CN104465995A - 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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- CN104465995A CN104465995A CN201310413811.XA CN201310413811A CN104465995A CN 104465995 A CN104465995 A CN 104465995A CN 201310413811 A CN201310413811 A CN 201310413811A CN 104465995 A CN104465995 A CN 104465995A
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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Abstract
The invention provides an organic light-emitting diode device comprising a substrate, a light extraction layer, a conductive anode, a light-emitting function layer and a conductive cathode. The substrate, the light extraction layer, the conductive anode, the light-emitting function layer and the conductive cathode are successively laminated. The light-emitting function layer emits light through the substrate under the voltage drive. The light extraction layer is characterized in that a polymer material is doped with a nanoparticle material and includes a plurality of light-transmitting layers with different nanoparticle contents; and the multiple light-transmitting layers with different nanoparticle contents are laminated along the direction from the substrate to the conductive anode. Because of the different nanoparticle contents in the light-transmitting layers, the body refractive index of the light extraction layer can be changed; and the more the contents, the larger the refractive index. Therefore, the light-transmitting layer approaching the conductive anode has the higher refractive index and the light-transmitting layer approaching the substrate has the lower refractive index, thereby realizing refractive index matching of the light extraction.
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 the preparation method of Organnic electroluminescent device that a kind of light extraction efficiency is high and 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, conductive anode, light emitting functional layer and the conductive cathode that stack gradually, wherein, described Organnic electroluminescent device also comprises the light-extraction layer be arranged between described substrate and described conductive anode, and described light-extraction layer material comprises Nano microsphere and is doped to the mixture formed in polymer, the mass ratio of described Nano microsphere and described 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, described light-extraction layer comprises multiple photic zone being provided with different Nano microsphere content, described multiple photic zone being provided with different Nano microsphere content is stacked to described conductive anode direction according to described substrate, described multiple euphotic Nano microsphere content increases successively according to described substrate to described conductive anode direction, in described light-extraction layer, in single photic zone, Nano microsphere diameter is identical, described multiple euphotic Nano microsphere diameter range 50nm ~ 1500nm, it is described that " individual euphotic Nano microsphere diameter reduces successively according to the direction of described substrate to described conductive anode, described single photic zone thickness range is 10 μm ~ 50 μm, described multiple euphotic thickness reduces successively according to described substrate to described conductive anode direction.
Wherein, described light-extraction layer comprises the first photic zone, the second photic zone and the 3rd photic zone that stack gradually, described first photic zone is near described substrate, described first photic zone to the 3rd euphotic Nano microsphere content according to 5% integral multiple gradient increase, described first photic zone reduces to the 3rd euphotic thickness according to 5 μm of integral multiple gradients.
Wherein, in described light-extraction layer, Nano microsphere total amount and described polymer quality proportion are 10:100 ~ 50:100.
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 anode thickness range is 70nm ~ 200nm, and described conductive cathode 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 "-three (2-naphthylphenyl amino) triphenylamine, N; N '-diphenyl-N, N '-two (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 '-two (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 '-two (9-carbazole) biphenyl, oxine aluminium, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene, N, N '-diphenyl-N, N '-two (1-naphthyls)-1,1 '-biphenyl-4,4 '-diamines;
Or the material of described luminescent layer is (4,4 '-two (2,2-diphenylethyllene)-1,1 '-biphenyl, 4,4 '-bis-[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.
The present invention also provides a kind of preparation method of Organnic electroluminescent device, and it comprises step:
One substrate is provided;
Preset silk screen printing order number with first and deposit described light-extraction layer on the substrate, described light-extraction layer material comprises Nano microsphere and is doped to the mixture formed in polymer; The mass ratio of described Nano microsphere and described 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; Described light-extraction layer forms multiple photic zone being provided with different Nano microsphere content on the substrate successively, described multiple euphotic Nano microsphere content increases successively, in described light-extraction layer, in single photic zone, Nano microsphere diameter is identical, described multiple euphotic Nano microsphere diameter range 50nm ~ 1500nm, described multiple euphotic Nano microsphere diameter reduces successively according to described, described single photic zone thickness range is 10 μm ~ 50 μm, described multiple euphotic thickness reduces successively, and described light-extraction layer is through photocuring or hot curing film forming;
In described light-extraction layer away from described substrate side vacuum sputtering conductive anode, described conductive anode is conductive oxide film;
At described conductive anode away from described light-extraction layer one 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, depositing in the step of described light-extraction layer on the substrate with the first default silk screen printing order number, described first silk screen printing order number scope is 200 ~ 1000, described light-extraction layer forms the first photic zone, the second photic zone and the 3rd photic zone on the substrate successively, described first photic zone to the 3rd euphotic Nano microsphere content according to 5% integral multiple gradient increase, described first photic zone reduces to the 3rd euphotic thickness according to 5 μm of integral multiple gradients.
Wherein, at described conductive anode away from described light-extraction layer one 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 light emitting functional layer is luminous through substrate 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, the present invention is provided with light-extraction layer between conductive anode and substrate, described light-extraction layer comprises multiple photic zone being provided with different Nano microsphere content, and in described multiple photic zone, Nano microsphere diameter and multiple photic zone thickness reduce to conductive anode direction according to substrate, and described multiple photic zone Nano microsphere content increases to conductive anode direction according to substrate.Photic zone due to the Nano microsphere of different content has different light transmittances, therefore arranges the euphotic thinner thickness that content is high, and the low photic zone thickness of content is thicker.By Nano microsphere content different in described photic zone, the bulk refractive index of light-extraction layer can be changed, generally that content is higher, refractive index is larger, the photic zone near conductive anode is made to have higher refractive index like this, refractive index near substrate is lower, thus realizes the index matching of light taking-up.
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.
The for a change refractive index of described Organnic electroluminescent device 100, increases light-extraction layer at the plane of light incidence of described substrate 10.In present embodiment, described first plane 10a is as the plane of incidence, and described light-extraction layer 11 is arranged at the first plane 10a of described substrate 10.Certainly, in other embodiments, if the second plane 10b of described substrate 10 is as the plane of incidence, then described light-extraction layer 11 can also be arranged at the second plane 10b of described substrate.
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 is doped in described polymeric material, and in described light-extraction layer, Nano microsphere and described polymer quality proportion are 10:100 ~ 50:100.Described Nano microsphere material 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 or the light-cured resin of the amide resin of the epoxy resin of hot curing or the acrylic resin of photocuring or hot curing.Described light-extraction layer 11 comprises multiple photic zone being provided with different Nano microsphere content, and described multiple photic zone being provided with different Nano microsphere content is stacked to described conductive anode direction according to described substrate.More specifically, in present embodiment, described light-extraction layer 11 comprises the first photic zone 11a, the second photic zone 11b and the 3rd photic zone 11c that stack gradually, and in described three photic zones, Nano microsphere content is all not identical.Described first photic zone 11a is positioned at described substrate 10 near described conductive anode 12 one side, described second photic zone 11b is positioned at described first photic zone 11a away from described substrate 10 one side, and described 3rd photic zone 11c is positioned at described second photic zone 11b away from described first photic zone 11a one side.In present embodiment, 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 photic zone that four, five or six are provided with different Nano microsphere content.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.
Due to multiple diameter difference stating described Nano microsphere in photic zone different impacts is played on the refraction of light, so the diameter range of Nano microsphere is 50nm ~ 1500nm in described multiple photic zone.Concrete, in described single photic zone, Nano microsphere diameter is identical, and described multiple euphotic Nano microsphere diameter increases successively according to the direction of described substrate to described conductive anode.As a kind of preferred version, in present embodiment, the Nano microsphere diameter of described first photic zone 11a, the second photic zone 11b and the 3rd photic zone 11c is all between 50nm ~ 800nm.For Nano microsphere diameter in more described photic zone affects the luminous efficiency of described Organnic electroluminescent device, in present embodiment, provide embodiment one, embodiment two, implement three and the light-extraction layer 11 of embodiment four.Corresponding described embodiment one, embodiment two, embodiment three and embodiment four provide Nano microsphere diameter in concrete described first photic zone 11a, the second photic zone 11b and the 3rd photic zone 11c respectively.Detailed data is see table 1.Certainly, in other embodiments, if described light-extraction layer 11 comprises four photic zones or five photic zones, then in described multiple photic zone, Nano microsphere diameter can also between 200nm ~ 1500nm scope, or other forms of combination between 50nm ~ 1500nm scope.
Because Nano microsphere described in described light-extraction layer mixes mutually with described polymer, in described light-extraction layer, Nano microsphere and described polymer quality proportion are 10:100 ~ 50:100, and described multiple euphotic Nano microsphere content increases to described conductive anode 12 direction successively according to described substrate 10.So described first photic zone 11a, Nano microsphere content difference between the second photic zone 11b and the 3rd photic zone 11c, different results is all produced to the luminous efficiency of described Organnic electroluminescent device 100.In present embodiment, described first photic zone to the 3rd euphotic Nano microsphere content according to 5% integral multiple gradient increase, detailed data is see table 1.Certainly, in other embodiments, described multiple euphotic Nano microsphere content can also increase according to the integral multiple gradient of 10%.Simultaneously, the light-extraction layer 11 of corresponding described embodiment one, embodiment two, embodiment three and embodiment four, provide Nano microsphere and polymer quality ratio in concrete described first photic zone 11a, the second photic zone 11b and the 3rd photic zone 11c, detailed data refers to table 1.Certainly, in other embodiments, in described first photic zone, the second photic zone and the 3rd photic zone, 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 described euphotic thickness to described Organnic electroluminescent device 100 has an impact equally.Described single photic zone thickness range is 10 μm ~ 50 μm.Described multiple photic zone thickness reduces successively according to substrate to described conductive anode direction.In present embodiment, described first photic zone reduces to the 3rd euphotic thickness according to 5 μm of integral multiple gradients, and detailed data is see table 1.Certainly, in other embodiments, described multiple euphotic thickness can also reduce according to 10 μm of integral multiple gradients.Meanwhile, the light-extraction layer 11 of corresponding described embodiment one, embodiment two, embodiment three and embodiment four, specifically provide the thickness of described first photic zone 11a, the second light projector layer 11b and the 3rd photic zone 11c, detailed data is see table 1.Certainly, in other embodiments, described first photic zone, the second photic zone and the 3rd euphotic thickness can also be other forms of combinations in preferable range.
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 any one transparent conductive oxide film of indium-zinc oxide or aluminium zinc oxide or 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 light emitting functional layer 13 and described electron transfer layer, and described electronic barrier layer is between described light emitting functional layer 13 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 '-two (9-carbazole) biphenyl, oxine aluminium, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene, N, N '-diphenyl-N, N '-two (1-naphthyls)-1,1 '-biphenyl-4,4 '-diamines.Or the material of described luminescent layer is (4,4 '-two (2,2-diphenylethyllene)-1,1 '-biphenyl, 4,4 '-bis-[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 '-three (2-naphthylphenyl is amino) triphenylamines, N, N '-diphenyl-N, N '-two (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 '-two (3-aminomethyl phenyl)-1,1 '-biphenyl-4,4 '-diamines) or 4; 4 ', 4 "-three (carbazole-9-base) triphenylamines.In present embodiment, described hole transmission layer adopts N, N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines, and 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 the Nano microsphere of more described light-extraction layer 11 containing multiple diameter affects the luminous efficiency of described Organnic electroluminescent device with the Nano microsphere containing single diameter.The invention provides the Organnic electroluminescent device of comparative example one.Described comparative example one and described first execution mode difference are that described light-extraction layer adopts single diameter to be the Nano microsphere of 500nm, and the mass ratio of described Nano microsphere and polymer is 35:100.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 comparative example two.Described comparative example two and the first execution mode difference are, 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 with first and deposit described light-extraction layer on the substrate, it is silicon dioxide that described light-extraction layer material comprises Nano microsphere material, 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, described nanospheres is doped in described polymeric material, described light-extraction layer forms multiple photic zone being provided with different Nano microsphere content on the substrate successively, described multiple euphotic Nano microsphere content increases successively, in described light-extraction layer, in single photic zone, Nano microsphere diameter is identical, described multiple euphotic Nano microsphere diameter range 50nm ~ 1500nm, described multiple euphotic Nano microsphere diameter reduces successively according to described, described single photic zone thickness range is 10 μm ~ 50 μm, described multiple euphotic thickness reduces successively, described light-extraction layer is through photocuring or hot curing film forming.
In present embodiment, preset silk screen printing order number one side in the two sides that described substrate is oppositely arranged with first and deposit described light-extraction layer, in the step of photocuring or hot curing film forming, described silk screen printing order number scope is 200 ~ 1000.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 11 is arranged at the first plane 10a of described substrate 10.Described light-extraction layer 11 forms the first photic zone 11a, the second photic zone 11b and the 3rd photic zone 11c on the substrate successively.Certainly, described light-extraction layer can also comprise four or five photic zones stacked gradually in other embodiments.More specifically, described first photic zone to described 3rd euphotic Nano microsphere diameter increases according to the gradient of 10nm integral multiple, and detailed data is see table 1.Described first photic zone to the 3rd euphotic Nano microsphere content according to 5% integral multiple gradient increase, detailed data is see table 1.Described first photic zone reduces to the 3rd euphotic thickness according to 5 μm of integral multiple gradients, and detailed data is see table 1.Certainly, in other embodiments, if described light-extraction layer also comprises the 4th photic zone or the 5th permeable layers, then described multiple euphotic Nano microsphere content can also increase according to the integral multiple gradient of 10%, described multiple euphotic thickness can also reduce according to 10 μm of integral multiple gradients, and described multiple euphotic Nano microsphere diameter can also increase according to 5nm integral multiple gradient.
103: in described light-extraction layer away from described substrate side vacuum sputtering conductive anode, described conductive anode is conductive oxide film.
In present embodiment, in described light-extraction layer away from described substrate side vacuum sputtering conductive anode, described conductive anode is in the step of conductive oxide film, using described substrate as bombardment target.Concrete, described conductive anode 12 is formed near described first plane 10a side, in the vacuum coating equipment of vacuum degree 10-4a, using described substrate 10 as negative potential, described conductive oxide raw material are as the bombardment of positive potential by lotus energy particle, described conductive oxide is sputtered onto in the light-extraction layer 11 on the first plane 10a of described substrate 10, forms conductive oxide film.Certainly, in other embodiments, described conductive anode 12 can also be formed on described second plane 10b.
104: at described conductive anode away from described light-extraction layer one side vacuum evaporation light emitting functional layer, described light emitting functional layer is luminous through substrate under the first predeterminated voltage.
In present embodiment, at described conductive anode away from described light-extraction layer one 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.In vacuum degree 10
-4avacuum coating equipment in, to hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and and the raw material of electron injecting layer vapour pressure is provided, raw material are gasified, and condense on described conductive anode, nucleation forms film then.In present embodiment, the film forming order of described light emitting functional layer 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 described conductive anode and conductive cathode, then after described hole transmission layer is formed, form electronic barrier layer, after described organic luminous 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, at described electron injecting layer away from described conductive anode one side vacuum evaporation conductive cathode, described conductive cathode is in the step of 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 the light-emitting layer, nucleation forms film then.In present embodiment, the raw material of described conductive cathode 14 are silver, and described conductive cathode 14 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.
First execution mode and comparative example one and comparative example two are carried out test and comparison, and described test luminous efficiency presets driving voltage at first of 6V to carry out, and described light emitting functional layer 13 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 luminescent device can be significantly improved, bring up to more than 18.1lm/W from initial 10.3lm/W, the efficiency that embodiment provided by the invention improves is higher, compared with comparative example one, its highest luminous efficiency has brought up to 26.21m/W, improves more than 40%, and relative contrast's example two, its efficiency improves 154%.
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 comprises the first photic zone 21a, the second photic zone 21b, the 3rd photic zone 21c and the 4th photic zone 21d.Described first photic zone 21a, the second photic zone 21b, the 3rd photic zone 21c and the 4th photic zone 21d stack gradually according to the direction of described substrate 20 to described conductive anode 22.Described light-extraction layer 21 adopts Properties of Polystyrene Nano Particles, and Nano microsphere diameter range is 200nm ~ 1500nm.Described polymeric material is light-cured acrylic resin, and the quality of described Nano microsphere and polymer is 10:100 ~ 30:100 than scope.
Same, in present embodiment, the light-extraction layer 21 that three kinds are different is provided in embodiment five, embodiment six and embodiment seven, and the thickness providing concrete described first photic zone 21a, the second photic zone 21b, the 3rd photic zone 21c and the 4th photic zone 21d of corresponding embodiment five, embodiment six and embodiment seven and Nano microsphere and polymer quality ratio.Detailed data refers to table 2.In present embodiment, provide first of embodiment five the euphotic Nano microsphere diameter to be 500nm, the second euphotic Nano microsphere diameter is 400nm, the 3rd euphotic Nano microsphere diameter 300nm, the 4th Nano microsphere diameter 200nm.In present embodiment, provide first of embodiment six the euphotic Nano microsphere diameter to be 1500nm, the second euphotic Nano microsphere diameter is 1300nm, and the 3rd euphotic Nano microsphere diameter is 1000nm, and the 4th euphotic Nano microsphere diameter is 700nm.In present embodiment, provide the first photic zone Nano microsphere diameter 900nm of embodiment seven, the second euphotic Nano microsphere diameter is 800nm, the 3rd euphotic Nano microsphere diameter 700nm, the 4th euphotic Nano microsphere diameter 600nm.Certainly, in other embodiments, in described light-extraction layer, Nano microsphere diameter can also be the other forms of combination in preferable range.
For the Nano microsphere of more described light-extraction layer 21 containing four 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 comparative example three.Described comparative example three and described second execution mode difference are that described light-extraction layer adopts single diameter to be the Nano microsphere of 800nm, and the mass ratio of described Nano microsphere and polymer is 30:100.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 comparative example four.Described comparative example four 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 comparative example three and comparative example four are carried out test and comparison, and described test luminous efficiency is carried out at the driving voltage of 6V.
Table 2 is the contrast test results obtained in present embodiment.After have employed light-extraction layer, the luminous efficiency of luminescent device can be significantly improved, bring up to more than 17.6lm/W from initial 10.3lm/W.The efficiency that embodiment provided by the invention improves is higher, and compared with comparative example three, its highest luminous efficiency has brought up to 28.2lm/W, improves more than 60%, and relative contrast's example four, its efficiency improves 174%.
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 comprises the first photic zone 31a, the second photic zone 31b, the 3rd photic zone 31c, the 4th photic zone 31d, the 5th photic zone 31e.Described first photic zone 31a, the second photic zone 31b, the 3rd photic zone 31c, the 4th photic zone 31d, the 5th photic zone 31e stack gradually to described conductive anode 31 direction according to described substrate 30.Described light-extraction layer 31 adopts silicon dioxide nanosphere, Nano microsphere diameter range 50nm ~ 1000nm.Described polymeric material is light-cured acrylic resin, and the quality of the Nano microsphere total amount in described light-extraction layer 31 and polymer is 10:100 ~ 50:100 than scope.
Same, in present embodiment, there is provided three kinds of embodiment eight, embodiment nine and embodiment ten different light-extraction layer 31, and corresponding embodiment eight, embodiment nine and embodiment ten provide the thickness of concrete described first photic zone 31a, the second photic zone 31b, the 3rd photic zone 31c, the 4th photic zone 31d and the 5th photic zone 31e and Nano microsphere and polymer quality ratio.Detailed data refers to table 3.In present embodiment, the first photic zone of embodiment eight, the second photic zone, the 3rd photic zone, the 4th photic zone and the 5th euphotic Nano microsphere diameter are followed successively by 600nm, 400nm, 200nm, 100nm and 50nm.In present embodiment, the first photic zone of embodiment nine, the second photic zone, the 3rd photic zone, the 4th photic zone and the 5th euphotic Nano microsphere diameter are followed successively by 1000nm, 900nm, 800nm, 700nm and 650nm.In present embodiment, the first photic zone of embodiment ten, the second photic zone, the 3rd photic zone, the 4th photic zone and the 5th euphotic Nano microsphere diameter 800nm, 700nm, 500nm, 300nm and 100nm successively.
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 comparative example five.Described comparative example five 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 40:100, and described light-extraction layer thickness is 100 μm.Correction data refers to table 3.
For more described light-extraction layer is on the impact of described Organnic electroluminescent device, the invention provides the Organnic electroluminescent device of comparative example six.Described comparative example six is from the 3rd different dwelling of execution mode, and described Organnic electroluminescent device cancels light-extraction layer.Correction data refers to table 3.
3rd execution mode and comparative example five and comparative example six are carried out test and comparison, and 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, after have employed light-extraction layer, the luminous efficiency of luminescent device can be significantly improved, bring up to more than 18.1lm/W from initial 10.3lm/W, the efficiency that embodiment provided by the invention improves is higher, compared with comparative example five, its highest luminous efficiency has brought up to 25.7lm/W, improves more than 40%, and relative contrast's example six, its efficiency improves 150%.
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, the present invention is provided with light-extraction layer between conductive anode and substrate, described light-extraction layer comprises multiple photic zone being provided with different Nano microsphere content, and in described photic zone, Nano microsphere diameter, Nano microsphere content and euphotic thickness all arrange according to a gradient.By Nano microsphere content different in described photic zone, the bulk refractive index of light-extraction layer can be changed, generally that content is higher, refractive index is larger, the photic zone near conductive anode is made to have higher refractive index like this, photic zone refractive index near substrate is lower, thus realizes the index matching of light taking-up.
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, conductive anode, light emitting functional layer and the conductive cathode that stack gradually, it is characterized in that, described Organnic electroluminescent device also comprises the light-extraction layer be arranged between described substrate and described conductive anode, and described light-extraction layer material comprises Nano microsphere and is doped to the mixture formed in polymer, the mass ratio of described Nano microsphere and described 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, described light-extraction layer comprises multiple photic zone being provided with different Nano microsphere content, described multiple photic zone being provided with different Nano microsphere content is stacked to described conductive anode direction according to described substrate, described multiple euphotic Nano microsphere content increases successively according to described substrate to described conductive anode direction, in described light-extraction layer, in single photic zone, Nano microsphere diameter is identical, described multiple euphotic Nano microsphere diameter range 50nm ~ 1500nm, described multiple euphotic Nano microsphere diameter reduces successively according to the direction of described substrate to described conductive anode, described single photic zone thickness range is 10 μm ~ 50 μm, described multiple euphotic thickness reduces successively according to described substrate to described conductive anode direction.
2. Organnic electroluminescent device according to claim 1, it is characterized in that, described light-extraction layer comprises the first photic zone, the second photic zone and the 3rd photic zone that stack gradually, described first photic zone is near described substrate, described first photic zone to the 3rd euphotic Nano microsphere content according to 5% integral multiple gradient increase, described first photic zone reduces to the 3rd euphotic thickness according to 5 μm of integral multiple gradients.
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 anode thickness range is 70nm ~ 200nm, and described conductive cathode 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 5, is characterized in that, described hole injection layer material is Phthalocyanine Zinc, CuPc or phthalocyanine platinum;
The material of described cave transport layer is 4,4 ', 4 "-three (2-naphthylphenyl amino) triphenylamine, N; N '-diphenyl-N, N '-two (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 '-two (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 '-two (9-carbazole) biphenyl, oxine aluminium, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene, N, N '-diphenyl-N, N '-two (1-naphthyls)-1,1 '-biphenyl-4,4 '-diamines;
Or the material of described luminescent layer is (4,4 '-two (2,2-diphenylethyllene)-1,1 '-biphenyl, 4,4 '-bis-[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;
Preset silk screen printing order number with first and deposit described light-extraction layer on the substrate, described light-extraction layer material comprises Nano microsphere and is doped to the mixture formed in polymer; The mass ratio of described Nano microsphere and described 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; Described light-extraction layer forms multiple photic zone being provided with different Nano microsphere content on the substrate successively, described multiple euphotic Nano microsphere content increases successively, in described light-extraction layer, in single photic zone, Nano microsphere diameter is identical, described multiple euphotic Nano microsphere diameter range 50nm ~ 1500nm, described multiple euphotic Nano microsphere diameter reduces successively according to described, described single photic zone thickness range is 10 μm ~ 50 μm, described multiple euphotic thickness reduces successively, and described light-extraction layer is through photocuring or hot curing film forming;
In described light-extraction layer away from described substrate side vacuum sputtering conductive anode, described conductive anode is conductive oxide film;
At described conductive anode away from described light-extraction layer one 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, depositing in the step of described light-extraction layer on the substrate with the first default silk screen printing order number, described first silk screen printing order number scope is 200 ~ 1000, described light-extraction layer forms the first photic zone, the second photic zone and the 3rd photic zone on the substrate successively, described first photic zone to the 3rd euphotic Nano microsphere content according to 5% integral multiple gradient increase, described first photic zone reduces to the 3rd euphotic thickness according to 5 μm of integral multiple gradients.
9. the preparation method of Organnic electroluminescent device according to claim 7, it is characterized in that, at described conductive anode away from described light-extraction layer one side vacuum evaporation light emitting functional layer, described light emitting functional layer under the first predeterminated voltage through in the step of substrate luminescence, described light emitting functional layer is luminous through substrate under the first predeterminated voltage, and described first predeterminated voltage is 6V.
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