to table 3.
For more described light-extraction layer 31 is on the impact of described Organnic electroluminescent device, the invention provides the Organnic electroluminescent device of the 6th contrast execution mode.Described 6th contrast execution mode is from the 3rd different dwelling of execution mode, and the Organnic electroluminescent device of described 6th contrast execution mode cancels light-extraction layer.Correction data refers to table 3.
3rd execution mode and the 5th contrast execution mode and the 6th are contrasted execution mode and carries out test and comparison, described test luminous efficiency is carried out at the driving voltage of 6V.
Table 3 is the test results obtained, as can be seen from the table, the 5th contrast execution mode and the 6th contrast execution mode is compared, after have employed light-extraction layer, the luminous efficiency of Organnic electroluminescent device can be significantly improved, bring up to more than 18.4lm/W from initial 10.3lm/W.The luminous efficiency that the Organnic electroluminescent device 300 of the 3rd execution mode provided by the invention improves is higher, contrast compared with execution mode with the 5th, its highest luminous efficiency has brought up to 31.2lm/W, improves more than 70%, and contrasting compared with execution mode with the 6th, its efficiency improves 203%.
The luminous efficiency of Organnic electroluminescent device tested by table 3
The preparation method of Organnic electroluminescent device provided by the invention and this Organnic electroluminescent device, because Nano microsphere has light scattering effect, the Nano microsphere of sizes can produce scattering to the light of multiple different wave length, change the reflection direction of incident light on its surface, thus change the cirtical angle of total reflection of overall light outgoing, thus increase light extraction efficiency.It is relative to the Nano microsphere of single size, effectively can solve the shortcoming that it strengthens narrower part wavelength dispersion effect, also can improve the problem that luminescent spectrum narrows simultaneously.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (9)
1. an Organnic electroluminescent device, described Organnic electroluminescent device comprises the substrate stacked gradually, conductive anode, light emitting functional layer and conductive cathode, it is characterized in that, described Organnic electroluminescent device also comprises the light-extraction layer be arranged on one or two surface of described substrate, and this light-extraction layer and described light emitting functional layer opposing or arrange in opposite directions, described light-extraction layer thickness range is 10 μm ~ 100 μm, the Nano microsphere that described light-extraction layer material comprises at least three kinds of different-diameters adulterates the mixture formed in the polymer, the mass ratio of described Nano microsphere and polymer is 10:100 ~ 50:100, the material of described Nano microsphere is the material of silicon dioxide or titanium dioxide or macromolecule polysterol, and the material of described polymer is the material of the amide resin of the epoxy resin of hot curing or the acrylic resin of photocuring or hot curing, the Nano microsphere of described at least three kinds of different-diameters comprises first group of Nano microsphere, second group of Nano microsphere and the 3rd group of Nano microsphere, described first group of Nano microsphere diameter range is 50nm ~ 199nm, described second group of Nano microsphere diameter range is 200nm ~ 599nm, described 3rd group of Nano microsphere diameter range is 600nm ~ 1500nm, described first group of Nano microsphere accounts for 5% ~ 40% of Nano microsphere total amount in described light-extraction layer, described second group of Nano microsphere accounts for 40% ~ 90% of Nano microsphere total amount in described light-extraction layer, described 3rd group of Nano microsphere accounts for 5% ~ 20% of Nano microsphere total amount in described light-extraction layer.
2. Organnic electroluminescent device according to claim 1, it is characterized in that, the Nano microsphere of described at least three kinds of different-diameters also comprises the 4th group of Nano microsphere, described 4th group of Nano microsphere diameter range is greater than 1500nm, and described 4th group of Nano microsphere accounts for Nano microsphere total amount in described light-extraction layer and be less than 5%.
3. Organnic electroluminescent device according to claim 1, is characterized in that, described conductive anode is indium and tin oxide film or indium-zinc oxide or aluminium zinc oxide or gallium zinc oxide; Described conductive cathode material is gold or silver or aluminium or magnesium or metal alloy.
4. the Organnic electroluminescent device according to claim 1 or 3, is characterized in that, described conductive cathode thickness range is 70nm ~ 200nm; Described conductive anode thickness range is 70nm ~ 200nm.
5. Organnic electroluminescent device according to claim 1, is characterized in that, described light emitting functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that stack gradually.
6. Organnic electroluminescent device according to claim 4, is characterized in that, described hole injection layer material is Phthalocyanine Zinc, CuPc or phthalocyanine platinum;
The layer material of described cave transport layer is 4,4', 4 "-three (2-naphthylphenyl is amino) triphenylamine, N; N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4; 4'-diamines, (4,4', 4 "-three (N-3-methylphenyl-N-phenyl is amino) triphenylamine, N; N'-diphenyl-N; N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines) or 4; 4', 4 "-three (carbazole-9-base) triphenylamine;
The material of luminescent layer comprises the composite material of material of main part doping guest materials composition, and the mass ratio of material of main part and guest materials is 1:100 ~ 20:100; Described guest materials is 4-(dintrile methyl)-2-butyl-6-(1; 1; 7; 7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, two (4; 6-difluorophenyl pyridinato-N; C2) pyridinecarboxylic closes iridium, two (4; 6-difluorophenyl pyridinato)-four (1-pyrazolyl) boric acid closes iridium (FIr6), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium, three (1-phenyl-isoquinolin) close iridium or three (2-phenylpyridines) close iridium; Described material of main part is 4,4'-bis-(9-carbazole) biphenyl, oxine aluminium, 1,3; 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene, N, N'-diphenyl-N, N'-bis-(1-naphthyls)-1; 1'-biphenyl-4,4'-diamines;
Or the material of described luminescent layer is (4,4'-bis-(2,2-diphenylethyllene)-1; 1'-biphenyl, 4,4'-two [4-(di-p-tolyl is amino) styryl] biphenyl, 5,6; 11,12-tetraphenyl naphthonaphthalene or dimethylquinacridone;
The material of described electron transfer layer is 2-(4-xenyl)-5-(the 4-tert-butyl group) phenyl-1; 3; 4-oxadiazole, 4,7-diphenyl-o-phenanthroline, 1,3; 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene, 2; 9-dimethyl-4,7-biphenyl-1,10-phenanthrolene or 1; 2,4-triazole derivative;
The material of described electron injecting layer is LiF.
7. a preparation method for Organnic electroluminescent device, is characterized in that, it comprises step:
One substrate is provided;
Silk screen printing order number light-extraction layer described in one or two deposited on silicon of described substrate is preset with first, through photocuring or hot curing film forming, wherein,
The Nano microsphere that described light-extraction layer material comprises at least three kinds of different-diameters adulterates the mixture formed in the polymer, and the mass ratio of described Nano microsphere and polymer is 10:100 ~ 50:100, the material of described Nano microsphere is the material of silicon dioxide or titanium dioxide or macromolecule polysterol, and the material of described polymer is the material of the amide resin of the epoxy resin of hot curing or the acrylic resin of photocuring or hot curing, the Nano microsphere of described at least three kinds of different-diameters comprises first group of Nano microsphere, second group of Nano microsphere and the 3rd group of Nano microsphere, described first group of Nano microsphere diameter range is 50nm ~ 199nm, described second group of Nano microsphere diameter range is 200nm ~ 599nm, described 3rd group of Nano microsphere diameter range is 600nm ~ 1500nm, described first group of Nano microsphere accounts for 5% ~ 40% of Nano microsphere total amount in described light-extraction layer, described second group of Nano microsphere accounts for 40% ~ 90% of Nano microsphere total amount in described light-extraction layer, described 3rd group of Nano microsphere accounts for 5% ~ 20% of Nano microsphere total amount in described light-extraction layer,
Vacuum sputtering conductive anode on the substrate, described conductive anode is conductive oxide film;
At described conductive anode away from described substrate side vacuum evaporation light emitting functional layer, described light emitting functional layer is luminous through substrate under the first predeterminated voltage;
In described light emitting functional layer away from described conductive anode one side vacuum evaporation conductive cathode, described conductive cathode is metallic film.
8. the preparation method of Organnic electroluminescent device according to claim 7, it is characterized in that, presetting silk screen printing order number in the step of light-extraction layer described in one or two deposited on silicon of described substrate with first, described first silk screen printing order number scope is 200 ~ 600.
9. the preparation method of Organnic electroluminescent device according to claim 7, it is characterized in that, at described conductive anode away from described substrate side vacuum evaporation light emitting functional layer, described light emitting functional layer is through in the step of substrate luminescence under the first predeterminated voltage, and described first predeterminated voltage is 6V.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106981581A (en) * | 2017-02-08 | 2017-07-25 | 广东工业大学 | A kind of organic electroluminescence device for improving light extraction efficiency |
| WO2021098856A1 (en) * | 2019-11-22 | 2021-05-27 | 纳晶科技股份有限公司 | Light-emitting device, display apparatus with same, and lighting apparatus |
| US11690249B2 (en) | 2018-05-28 | 2023-06-27 | Corning Incorporated | Light extraction substrate of organic light-emitting device and method of fabricating the same |
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2013
- 2013-09-12 CN CN201310413804.XA patent/CN104466008A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106981581A (en) * | 2017-02-08 | 2017-07-25 | 广东工业大学 | A kind of organic electroluminescence device for improving light extraction efficiency |
| US11690249B2 (en) | 2018-05-28 | 2023-06-27 | Corning Incorporated | Light extraction substrate of organic light-emitting device and method of fabricating the same |
| WO2021098856A1 (en) * | 2019-11-22 | 2021-05-27 | 纳晶科技股份有限公司 | Light-emitting device, display apparatus with same, and lighting apparatus |
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