CN104733627A - Organic light-emitting device and manufacturing method thereof - Google Patents

Organic light-emitting device and manufacturing method thereof Download PDF

Info

Publication number
CN104733627A
CN104733627A CN201310706654.1A CN201310706654A CN104733627A CN 104733627 A CN104733627 A CN 104733627A CN 201310706654 A CN201310706654 A CN 201310706654A CN 104733627 A CN104733627 A CN 104733627A
Authority
CN
China
Prior art keywords
layer
fullerene
nanometers
fullerene derivate
thickness
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201310706654.1A
Other languages
Chinese (zh)
Inventor
周明杰
黄辉
陈吉星
王平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
Original Assignee
Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Oceans King Lighting Science and Technology Co Ltd, Shenzhen Oceans King Lighting Engineering Co Ltd filed Critical Oceans King Lighting Science and Technology Co Ltd
Priority to CN201310706654.1A priority Critical patent/CN104733627A/en
Publication of CN104733627A publication Critical patent/CN104733627A/en
Pending legal-status Critical Current

Links

Abstract

An organic light-emitting device comprises an anode layer, a hole injection layer, a hole transfer layer, a light-emitting layer, an electron transfer layer, an electron injection layer and a cathode layer which are sequentially stacked on a substrate. The electron injection layer comprises a fullerene doping layer, a titanium dioxide doping layer and a fullerene derivative layer which are sequentially stacked on the electron transfer layer. The cathode layer is stacked on the fullerene derivative layer. The fullerene doping layer is made of a first fullerene derivative and a lithium salt doped in the first fullerene derivative. The titanium dioxide doping layer is made of titanium dioxide and a thiophere compound doped in the titanium dioxide. The fullerene derivative layer is made of a second fullerene derivative. The organic light-emitting device is high in light-emitting efficiency. The invention further provides a manufacturing method of the organic light-emitting device.

Description

Organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to organic electroluminescent field, particularly a kind of organic electroluminescence device and preparation method thereof.
Background technology
1987, C.W.Tang and VanSlyke of Eastman Kodak company of the U.S. reported the breakthrough in organic electroluminescent research.Ultrathin film technology is utilized to prepare high brightness, high efficiency double-deck organic electroluminescence device (OLED).Under 10V, brightness reaches 1000cd/m 2, its luminous efficiency is 1.51lm/W, the life-span is greater than 100 hours.
In traditional luminescent device, all low than hole transport speed two or three orders of magnitude of electron transfer rate, therefore, very easily cause the low of exciton recombination probability, and make the region of its compound not at light-emitting zone, thus luminous efficiency is reduced.
Summary of the invention
Given this, organic electroluminescence device that a kind of luminous efficiency is higher and preparation method thereof is provided to provide.
A kind of organic electroluminescence device, comprise the anode layer stacked gradually on substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer, described electron injecting layer comprises the fullerene doped layer stacked gradually on described electron transfer layer, titania additive layer and fullerene derivate layer, described cathode layer is laminated on described fullerene derivate layer, the material of described fullerene doped layer comprises the first fullerene derivate and is doped in the lithium salts in described first fullerene derivate, the material of described titania additive layer comprises titanium dioxide and is doped in the thiophene compound in described titanium dioxide, the material of described fullerene derivate layer is the second fullerene derivate, described first fullerene derivate and described second fullerene derivate are selected from football alkene respectively, carbon 70, [6, 6]-phenyl-C61-methyl butyrate and [6, 6] one in-phenyl-C71-methyl butyrate.
Wherein in an embodiment, described in the material of described fullerene doped layer, the mass ratio of lithium salts and described first fullerene derivate is 0.1:1 ~ 0.4:1.
Wherein in an embodiment, described lithium salts is lithia, lithium fluoride, lithium chloride or lithium bromide.
Wherein in an embodiment, described in the material of described titania additive layer, the mass ratio of titanium dioxide and described thiophene compound is 20:1 ~ 40:1.
Wherein in an embodiment, described thiophene compound is 3 methyl thiophene, 3 methyl thiophene, 3-octyl thiophene or 3-dodecylthiophene.
Wherein in an embodiment, the particle diameter of described titanium dioxide is 20 nanometer ~ 50 nanometers.
Wherein in an embodiment, the thickness of described fullerene doped layer is 15 nanometer ~ 30 nanometers; The thickness of described titania additive layer is 20 nanometer ~ 50 nanometers; The thickness of described fullerene derivate layer is 50 nanometer ~ 70 nanometers.
Wherein in an embodiment, described substrate is glass;
The material of described anode layer is indium and tin oxide film, mix the zinc-oxide film of aluminium or mix the zinc-oxide film of indium, and the thickness of described anode layer is 50 nanometer ~ 300 nanometers;
The material of described hole injection layer is molybdenum trioxide, tungstic acid or vanadic oxide, and the thickness of described hole injection layer is 20 nanometer ~ 80 nanometers;
The material of described hole transmission layer is 1,1-bis-[4-[N, N'-bis-(p-tolyl) is amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-base) triphenylamine or N, N'-(1-naphthyl)-N, N'-diphenyl-4,4'-benzidine, the thickness of described hole transmission layer is 20 nanometer ~ 60 nanometers;
The material of described luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl of 4'-or oxine aluminium, the thickness of described luminescent layer is 5 nanometer ~ 40 nanometers;
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole, and the thickness of described electron transfer layer is 40 nanometer ~ 250 nanometers;
The material of described cathode layer is silver, aluminium, platinum or gold, and the thickness of described cathode layer is 80 nanometer ~ 250 nanometers.
A preparation method for organic electroluminescence device, comprises the steps:
There is provided substrate, magnetron sputtering prepares anode layer on the substrate;
On described anode layer, hole injection layer is prepared in vacuum evaporation;
On described hole injection layer, hole transmission layer is prepared in vacuum evaporation;
Luminescent layer is prepared in vacuum evaporation on the hole transport layer;
Electron transfer layer is prepared in vacuum evaporation on the light-emitting layer;
Thermal resistance evaporation prepares fullerene doped layer on the electron transport layer, on described fullerene doped layer, electron beam evaporation plating prepares titania additive layer, thermal resistance evaporation fullerene derivate layer on described titania additive layer, obtain being laminated in the electron injecting layer on described electron transfer layer, wherein, the material of described fullerene doped layer comprises the first fullerene derivate and is doped in the lithium salts in described first fullerene derivate, the material of described titania additive layer comprises titanium dioxide and is doped in the thiophene compound in described titanium dioxide, the material of described fullerene derivate layer is the second fullerene derivate, described first fullerene derivate and described second fullerene derivate are selected from football alkene respectively, carbon 70, [6, 6]-phenyl-C61-methyl butyrate and [6, 6] one in-phenyl-C71-methyl butyrate, and
On described fullerene derivate layer, cathode layer is prepared in vacuum evaporation.
Wherein in an embodiment, before magnetron sputtering prepares described anode layer on the substrate, also comprise the cleaning step to described substrate: described substrate is used distilled water, ethanol purge successively, then soaks in isopropyl alcohol.
The electron injecting layer of above-mentioned organic electroluminescence device comprises the fullerene doped layer stacked gradually on electron transfer layer, titania additive layer and fullerene derivate layer, the lithium salts that fullerene doped layer comprises the first fullerene derivate and is doped in the first fullerene derivate, first fullerene derivate is selected from football alkene (C60), carbon 70(C70), [6, 6]-phenyl-C61-methyl butyrate (PC61BM) and [6, 6] one in-phenyl-C71-methyl butyrate (PC71BM), these materials can improve the film forming of rete, these first fullerene derivates are electron rich material simultaneously, be conducive to improving electron transfer rate, and lithium salts has higher work function, stacked one deck fullerene doped layer on the electron transport layer, the injectability of electronics can be improved, be conducive to the raising of the luminous efficiency of organic electroluminescence device, titania additive layer comprises titanium dioxide and is doped in the thiophene compound in titanium dioxide, because the specific area of titanium dioxide is large, porosity is high, can make light generation scattering, make the light launched to both sides get back to centre, thiophene compound segment is regular, be doped to after in titanium dioxide, the crystal regularity of titanium dioxide can be improved, add the scattering of high light further, improve the luminous efficiency of organic electroluminescence device further, in addition, because titanium dioxide belongs to metal oxide, and titanium atom radius is larger, rete is relatively coarse, by one deck stacked on titania additive layer with football alkene (C60), carbon 70(C70), [6, 6]-phenyl-C61-methyl butyrate (PC61BM) and [6, 6] a kind of in-phenyl-C71-methyl butyrate (PC71BM) is the fullerene derivate layer of material, can the surface of smooth titania additive layer, make it more level and smooth, reduce film defects, be conducive to the transmission of electronics, thus further improve the luminous efficiency of organic electroluminescence device, therefore, the organic electroluminescence device with said structure has higher luminous efficiency.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is the flow chart of the preparation method of the organic electroluminescence device of an execution mode;
Structure prepared by Fig. 3 embodiment 1 is Glass/ITO/MoO 3/ NPB/Bcz VBi/TPBi/C60:LiF/TiO 2: structure prepared by the organic electroluminescence device of 3HT/C60/Ag and comparative example 1 is Glass//ITO/MoO 3/ NPB/BCz VBi/TPBi/Cs 2cO 3the graph of relation of the brightness-luminous efficiency of the organic electroluminescence device of/Ag, wherein, the relation curve of brightness-luminous efficiency of the organic electroluminescence device of the embodiment 1 that curve 1 represents, the relation curve of the brightness-luminous efficiency of the organic electroluminescence device of comparative example 1 that what curve 2 represented is.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments organic electroluminescence device and preparation method thereof is described in further detail below.
As shown in Figure 1, the organic electroluminescence device 100 of one execution mode, comprises the anode layer 120 stacked gradually on substrate 110, hole injection layer 130, hole transmission layer 140, luminescent layer 150, electron transfer layer 160, electron injecting layer 170 and cathode layer 180.
Substrate 110 is glass.
The material of anode layer 120 can be the conventional conductive film in this area, is preferably indium and tin oxide film (ITO), the zinc-oxide film (AZO) mixing aluminium and the one of mixing in the zinc-oxide film (IZO) of indium; Be more preferably indium and tin oxide film (ITO).
The thickness of anode layer 120 is 50 nanometer ~ 300 nanometers; Be preferably 120 nanometers.
Hole injection layer 130 material is molybdenum trioxide (MoO 3), tungstic acid (WO 3) or vanadic oxide (V 2o 5); Be preferably molybdenum trioxide (MoO 3).
The thickness of hole injection layer 130 is 20 nanometer ~ 80 nanometers; Be preferably 45 nanometers.
The material of hole transmission layer 140 is 1,1-bis-[4-[N, N'-bis-(p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) or N, N'-(1-naphthyl)-N, N'-diphenyl-4,4'-benzidine (NPB); Be preferably N, N'-(1-naphthyl)-N, N'-diphenyl-4,4'-benzidine (NPB).
The thickness of hole transmission layer 140 is 20 nanometer ~ 60 nanometers; Be preferably 58 nanometers.
The material of luminescent layer 150 is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-or oxine aluminium (Alq 3); Be preferably two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCz VBi) of 4,4'-.
The thickness of luminescent layer 150 is 5 nanometer ~ 40 nanometers; Be preferably 23 nanometers.
The material of electron transfer layer 160 is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBi); Be preferably N-aryl benzimidazole (TPBi).
The thickness of electron transfer layer 160 is 40 nanometer ~ 250 nanometers; Be preferably 75 nanometers.
Electron injecting layer 170 comprises the fullerene doped layer 172 stacked gradually on electron transfer layer 160, titania additive layer 174 and fullerene derivate layer 176.
Wherein, the material of fullerene doped layer 172 lithium salts that comprises the first fullerene derivate and be doped in the first fullerene derivate.Wherein, in the material of fullerene doped layer 172, the mass ratio of lithium salts and the first fullerene derivate is 0.1:1 ~ 0.4:1.In this proportion, lithium salts can reach its optimum efficiency, and meanwhile, fullerene derivate and lithium salts can form good n and adulterate, and improves electric transmission; Lower than this ratio, lithium salts effect is lower, brings difficulty to doping simultaneously; Because lithium salts evaporating temperature is higher than fullerene, if higher than this ratio, the evaporating temperature of whole doped layer can be made to improve, be unfavorable for processing preparation; First fullerene derivate is selected from football alkene (C60), carbon 70(C70), one in [6,6]-phenyl-C61-methyl butyrate (PC61BM) and [6,6]-phenyl-C71-methyl butyrate (PC71BM).These first fullerene derivates have higher film forming, and these first fullerene derivates are electron rich material simultaneously, are conducive to improving electron transfer rate.Lithium salts is lithia (Li 2o), lithium fluoride (LiF), lithium chloride (LiCl) or lithium bromide (LiBr).These lithium salts have higher work function, by these lithium salt dopings in the first fullerene derivate, and will the fullerene doped layer 172 of this material be used to be layered on electron transfer layer 160, the injectability of electronics can be improved, thus be conducive to the raising of the luminous efficiency of organic electroluminescence device 100.
The thickness of fullerene doped layer 172 is 15 nanometer ~ 30 nanometers.
Wherein, the material of titania additive layer 174 is the thiophene compound comprising titanium dioxide and be doped in titanium dioxide.Because the specific area of titanium dioxide is large, porosity is high, light generation scattering can be made, the light launched to both sides is made to get back to centre, thiophene compound segment is regular, is doped to after in titanium dioxide, can improve the crystal regularity of titanium dioxide, add the scattering of high light further, improve the luminous efficiency of organic electroluminescence device 100 further.Preferably, the particle diameter of titanium dioxide is preferably 20 nanometer ~ 50 nanometers.The titanium dioxide of this particle size range can add the scattering of high light, if particle diameter is excessive, likely forms reunion form, is unfavorable for film forming.Wherein, in the material of titania additive layer, the mass ratio of titanium dioxide and thiophene compound is 20:1 ~ 40:1.In the material of titania additive layer, the mass ratio of titanium dioxide and thiophene compound is 20:1 ~ 40:1, can add the scattering of high light, and as ratio is too high, then titanium dioxide is too much, then improve the temperature of preparation; As ratio is too low, then titanium dioxide does not fully mix in the film, is unfavorable for the uniformity of scattering.Thiophene compound is 3 methyl thiophene (3HT), 3 methyl thiophene (3AT), 3-octyl thiophene (3OT) or 3-dodecylthiophene (3DDT).Because segment is regular, after these thiophene compounds and titania additive, titanium dioxide can be made to disperse uniformly in the film.
The thickness of titania additive layer 174 is 20 nanometer ~ 50 nanometers.
Wherein, the material of fullerene derivate layer 176 is the second fullerene derivate.Because titanium dioxide belongs to metal oxide, and titanium atom radius is larger, rete is relatively coarse, can the surface of smooth titania additive layer 174 by 176, one deck fullerene derivate layer stacked on titania additive layer 174, make it more level and smooth, reduce film defects, be conducive to the transmission of electronics, thus further improve the luminous efficiency of organic electroluminescence device 100.Wherein, the second fullerene derivate is selected from football alkene (C60), carbon 70(C70), one in [6,6]-phenyl-C61-methyl butyrate (PC61BM) and [6,6]-phenyl-C71-methyl butyrate (PC71BM).These second fullerene derivates have higher film forming, and these second fullerene derivates are electron rich material simultaneously, are conducive to improving electron transfer rate.
The thickness of fullerene derivate layer 176 is 50 nanometer ~ 70 nanometers.
Cathode layer 180 is laminated on fullerene derivate layer 176.The material of cathode layer 180 is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au); Be preferably silver (Ag).
The thickness of cathode layer 180 is 80 nanometer ~ 250 nanometers; Be preferably 180 nanometers.
The electron injecting layer 170 of above-mentioned organic electroluminescence device 100 comprises the fullerene doped layer 172 stacked gradually on electron transfer layer 160, titania additive layer 174 and fullerene derivate layer 176, the lithium salts that fullerene doped layer 172 comprises the first fullerene derivate and is doped in the first fullerene derivate, first fullerene derivate is selected from football alkene (C60), carbon 70(C70), [6, 6]-phenyl-C61-methyl butyrate (PC61BM) and [6, 6] one in-phenyl-C71-methyl butyrate (PC71BM), these materials can improve the film forming of rete, these first fullerene derivates are electron rich material simultaneously, be conducive to improving electron transfer rate, and lithium salts has higher work function, stacked one deck fullerene doped layer 172 on electron transfer layer 160, the injectability of electronics can be improved, be conducive to the raising of the luminous efficiency of organic electroluminescence device 100, titania additive layer 174 comprises titanium dioxide and is doped in the thiophene compound in titanium dioxide, because the specific area of titanium dioxide is large, porosity is high, can make light generation scattering, make the light launched to both sides get back to centre, thiophene compound segment is regular, be doped to after in titanium dioxide, the crystal regularity of titanium dioxide can be improved, add the scattering of high light further, improve the luminous efficiency of organic electroluminescence device 100 further, in addition, because titanium dioxide belongs to metal oxide, and titanium atom radius is larger, rete is relatively coarse, by one deck stacked on titania additive layer 174 with football alkene (C60), carbon 70(C70), [6, 6]-phenyl-C61-methyl butyrate (PC61BM) and [6, 6] a kind of in-phenyl-C71-methyl butyrate (PC71BM) is the fullerene derivate layer 176 of material, can the surface of smooth titania additive layer 174, make it more level and smooth, reduce film defects, be conducive to the transmission of electronics, thus further improve the luminous efficiency of organic electroluminescence device 100, therefore, the organic electroluminescence device 100 with said structure has higher luminous efficiency.
As shown in Figure 2, the preparation method of the organic electroluminescence device of an execution mode, comprises the steps:
S310: provide substrate, on substrate, magnetron sputtering prepares anode layer.
Wherein, substrate is glass.
Wherein, anode layer material can be the conventional conductive film in this area, be preferably indium and tin oxide film (ITO), the zinc-oxide film (AZO) mixing aluminium and the one of mixing in the zinc-oxide film (IZO) of indium; Be more preferably indium and tin oxide film (ITO).
The thickness of anode layer is 50 nanometer ~ 300 nanometers; Be preferably 120 nanometers.
Wherein, before magnetron sputtering prepares anode layer on substrate, also comprise the cleaning step to substrate: substrate is used distilled water, ethanol purge successively, then soaks in isopropyl alcohol.
Preferably, magnetron sputtering is prepared the technological parameter of anode layer and is: the accelerating voltage of magnetron sputtering is 300V ~ 800V; Magnetic field is 50G ~ 200G; Power density is 1W/cm 2~ 40W/cm 2.If technological parameter not in above-mentioned scope, then can affect the film forming of film, have impact to the stability of substrate, meanwhile, have impact to the stability of target, voltage is too high, and target is impaired.
S320: hole injection layer is prepared in vacuum evaporation on the anode layer.
Wherein, the material of hole injection layer is molybdenum trioxide (MoO 3), tungstic acid (WO 3) or vanadic oxide (V 2o 5); Be preferably molybdenum trioxide (MoO 3).
The thickness of hole injection layer is 20 nanometer ~ 80 nanometers; Be preferably 45 nanometers.
Preferably, the evaporation rate of hole injection layer is 1nm/s ~ 10nm/s.
S330: hole transmission layer is prepared in vacuum evaporation on hole injection layer.
Wherein, the material of hole transmission layer is 1,1-bis-[4-[N, N'-bis-(p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) or N, N'-(1-naphthyl)-N, N'-diphenyl-4,4'-benzidine (NPB); Be preferably N, N'-(1-naphthyl)-N, N'-diphenyl-4,4'-benzidine (NPB).
The thickness of hole transmission layer is 20 nanometer ~ 60 nanometers; Be preferably 58 nanometers.
S340: luminescent layer is prepared in vacuum evaporation on hole transmission layer.
Wherein, the material of luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4,4'-two (9-ethyl-3-carbazole vinyl)-1,1'-biphenyl (BCz VBi) or oxine aluminium (Alq 3); Be preferably two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCz VBi) of 4,4'-.
The thickness of luminescent layer is 5 nanometer ~ 40 nanometers; Be preferably 23 nanometers.
S350: electron transfer layer is prepared in vacuum evaporation on luminescent layer.
Wherein, the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBi); Be preferably N-aryl benzimidazole (TPBi).
The thickness of electron transfer layer is 40 nanometer ~ 250 nanometers; Be preferably 75 nanometers.
Preferably, the evaporation rate in step S330, S340 and S350 during vacuum evaporation is 0.1nm/s ~ 1nm/s.
S360: thermal resistance evaporation prepares fullerene doped layer on the electron transport layer, on fullerene doped layer, electron beam evaporation plating prepares titania additive layer, thermal resistance evaporation fullerene derivate layer on titania additive layer, obtain the electron injecting layer be laminated on electron transfer layer, wherein, the lithium salts that the material of fullerene doped layer comprises the first fullerene derivate and is doped in the first fullerene derivate, the material of titania additive layer comprises titanium dioxide and is doped in the thiophene compound in titanium dioxide, the material of fullerene derivate layer is the second fullerene derivate.
In the material of fullerene doped layer, the mass ratio of lithium salts and the first fullerene derivate is 0.1:1 ~ 0.4:1.First fullerene derivate is selected from football alkene (C60), carbon 70(C70), one in [6,6]-phenyl-C61-methyl butyrate (PC61BM) and [6,6]-phenyl-C71-methyl butyrate (PC71BM).These first fullerene derivates have higher film forming, and these first fullerene derivates are electron rich material simultaneously, are conducive to improving electron transfer rate.Lithium salts is lithia (Li 2o), lithium fluoride (LiF), lithium chloride (LiCl) or lithium bromide (LiBr).These lithium salts have higher work function, by these lithium salt dopings in the first fullerene derivate, preparation uses the fullerene doped layer of this material can improve the injectability of electronics on the electron transport layer, thus is conducive to the raising of the luminous efficiency of organic electroluminescence device.
The thickness of fullerene doped layer is 15 nanometer ~ 30 nanometers.
Wherein, in the material of titania additive layer, the mass ratio of titanium dioxide and thiophene compound is 20:1 ~ 40:1.Titanium dioxide (TiO 2) particle diameter be preferably 20 nanometer ~ 50 nanometers.Wherein, thiophene compound is 3 methyl thiophene (3HT), 3 methyl thiophene (3AT), 3-octyl thiophene (3OT) or 3-dodecylthiophene (3DDT).Because the specific area of titanium dioxide is large, porosity is high, light generation scattering can be made, the light launched to both sides is made to get back to centre, thiophene compound segment is regular, is doped to after in titanium dioxide, can improve the crystal regularity of titanium dioxide, add the scattering of high light further, improve the luminous efficiency of organic electroluminescence device further.
The thickness of titania additive layer is 20 nanometer ~ 50 nanometers.
Preferably, energy density when electron beam evaporation plating prepares titania additive layer on fullerene doped layer is 10W/cm 2~ 100W/cm 2.This energy density can make titanium dioxide stablize lasting evaporation out; If energy density is too low, titanium dioxide can not stablize lasting evaporation out, and energy density is too high, and the organic layer prepared can be made impaired.
Wherein, the second fullerene derivate is selected from football alkene (C60), carbon 70(C70), one in [6,6]-phenyl-C61-methyl butyrate (PC61BM) and [6,6]-phenyl-C71-methyl butyrate (PC71BM).These second fullerene derivates have higher film forming, and these second fullerene derivates are electron rich material simultaneously, are conducive to improving electron transfer rate.Because titanium dioxide belongs to metal oxide, and titanium atom radius is larger, rete is relatively coarse, then can the surface of smooth titania additive layer by preparing one deck fullerene derivate layer on titania additive layer, make it more level and smooth, reduce film defects, be conducive to the transmission of electronics, thus further improve the luminous efficiency of organic electroluminescence device.
The thickness of fullerene derivate layer is 50 nanometer ~ 70 nanometers.
S370: cathode layer is prepared in vacuum evaporation on fullerene derivate layer.
Wherein, the material of cathode layer is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au); Be preferably silver (Ag).
The thickness of cathode layer is 80 nanometer ~ 250 nanometers; Be preferably 180 nanometers.
Preferably, the evaporation rate of cathode layer is 1nm/s ~ 10nm/s.
Preferably, operating pressure during vacuum evaporation in step S320, S330, S340 and S350 is 2 × 10 -3~ 5 × 10 -5pa.
Preparation method's operation of above-mentioned organic electroluminescence device is simple, and easily operate, the qualification rate of finished product is high, effectively improves production efficiency, reduces production cost, is applicable to industrialization and produces.
It is below specific embodiment part, wherein, test and Preparation equipment are high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), the USB4000 fiber spectrometer testing electroluminescent spectrum of U.S. marine optics Ocean Optics, the Keithley2400 of Keithley company of the U.S. tests electric property, the CS-100A colorimeter test brightness of Japanese Konica Minolta company and colourity:
Embodiment 1
The structure of the organic electroluminescence device of the present embodiment is: Glass/ITO/MoO 3/ NPB/Bcz VBi/TPBi/C60:LiF/TiO 2: 3HT/C60/Ag.
Being prepared as follows of the organic electroluminescence device of this embodiment:
(1) provide glass substrate, substrate is used distilled water, ethanol purge successively, then in isopropyl alcohol, soak a night, glass substrate is expressed as: Glass; Then on substrate, magnetron sputtering prepares anode layer, and wherein, the accelerating voltage of magnetron sputtering is 700V, and magnetic field is 120G, and power is 250W/cm 2, the material of anode layer is indium and tin oxide film (ITO), and anode layer is expressed as: ITO, and thickness is 120 nanometers.
(2) hole injection layer is prepared in vacuum evaporation on the anode layer: the material of hole injection layer is molybdenum trioxide (MoO 3), evaporation rate is 2nm/s, and hole injection layer is expressed as: MoO 3, thickness 45 nanometer.
(3) on hole injection layer, hole transmission layer is prepared in vacuum evaporation: the material of hole transmission layer is N, N'-(1-naphthyl)-N, N'-diphenyl-4,4'-benzidine (NPB), evaporation rate is 0.2nm/s, and hole transmission layer is expressed as: NPB, and thickness is 58 nanometers.
(4) on hole transmission layer, luminescent layer is prepared in vacuum evaporation: the material of luminescent layer is 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCz VBi) of 4'-, evaporation rate is 0.2nm/s, luminescent layer is expressed as: Bcz VBi, and thickness is 23 nanometers.
(5) on luminescent layer, electron transfer layer is prepared in vacuum evaporation: the material of electron transfer layer is N-aryl benzimidazole (TPBi), and evaporation rate is 0.2nm/s, and electron transfer layer is expressed as: TPBi, and thickness is 75 nanometers.
(6) thermal resistance evaporation prepares fullerene doped layer on the electron transport layer, on fullerene doped layer, electron beam evaporation plating prepares titania additive layer, thermal resistance evaporation fullerene derivate layer on titania additive layer, obtain the electron injecting layer be laminated on electron transfer layer: the material of fullerene doped layer is the football alkene (C60) that lithium fluoride (LiF) adulterates, and lithium fluoride (LiF) is 0.2:1 with the mass ratio of football alkene (C60), fullerene doped layer is expressed as C60:LiF, and thickness is 25 nanometers;
The material of titania additive layer is the titanium dioxide (TiO that 3 methyl thiophene (3HT) adulterates 2), and 3 methyl thiophene (3HT) and titanium dioxide (TiO 2) mass ratio be 1:25, wherein, titanium dioxide (TiO 2) particle diameter be 30 nanometers, the energy density of electron beam evaporation plating titania additive layer is 40W/cm 2, titania additive layer is expressed as: TiO 2: 3HT, thickness is 60 nanometers;
The material of fullerene derivate layer is football alkene (C60), and fullerene derivate layer is expressed as: C60, and thickness is 2 nanometers.Then electron injecting layer is expressed as: C60:LiF/TiO 2: 3HT/C60.
(7) on fullerene derivate layer, cathode layer is prepared in vacuum evaporation: the material of cathode layer is silver (Ag), and cathode layer is expressed as: Ag, and thickness is 180 nanometers, and the evaporation rate of vacuum evaporation cathode layer is 2nm/s.
The structure obtaining the present embodiment is Glass/ITO/MoO 3/ NPB/Bcz VBi/TPBi/C60:LiF/TiO 2: the organic electroluminescence device of 3HT/C60/Ag, wherein, brace "/" represents layer structure, and the colon ": " in C60:LiF represents doping mixing, lower same; Operating pressure during vacuum evaporation in above-mentioned steps (2), (3), (4) and (5) is 8 × 10- 4pa.
Embodiment 2
The structure of the organic electroluminescence device of the present embodiment is: Glass/IZO/V 2o 5/ TAPC/ADN/TPBi/C70:Li 2o/TiO 2: 3AT/C70/Al.
Being prepared as follows of the organic electroluminescence device of this embodiment:
(1) provide glass substrate, substrate is used distilled water, ethanol purge successively, then in isopropyl alcohol, soak a night, glass substrate is expressed as: Glass; Then on substrate, magnetron sputtering prepares anode layer, and wherein, the accelerating voltage of magnetron sputtering is 300V, and magnetic field is 50G, and power is 40W/cm 2, the material of anode layer is the zinc-oxide film (IZO) mixing indium, and anode layer is expressed as: IZO, and thickness is 300 nanometers.
(2) hole injection layer is prepared in vacuum evaporation on the anode layer: the material of hole injection layer is vanadic oxide (V 2o 5), evaporation rate is 10nm/s, and hole injection layer is expressed as: V 2o 5, thickness 20 nanometer.
(3) on hole injection layer, hole transmission layer is prepared in vacuum evaporation: the material of hole transmission layer is 1,1-bis-[4-[N, N'-bis-(p-tolyl) is amino] phenyl] cyclohexane (TAPC), evaporation rate is 1nm/s, hole transmission layer is expressed as: TAPC, and thickness is 45 nanometers.
(4) on hole transmission layer, luminescent layer is prepared in vacuum evaporation: the material of luminescent layer is 9,10-bis--β-naphthylene anthracene (ADN), and evaporation rate is 1nm/s, and luminescent layer is expressed as: ADN, and thickness is 5 nanometers.
(5) on luminescent layer, electron transfer layer is prepared in vacuum evaporation: the material of electron transfer layer is N-aryl benzimidazole (TPBi), and evaporation rate is 1nm/s, and electron transfer layer is expressed as: TPBi, and thickness is 65 nanometers.
(6) thermal resistance evaporation prepares fullerene doped layer on the electron transport layer, on fullerene doped layer, electron beam evaporation plating prepares titania additive layer, thermal resistance evaporation fullerene derivate layer on titania additive layer, obtains the electron injecting layer be laminated on electron transfer layer: the material of fullerene doped layer is lithia (Li 2o) the carbon 70(C70 adulterated), and lithia (Li 2o) with carbon 70(C70) mass ratio be 0.1:1, fullerene doped layer is expressed as C70:Li 2o, thickness is 30 nanometers;
The material of titania additive layer is the titanium dioxide (TiO that 3 methyl thiophene (3AT) adulterates 2), and 3 methyl thiophene (3AT) and titanium dioxide (TiO 2) mass ratio be 1:20, wherein, titanium dioxide (TiO 2) particle diameter be 50 nanometers, the energy density of electron beam evaporation plating titania additive layer is 100W/cm 2, titania additive layer is expressed as: TiO 2: 3AT, thickness is 50 nanometers;
The material of fullerene derivate layer is carbon 70(C70), fullerene derivate layer is expressed as: C70, and thickness is 1 nanometer.Then electron injecting layer is expressed as: C70:Li 2o/TiO 2: 3AT/C70.
(7) on fullerene derivate layer, cathode layer is prepared in vacuum evaporation: the material of cathode layer is aluminium (Al), and cathode layer is expressed as: Al, and thickness is 80 nanometers, and the evaporation rate of vacuum evaporation cathode layer is 10nm/s.
The structure obtaining the present embodiment is Glass/IZO/V 2o 5/ TAPC/ADN/TPBi/C70:Li 2o/TiO 2: the organic electroluminescence device of 3AT/C70/Al.Operating pressure during vacuum evaporation in above-mentioned steps (2), (3), (4) and (5) is 2 × 10 -3pa.
Embodiment 3
The structure of the organic electroluminescence device of the present embodiment is: Glass/AZO/WO 3/ NPB/Alq 3/ Bphen/PC61BM:LiCl/TiO 2: 3OT/PC61BM/Au.
Being prepared as follows of the organic electroluminescence device of this embodiment:
(1) provide glass substrate, substrate is used distilled water, ethanol purge successively, then in isopropyl alcohol, soak a night, glass substrate is expressed as: Glass; Then on substrate, magnetron sputtering prepares anode layer, and wherein, the accelerating voltage of magnetron sputtering is 800V, and magnetic field is 200G, and power is 1W/cm 2, the material of anode layer is the zinc-oxide film (AZO) mixing aluminium, and anode layer is expressed as: AZO, and thickness is 150 nanometers.
(2) hole injection layer is prepared in vacuum evaporation on the anode layer: the material of hole injection layer is tungstic acid (WO 3), evaporation rate is 1nm/s, and hole injection layer is expressed as: WO 3, thickness 55 nanometer.
(3) on hole injection layer, hole transmission layer is prepared in vacuum evaporation: the material of hole transmission layer is N, N'-(1-naphthyl)-N, N'-diphenyl-4,4'-benzidine (NPB), evaporation rate is 0.1nm/s, and hole transmission layer is expressed as: NPB, and thickness is 60 nanometers.
(4) on hole transmission layer, luminescent layer is prepared in vacuum evaporation: the material of luminescent layer is oxine aluminium (Alq 3), evaporation rate is 0.1nm/s, and luminescent layer is expressed as: Alq 3, thickness is 40 nanometers.
(5) on luminescent layer, electron transfer layer is prepared in vacuum evaporation: the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), and evaporation rate is 0.1nm/s, and electron transfer layer is expressed as: Bphen, and thickness is 35 nanometers
(6) thermal resistance evaporation prepares fullerene doped layer on the electron transport layer, on fullerene doped layer, electron beam evaporation plating prepares titania additive layer, thermal resistance evaporation fullerene derivate layer on titania additive layer, obtain the electron injecting layer be laminated on electron transfer layer: the material of fullerene doped layer be lithium chloride (LiCl) adulterate [6, 6]-phenyl-C61-methyl butyrate (PC61BM), and lithium chloride (LiCl) and [6, the mass ratio of 6]-phenyl-C61-methyl butyrate (PC61BM) is 0.4:1, fullerene doped layer is expressed as PC61BM:LiCl, thickness is 15 nanometers,
The material of titania additive layer is the titanium dioxide (TiO that 3-octyl thiophene (3OT) adulterates 2), and 3-octyl thiophene (3OT) and titanium dioxide (TiO 2) mass ratio be 1:40, wherein, titanium dioxide (TiO 2) particle diameter be 20 nanometers, the energy density of electron beam evaporation plating titania additive layer is 10W/cm 2, titania additive layer is expressed as: TiO 2: 3OT, thickness is 70 nanometers;
The material of fullerene derivate layer is [6,6]-phenyl-C61-methyl butyrate (PC61BM), and fullerene derivate layer is expressed as: PC61BM, and thickness is 10 nanometers.Then electron injecting layer is expressed as: PC61BM:LiCl/TiO 2: 3OT/PC61BM.
(7) on fullerene derivate layer, cathode layer is prepared in vacuum evaporation: the material of cathode layer is gold (Au), and cathode layer is expressed as: Au, and thickness is 250 nanometers, and the evaporation rate of vacuum evaporation cathode layer is 1nm/s.
The structure obtaining the present embodiment is Glass/AZO/WO 3/ NPB/Alq 3/ Bphen/PC61BM:LiCl/TiO 2: the organic electroluminescence device of 3OT/PC61BM/Au; Operating pressure during vacuum evaporation in above-mentioned steps (2), (3), (4) and (5) is 5 × 10 -5pa.
Embodiment 4
The structure of the organic electroluminescence device of the present embodiment is: Glass/IZO/MoO 3/ TCTA/DCJTB/TAZ/PC71BM:LiBr/TiO 2: 3DDT/PC71BM/Pt.
Being prepared as follows of the organic electroluminescence device of this embodiment:
(1) provide glass substrate, substrate is used distilled water, ethanol purge successively, then in isopropyl alcohol, soak a night, glass substrate is expressed as: Glass; Then on substrate, magnetron sputtering prepares anode layer, and wherein, the accelerating voltage of magnetron sputtering is 600V, and magnetic field is 100G, and power is 30W/cm 2, the material of anode layer is the zinc-oxide film (IZO) mixing indium, and anode layer is expressed as: IZO, and thickness is 50 nanometers.
(2) hole injection layer is prepared in vacuum evaporation on the anode layer: the material of hole injection layer is molybdenum trioxide (MoO 3), evaporation rate is 6nm/s, and hole injection layer is expressed as: MoO 3, thickness 80 nanometer.
(3) on hole injection layer, hole transmission layer is prepared in vacuum evaporation: the material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), evaporation rate is 0.5nm/s, hole transmission layer is expressed as: TCTA, and thickness is 60 nanometers.
(4) on hole transmission layer, luminescent layer is prepared in vacuum evaporation: the material of luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), evaporation rate is 0.5nm/s, luminescent layer is expressed as: DCJTB, and thickness is 8 nanometers.
(5) on luminescent layer, electron transfer layer is prepared in vacuum evaporation: the material of electron transfer layer is 1,2,4-triazole derivative TAZ, and evaporation rate is 0.5nm/s, and electron transfer layer is expressed as: TAZ, and thickness is 200 nanometers.
(6) thermal resistance evaporation prepares fullerene doped layer on the electron transport layer, on fullerene doped layer, electron beam evaporation plating prepares titania additive layer, thermal resistance evaporation fullerene derivate layer on titania additive layer, obtain the electron injecting layer be laminated on electron transfer layer: the material of fullerene doped layer be lithium bromide (LiBr) adulterate [6, 6]-phenyl-C71-methyl butyrate (PC71BM), and lithium bromide (LiBr) and [6, the mass ratio of 6]-phenyl-C71-methyl butyrate (PC71BM) is 0.25:1, fullerene doped layer is expressed as PC71BM:LiBr, thickness is 18 nanometers,
The material of titania additive layer is the titanium dioxide (TiO that 3-dodecylthiophene (3DDT) adulterates 2), and 3-dodecylthiophene (3DDT) and titanium dioxide (TiO 2) mass ratio be 1:38, wherein, titanium dioxide (TiO 2) particle diameter be 40 nanometers, the energy density of electron beam evaporation plating titania additive layer is 35W/cm 2, titania additive layer is expressed as: TiO 2: 3DDT, thickness is 55 nanometers;
The material of fullerene derivate layer is [6,6]-phenyl-C71-methyl butyrate (PC71BM), and fullerene derivate layer is expressed as: PC71BM, and thickness is 5 nanometers.Then electron injecting layer is expressed as: PC71BM:LiBr/TiO 2: 3DDT/PC71BM.
(7) on fullerene derivate layer, cathode layer is prepared in vacuum evaporation: the material of cathode layer is platinum (Pt), and cathode layer is expressed as: Pt, and thickness is 160 nanometers, and the evaporation rate of vacuum evaporation cathode layer is 6nm/s.
The structure obtaining the present embodiment is Glass/IZO/MoO 3/ TCTA/DCJTB/TAZ/PC71BM:LiBr/TiO 2: the organic electroluminescence device of 3DDT/PC71BM/Pt; Operating pressure during vacuum evaporation in above-mentioned steps (2), (3), (4) and (5) is 2 × 10 -4pa.
Comparative example 1
The structure of the organic electroluminescence device of comparative example 1 is: Glass/ITO/MoO 3/ NPB/BCz VBi/TPBi/Cs 2cO 3/ Ag
Being prepared as follows of the organic electroluminescence device of comparative example 1:
(1) provide glass substrate, glass substrate is expressed as: Glass; Then on substrate, magnetron sputtering prepares anode layer, and wherein, the accelerating voltage of magnetron sputtering is 700V, and magnetic field is 120G, and power is 250W/cm 2, the material of anode layer is indium and tin oxide film (ITO), and anode layer is expressed as: ITO, and thickness is 120 nanometers.
(2) hole injection layer is prepared in vacuum evaporation on the anode layer: the material of hole injection layer is molybdenum trioxide (MoO 3), evaporation rate is 2nm/s, and hole injection layer is expressed as: MoO 3, thickness 20 nanometer.
(3) on hole injection layer, hole transmission layer is prepared in vacuum evaporation: the material of hole transmission layer is N, N'-(1-naphthyl)-N, N'-diphenyl-4,4'-benzidine (NPB), evaporation rate is 0.2nm/s, and hole transmission layer is expressed as: NPB, and thickness is 58 nanometers.
(4) on hole transmission layer, luminescent layer is prepared in vacuum evaporation: the material of luminescent layer is 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-, evaporation rate is 0.2nm/s, luminescent layer is expressed as: BczVBi, and thickness is 23 nanometers.
(5) on luminescent layer, electron transfer layer is prepared in vacuum evaporation: the material of electron transfer layer is N-aryl benzimidazole (TPBi), and evaporation rate is 0.2nm/s, and electron transfer layer is expressed as: TPBi, and thickness is 75 nanometers.
(6) electron injecting layer is prepared on the electron transport layer: the material of electron injecting layer is cesium carbonate (Cs 2cO 3), electron injecting layer is expressed as: Cs 2cO 3.
(7) on electron injecting layer, cathode layer is prepared in vacuum evaporation: the material of cathode layer is silver (Ag), and cathode layer is expressed as: Ag, and thickness is 180 nanometers, and the evaporation rate of vacuum evaporation cathode layer is 2nm/s.
The structure obtaining comparative example 1 is Glass//ITO/MoO 3/ NPB/BCz VBi/TPBi/Cs 2cO 3the organic electroluminescence device of/Ag; Operating pressure during vacuum evaporation in above-mentioned steps (2), (3), (4) and (5) is 8 × 10 -4pa.
What Fig. 3 represented is structure prepared by embodiment 1 is Glass/ITO/MoO 3/ NPB/Bcz VBi/TPBi/C60:LiF/TiO 2: structure prepared by the organic electroluminescence device of 3HT/C60/Ag and comparative example 1 is Glass//ITO/MoO 3/ NPB/BCz VBi/TPBi/Cs 2cO 3the graph of relation of the brightness-luminous efficiency of the organic electroluminescence device of/Ag, wherein, structure prepared by the embodiment 1 that curve 1 represents is Glass/ITO/MoO 3/ NPB/Bcz VBi/TPBi/C60:LiF/TiO 2: the relation curve of the brightness-luminous efficiency of the organic electroluminescence device of 3HT/C60/Ag, what curve 2 represented is structure prepared by comparative example 1 is Glass//ITO/MoO 3/ NPB/BCz VBi/TPBi/Cs 2cO 3the relation curve of the brightness-luminous efficiency of the organic electroluminescence device of/Ag.As can be seen from Figure 3, under different brightness, the luminous efficiency of the organic electroluminescence device of embodiment 1 is all large than the luminous efficiency of the organic electroluminescence device of comparative example 1, the maximum luminous efficiency of the organic electroluminescence device of embodiment 1 is 4.56lm/W, and the luminous efficiency of the organic electroluminescence device of comparative example 1 is only 3.51lm/W, while the luminous efficiency of comparative example 1 declines fast along with the increase of brightness, this explanation, the electron injecting layer of the organic electroluminescence device of embodiment 1 is conducive to improving electron transfer rate, improve the injectability of electronics, make light generation scattering, reduce film defects, the luminous efficiency of final raising organic electroluminescence device.And embodiment 2 ~ 4 all has the performance similar with embodiment 1 and effect.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.

Claims (10)

1. an organic electroluminescence device, comprise the anode layer stacked gradually on substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer, it is characterized in that, described electron injecting layer comprises the fullerene doped layer stacked gradually on described electron transfer layer, titania additive layer and fullerene derivate layer, described cathode layer is laminated on described fullerene derivate layer, the material of described fullerene doped layer comprises the first fullerene derivate and is doped in the lithium salts in described first fullerene derivate, the material of described titania additive layer comprises titanium dioxide and is doped in the thiophene compound in described titanium dioxide, the material of described fullerene derivate layer is the second fullerene derivate, described first fullerene derivate and described second fullerene derivate are selected from football alkene respectively, carbon 70, [6, 6]-phenyl-C61-methyl butyrate and [6, 6] one in-phenyl-C71-methyl butyrate.
2. organic electroluminescence device according to claim 1, is characterized in that, described in the material of described fullerene doped layer, the mass ratio of lithium salts and described first fullerene derivate is 0.1:1 ~ 0.4:1.
3. organic electroluminescence device according to claim 1 and 2, is characterized in that, described lithium salts is lithia, lithium fluoride, lithium chloride or lithium bromide.
4. organic electroluminescence device according to claim 1, is characterized in that, described in the material of described titania additive layer, the mass ratio of titanium dioxide and described thiophene compound is 20:1 ~ 40:1.
5. the organic electroluminescence device according to claim 1 or 4, is characterized in that, described thiophene compound is 3 methyl thiophene, 3 methyl thiophene, 3-octyl thiophene or 3-dodecylthiophene.
6. the organic electroluminescence device according to claim 1 or 4, is characterized in that, the particle diameter of described titanium dioxide is 20 nanometer ~ 50 nanometers.
7. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described fullerene doped layer is 15 nanometer ~ 30 nanometers; The thickness of described titania additive layer is 20 nanometer ~ 50 nanometers; The thickness of described fullerene derivate layer is 50 nanometer ~ 70 nanometers.
8. organic electroluminescence device according to claim 1, is characterized in that, described substrate is glass;
The material of described anode layer is indium and tin oxide film, mix the zinc-oxide film of aluminium or mix the zinc-oxide film of indium, and the thickness of described anode layer is 50 nanometer ~ 300 nanometers;
The material of described hole injection layer is molybdenum trioxide, tungstic acid or vanadic oxide, and the thickness of described hole injection layer is 20 nanometer ~ 80 nanometers;
The material of described hole transmission layer is 1,1-bis-[4-[N, N'-bis-(p-tolyl) is amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-base) triphenylamine or N, N'-(1-naphthyl)-N, N'-diphenyl-4,4'-benzidine, the thickness of described hole transmission layer is 20 nanometer ~ 60 nanometers;
The material of described luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl of 4'-or oxine aluminium, the thickness of described luminescent layer is 5 nanometer ~ 40 nanometers;
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole, and the thickness of described electron transfer layer is 40 nanometer ~ 250 nanometers;
The material of described cathode layer is silver, aluminium, platinum or gold, and the thickness of described cathode layer is 80 nanometer ~ 250 nanometers.
9. a preparation method for organic electroluminescence device, is characterized in that, comprises the steps:
There is provided substrate, magnetron sputtering prepares anode layer on the substrate;
On described anode layer, hole injection layer is prepared in vacuum evaporation;
On described hole injection layer, hole transmission layer is prepared in vacuum evaporation;
Luminescent layer is prepared in vacuum evaporation on the hole transport layer;
Electron transfer layer is prepared in vacuum evaporation on the light-emitting layer;
Thermal resistance evaporation prepares fullerene doped layer on the electron transport layer, on described fullerene doped layer, electron beam evaporation plating prepares titania additive layer, thermal resistance evaporation fullerene derivate layer on described titania additive layer, obtain being laminated in the electron injecting layer on described electron transfer layer, wherein, the material of described fullerene doped layer comprises the first fullerene derivate and is doped in the lithium salts in described first fullerene derivate, the material of described titania additive layer comprises titanium dioxide and is doped in the thiophene compound in described titanium dioxide, the material of described fullerene derivate layer is the second fullerene derivate, described first fullerene derivate and described second fullerene derivate are selected from football alkene respectively, carbon 70, [6, 6]-phenyl-C61-methyl butyrate and [6, 6] one in-phenyl-C71-methyl butyrate, and
On described fullerene derivate layer, cathode layer is prepared in vacuum evaporation.
10. the preparation method of organic electroluminescence device according to claim 9, it is characterized in that, before magnetron sputtering prepares described anode layer on the substrate, also comprise the cleaning step to described substrate: described substrate is used distilled water, ethanol purge successively, then soaks in isopropyl alcohol.
CN201310706654.1A 2013-12-19 2013-12-19 Organic light-emitting device and manufacturing method thereof Pending CN104733627A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310706654.1A CN104733627A (en) 2013-12-19 2013-12-19 Organic light-emitting device and manufacturing method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310706654.1A CN104733627A (en) 2013-12-19 2013-12-19 Organic light-emitting device and manufacturing method thereof

Publications (1)

Publication Number Publication Date
CN104733627A true CN104733627A (en) 2015-06-24

Family

ID=53457314

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310706654.1A Pending CN104733627A (en) 2013-12-19 2013-12-19 Organic light-emitting device and manufacturing method thereof

Country Status (1)

Country Link
CN (1) CN104733627A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111162173A (en) * 2019-12-30 2020-05-15 电子科技大学 Organic photoelectric detector with doped electron transport layer and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111162173A (en) * 2019-12-30 2020-05-15 电子科技大学 Organic photoelectric detector with doped electron transport layer and preparation method thereof

Similar Documents

Publication Publication Date Title
CN104037328A (en) Organic light emitting diode and preparation method thereof
CN104733624A (en) Organic electroluminescence device and preparing method thereof
CN104183778A (en) Organic electroluminescent device and preparation method thereof
CN104124368A (en) Organic light-emitting device and preparation method thereof
CN104733627A (en) Organic light-emitting device and manufacturing method thereof
CN104518102A (en) Organic electroluminescent device and preparation method thereof
CN104733635A (en) Organic light-emitting device and preparation method thereof
CN104518145A (en) Organic electroluminescent device and method for preparing same
CN104733637A (en) Organic light-emitting device and manufacturing method thereof
CN104518108A (en) Organic electroluminescent device and method for preparing same
CN104638197A (en) Organic light-emitting device and production method thereof
CN104518150A (en) Organic electroluminescent device and method for preparing same
CN103972408A (en) Organic light-emitting device and method for manufacturing same
CN103972421A (en) Organic light-emitting device and production method thereof
CN104733630A (en) Organic light-emitting device and manufacturing method thereof
CN104638141A (en) Organic light-emitting device and production method thereof
CN104518138A (en) Organic electroluminescent device and preparation method thereof
CN104518106A (en) Organic light-emitting device and making method thereof
CN104425733A (en) Organic electroluminescence device and manufacturing method thereof
CN104518109A (en) Organic electroluminescent device and method for preparing same
CN104347812A (en) Organic electroluminescence device and preparation method thereof
CN104733625A (en) Organic light-emitting device and manufacturing method thereof
CN104347803A (en) Organic electroluminescence device and preparation method thereof
CN104733628A (en) Organic light-emitting device and manufacturing method thereof
CN104078568A (en) Organic light-emitting diode and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20150624