CN104009178A - Organic electroluminescent device and preparation method - Google Patents
Organic electroluminescent device and preparation method Download PDFInfo
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- CN104009178A CN104009178A CN201310059582.6A CN201310059582A CN104009178A CN 104009178 A CN104009178 A CN 104009178A CN 201310059582 A CN201310059582 A CN 201310059582A CN 104009178 A CN104009178 A CN 104009178A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/854—Arrangements for extracting light from the devices comprising scattering means
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
- H10K71/166—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using selective deposition, e.g. using a mask
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
- H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
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- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses an organic electroluminescent device and its preparation method. A polymer layer is firstly prepared on a glass substrate, thus reducing refractive index difference between the glass substrate and the air. A scattering layer is prepared on the polymer layer. Then, light which reaches a polymer can be scattered, and light which is emitted to two sides can return to the middle. Thus, luminous efficiency is raised. Transmission band of silicon oxide is wide, and silicon oxide has a high anti-reflection effect. Refractive index difference between the polymer layer and the air also can be further minimized, total reflection probability is reduced, and more light is emitted to the air. The preparation method is simple and easy to control and operate, and raw materials are easily available.
Description
Technical field
The invention belongs to organic electroluminescent field, be specifically related to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) is a kind ofly to take organic material as luminescent material, the energy conversion device that can be luminous energy the electric energy conversion applying.It has the outstanding properties such as ultra-thin, self-luminous, response are fast, low-power consumption, in fields such as demonstration, illuminations, has application prospect very widely.
The structure of organic electroluminescence device is sandwich structure, accompanies one or more layers organic film between negative electrode and conductive anode.In containing the device of sandwich construction, inner side, the two poles of the earth mainly comprises luminescent layer, implanted layer and transport layer.Organic electroluminescence device is carrier injection type luminescent device, at anode and negative electrode, add after operating voltage, hole is from anode, electronics is injected into respectively the organic material layer of device work from negative electrode, it is luminous that two kinds of charge carriers form hole-duplet in luminous organic material, and then light sends from electrode.
In traditional luminescent device, all generally that to take indium tin oxide transparent conducting film (ITO) substrate of glass be exiting surface, in this structure, the outgoing meeting of light is first reflected through the absorption of ITO electric conducting material, then carries out absorption and the reflection of a substrate of glass, finally just can shine in air, but there is refringence between glass and ITO interface, can make light, when ITO arrives glass, total reflection occur, cause the loss of bright dipping, thereby it be lower to cause integral body to go out optical property.
Summary of the invention
In order to address the above problem, the present invention aims to provide a kind of organic electroluminescence device having compared with high light-emitting efficiency.The present invention also provides a kind of preparation method of organic electroluminescence device.
First aspect, the invention provides a kind of organic electroluminescence device, comprise the light removing layer, substrate of glass, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described smooth removing layer comprises polymeric layer and scattering layer, the material of described polymeric layer comprises poly-3,4-dioxy ethene thiophene and polyphenyl sulfonate, the material of described scattering layer is that refractive index is greater than 2.0 metal oxide and according to mass fraction 10 ~ 50%, is doped to the mixture forming in Si oxide.
Two sides in clean substrate of glass arranges respectively light removing layer and anode.
Preferably, substrate of glass is refractive index higher than 1.8 optical glass, and described optical glass is greater than 90% to the transmitance of visible ray.
Preferably, the glass trade mark that substrate of glass is selected is N-LAF36, N-LASF31A, N-LASF41 or N-LASF44.
This trade mark is the German Xiao Te trade mark (SCHOTT), wherein, the international glass code of N-LAF36 glass is 800424.443, the international glass code of N-LASF31A glass is 883408.551, the international glass code of N-LASF41 glass is that the international glass code of 835431.485, N-LASF44 glass is 804465.444.
In substrate of glass, set gradually polymeric layer and scattering layer as light removing layer.
The material of polymeric layer comprises poly-3,4-dioxy ethene thiophene and polyphenyl sulfonate (PEDOT:PSS).Poly-3,4-dioxy ethene thiophene and polyphenyl sulfonate refractive index are low, and light is had to good scattering process, and have good matching with substrate of glass.
Preferably, poly-3,4-dioxy ethene thiophene and described polyphenyl sulfonate are common commercial goods.
Preferably, the weight ratio of poly-3,4-dioxy ethene thiophene and described polyphenyl sulfonate is 2:1 ~ 6:1.
Preferably, the thickness of polymeric layer is 20 ~ 80nm.
By adopting refractive index to be greater than 1.8, visible light transmissivity is greater than to 90% optical glass as the substrate of device, eliminate the total reflection between glass and anode, more light is incided in substrate; In substrate of glass, first prepare polymeric layer, polymeric layer refractive index is 1.6 left and right, can reduce the refringence between glass substrate and air, and the ratio that makes light arrive air from glass increases.
Scattering layer is set on polymeric layer.The material of scattering layer is that refractive index is greater than the mixture that 2.0 metal oxide and Si oxide form.Wherein, it is object that refractive index is greater than 2.0 metal oxide, and Si oxide is main body, and the quality that refractive index is greater than 2.0 metal oxide is 10 ~ 50% of Si oxide quality, and both mass ratioes are 1 ~ 5:10.
Preferably, refractive index is greater than 2.0 metal oxide the transmitance of light is greater than to 70%.
Preferably, to be greater than 2.0 metal oxide be hafnium oxide (HfO to refractive index
2), niobium pentaoxide (Nb
2o
5) or tantalum pentoxide (Ta
2o
5).
Preferably, Si oxide is silicon dioxide (SiO
2) or silicon monoxide (SiO).
Preferably, the thickness of scattering layer is 50 ~ 500nm.
On polymeric layer, prepare again scattering layer, can make the light that arrives polymer produce scattering, in the middle of making can get back to the light of both sides transmitting, thereby improve light extraction efficiency, simultaneously, the transmission wide waveband of Si oxide, does not absorb in very wide scope interior focusing, has stronger anti-reflection effect, and light scattering layer is doped with low-index material, also can further dwindle the refringence between polymeric layer and air, reduce total reflection probability, more light is shone in air.
Anode is arranged on the another side of substrate of glass.
Preferably, the material of anode is transparent conductive film, is selected from indium tin oxide (ITO), aluminium zinc oxide (AZO) or indium-zinc oxide (IZO).More preferably, the material of anode is ITO.
Preferably, the thickness of anode is 80 ~ 300nm.More preferably, the thickness of anode is 120nm.
On anode, set gradually hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode.
Preferably, the material of hole injection layer is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5).More preferably, the material of hole injection layer is MoO
3.
Preferably, the thickness of hole injection layer is 20 ~ 80nm.More preferably, the thickness of hole injection layer is 25nm.
Preferably, the material of hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA) or N; N '-diphenyl-N; N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB).More preferably, the material of hole transmission layer is NPB.
Preferably, the thickness of hole transmission layer is 20 ~ 60nm.More preferably, the thickness of hole transmission layer is 30nm.
Preferably, the material of luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis-(betanaphthyl) anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) or oxine aluminium (Alq
3).More preferably, the material of luminescent layer is Alq
3.
Preferably, the thickness of luminescent layer is 5 ~ 40nm.More preferably, the thickness of luminescent layer is 20nm.
Preferably, the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).
More preferably, 1,2,4-triazole derivative is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).More preferably, the material of electron transfer layer is TAZ.
Preferably, the thickness of electron transfer layer is 40 ~ 250nm.More preferably, the thickness of electron transfer layer is 80nm.
Preferably, the material of electron injecting layer is cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) or lithium fluoride (LiF).More preferably, the material of electron injecting layer is CsF.
Preferably, the thickness of electron injecting layer is 0.5 ~ 10nm.More preferably, the thickness of electron injecting layer is 1nm.
Preferably, the material of negative electrode is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au).More preferably, the material of negative electrode is silver.
Preferably, the thickness of negative electrode is 80 ~ 250nm.More preferably, the thickness of negative electrode is 150nm.
Second aspect, the invention provides a kind of preparation method of organic electroluminescence device, comprises the following steps:
Clean substrate of glass is provided;
In the one side of described substrate of glass, prepare light removing layer, described smooth removing layer comprises polymeric layer and scattering layer:
The preparation process of described polymeric layer is, will gather 3,4-dioxy ethene thiophene and the polyphenyl sulfonate aqueous solution is spin-coated on described glass basic surface, then dries; In described poly-3,4-dioxy ethene thiophene and the polyphenyl sulfonate aqueous solution, the mass fraction of poly-3,4-dioxy ethene thiophene is 1% ~ 5%, and the weight ratio of described poly-3,4-dioxy ethene thiophene and described polyphenyl sulfonate is 2:1 ~ 6:1;
The preparation process of described scattering layer is, refractive index is greater than to 2.0 metal oxide and according to mass fraction 10 ~ 50%, is doped to the mixture forming in Si oxide and arrives described polymeric layer surface by electron beam evaporation plating;
At described substrate of glass another side magnetron sputtering transparent conductive film, prepare anode again, the condition of described magnetron sputtering is accelerating voltage 300 ~ 800V, magnetic field 50 ~ 200G, power density 1 ~ 40W/cm
2;
On described anode, thermal resistance evaporation is prepared hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively, and described thermal resistance evaporation condition is pressure 5 * 10
-5~ 2 * 10
-3pa, speed 0.1 ~ 1nm/s;
On described electron injecting layer, thermal resistance evaporation is prepared negative electrode, and described thermal resistance evaporation condition is pressure 5 * 10
-5~ 2 * 10
-3pa, speed 1 ~ 10nm/s.
By the cleaning to substrate of glass, remove the organic pollution of glass basic surface.
Particularly, the clean operation of substrate of glass is: substrate of glass is used to distilled water, alcohol flushing successively, be then placed on soaked overnight in isopropyl alcohol, remove the organic pollution of glass surface, obtain clean substrate of glass.
Preferably, substrate of glass is refractive index higher than 1.8 optical glass, and the transmitance of visible ray is greater than to 90%.
Preferably, the glass trade mark that substrate of glass is selected is N-LAF36, N-LASF31A, N-LASF41 or N-LASF44.
This trade mark is the German Xiao Te trade mark (SCHOTT), wherein, the international glass code of N-LAF36 glass is 800424.443, the international glass code of N-LASF31A glass is 883408.551, the international glass code of N-LASF41 glass is that the international glass code of 835431.485, N-LASF44 glass is 804465.444.
In substrate of glass, set gradually polymeric layer and scattering layer as light removing layer.
The material of polymeric layer comprises poly-3,4-dioxy ethene thiophene and polyphenyl sulfonate (PEDOT:PSS).Poly-3,4-dioxy ethene thiophene and polyphenyl sulfonate refractive index are low, and light is had to good scattering process, and have good matching with substrate of glass.
To gather 3,4-dioxy ethene thiophene and the polyphenyl sulfonate aqueous solution is spin-coated on glass basic surface, and then dry and obtain polymeric layer.
Preferably, poly-3,4-dioxy ethene thiophene and the polyphenyl sulfonate aqueous solution are commercially available general goods.
Preferably, the weight ratio of poly-3,4-dioxy ethene thiophene and described polyphenyl sulfonate is 2:1 ~ 6:1.
Preferably, in poly-3,4-dioxy ethene thiophene and the polyphenyl sulfonate aqueous solution, the mass fraction of poly-3,4-dioxy ethene thiophene is 1% ~ 5%.
Preferably, the thickness of polymeric layer is 20 ~ 80nm.
Preferably, spin coating condition is rotating speed 2000 ~ 6000rpm, time 10 ~ 30s.
Preferably, the condition of oven dry is 50 ~ 200 ℃ of temperature, time 10 ~ 30min.
By adopting refractive index to be greater than 1.8, visible light transmissivity is greater than to 90% optical glass as the substrate of device, eliminate the total reflection between glass and anode, more light is incided in substrate; In substrate of glass, first prepare polymeric layer, polymeric layer refractive index is 1.6 left and right, can reduce the refringence between glass substrate and air, and the ratio that makes light arrive air from glass increases.
Scattering layer is arranged on polymeric layer by the method for electron beam evaporation plating.
Preferably, condition during electron beam evaporation plating scattering layer is energy density 10 ~ 100W/cm
2.
The material of scattering layer is that refractive index is greater than the mixture that 2.0 metal oxide and Si oxide form.Wherein, it is object that refractive index is greater than 2.0 metal oxide, and Si oxide is main body, and the quality that refractive index is greater than 2.0 metal oxide is 10 ~ 50% of Si oxide quality, and both mass ratioes are 1 ~ 5:10.
Preferably, refractive index is greater than 2.0 metal oxide the transmitance of light is greater than to 70%.
Preferably, to be greater than 2.0 metal oxide be hafnium oxide (HfO to refractive index
2), niobium pentaoxide (Nb
2o
5) or tantalum pentoxide (Ta
2o
5).
Preferably, Si oxide is silicon dioxide (SiO
2) or silicon monoxide (SiO).
Preferably, the thickness of scattering layer is 50 ~ 500nm.
On polymeric layer, prepare again scattering layer, can make the light that arrives polymer produce scattering, in the middle of making can get back to the light of both sides transmitting, thereby improve light extraction efficiency, simultaneously, the transmission wide waveband of Si oxide, does not absorb in very wide scope interior focusing, has stronger anti-reflection effect, and light scattering layer is doped with low-index material, also can further dwindle the refringence between polymeric layer and air, reduce total reflection probability, more light is shone in air.
Anode is arranged on the another side of substrate of glass by the method for magnetron sputtering.
Preferably, the condition of magnetron sputtering is accelerating voltage 600 ~ 700V, magnetic field 100 ~ 120G, power density 25 ~ 30W/cm
2.
Preferably, the material of anode is transparent conductive film, is selected from indium tin oxide (ITO), aluminium zinc oxide (AZO) or indium-zinc oxide (IZO).More preferably, the material of anode is ITO.
Preferably, the thickness of anode is 80 ~ 300nm.More preferably, the thickness of anode is 120nm.
On anode, the method by thermal resistance evaporation sets gradually hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode.
Preferably, condition when thermal resistance evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer is pressure 2 * 10
-4~ 8 * 10
-4pa, speed 0.2 ~ 0.5nm/s.
Preferably, condition during thermal resistance evaporation negative electrode is pressure 2 * 10
-4~ 8 * 10
-4pa, speed 2 ~ 6nm/s.
Preferably, the material of hole injection layer is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5).More preferably, the material of hole injection layer is MoO
3.
Preferably, the thickness of hole injection layer is 20 ~ 80nm.More preferably, the thickness of hole injection layer is 25nm.
Preferably, the material of hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA) or N; N '-diphenyl-N; N '-bis-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB).More preferably, the material of hole transmission layer is NPB.
Preferably, the thickness of hole transmission layer is 20 ~ 60nm.More preferably, the thickness of hole transmission layer is 30nm.
Preferably, the material of luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis-(betanaphthyl) anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) or oxine aluminium (Alq
3).More preferably, the material of luminescent layer is Alq
3.
Preferably, the thickness of luminescent layer is 5 ~ 40nm.More preferably, the thickness of luminescent layer is 20nm.
Preferably, the material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).
More preferably, 1,2,4-triazole derivative is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).More preferably, the material of electron transfer layer is TAZ.
Preferably, the thickness of electron transfer layer is 40 ~ 250nm.More preferably, the thickness of electron transfer layer is 80nm.
Preferably, the material of electron injecting layer is cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) or lithium fluoride (LiF).More preferably, the material of electron injecting layer is CsF.
Preferably, the thickness of electron injecting layer is 0.5 ~ 10nm.More preferably, the thickness of electron injecting layer is 1nm.
Preferably, the material of negative electrode is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au).More preferably, the material of negative electrode is silver.
Preferably, the thickness of negative electrode is 80 ~ 250nm.More preferably, the thickness of negative electrode is 150nm.
The present invention has following beneficial effect:
(1) adopt refractive index to be greater than 1.8, visible light transmissivity is greater than to 90% optical glass as the substrate of device, eliminate the total reflection between glass and anode, more light is incided in substrate; In substrate of glass, first prepare polymeric layer, polymeric layer refractive index is 1.6 left and right, can reduce the refringence between glass substrate and air, and the ratio that makes light arrive air from glass increases.
(2) on polymeric layer, prepare again scattering layer, can make the light that arrives polymer produce scattering, in the middle of making can get back to the light of both sides transmitting, thereby improve light extraction efficiency, simultaneously, the transmission wide waveband of Si oxide, does not absorb in very wide scope interior focusing, has stronger anti-reflection effect, and light scattering layer is doped with low-index material, also can further dwindle the refringence between polymeric layer and air, reduce total reflection probability, more light is shone in air.
(3) preparation method of the present invention is simple, be easy to control and operation, and raw material easily obtains.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the structure chart of the organic electroluminescence device that provides of the embodiment of the present invention 1;
Fig. 2 is organic electroluminescence device and the current density of existing organic electroluminescence device and the graph of a relation of luminous efficiency that the embodiment of the present invention 1 provides.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
A preparation method for organic electroluminescence device, comprises the following steps:
(1) after N-LASF44 distilled water for glass, alcohol flushing is clean, be placed in isopropyl alcohol and soak an evening, obtain clean substrate of glass;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), rotating speed with 4000rpm is arranged on PEDOT:PSS aqueous solution spin coating 15s in clean substrate of glass, at 100 ℃, dry 15min afterwards, obtain the polymeric layer that thickness is 50nm, wherein, in the PEDOT:PSS aqueous solution, the mass fraction of PEDOT is that the weight ratio of 3.5%, PEDOT and PSS is 3:1;
By HfO
2: SiO
2mixture is arranged on polymeric layer by electron beam evaporation plating, obtains the scattering layer that thickness is 200nm, wherein HfO
2: SiO
2mixture is by HfO
2according to mass fraction 40%, be doped to SiO
2the mixture of middle formation, the condition of electron beam evaporation plating is energy density 30W/cm
2;
(3) by magnetron sputtering ITO, prepare anode, thickness is 120nm, and condition is accelerating voltage 700V, magnetic field 120G, power density 25W/cm
2;
(4) at pressure, be then 8 * 10
-4under the condition of Pa, with the evaporation speed of 0.2nm/s thermal resistance evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer successively on anode, with the evaporation speed of 2nm/s in electron injecting layer surface resistance of heat transfer evaporation silvery for negative electrode, obtain organic electroluminescence device.
Particularly, in the present embodiment, the material of hole injection layer is MoO
3, thickness is 25nm; The material of hole transmission layer is NPB, and thickness is 30nm; The material of luminescent layer is Alq
3, thickness is 20nm; The material of electron transfer layer is TAZ, and thickness is 80nm; The material of electron injecting layer is CsF, and thickness is 1nm; The material of negative electrode is silver, and thickness is 150nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: HfO
2: SiO
2/ PEDOT:PSS/N-LASF44 glass/ITO/MoO
3/ NPB/Alq
3/ TAZ/CsF/Ag.Utilize the Keithley2400 test electric property of U.S. Keithley company, colorimeter (Japanese Konica Minolta company, model: CS-100A) test brightness and colourity, fiber spectrometer (U.S. marine optics company, model: USB4000) testing electroluminescent spectrum.
Fig. 1 is the structural representation of the organic electroluminescence device of the present embodiment.As shown in Figure 1, the structure of this organic electroluminescence device comprises light removing layer 10, substrate of glass 20, anode 30, hole injection layer 40, hole transmission layer 50, luminescent layer 60, electron transfer layer 70, electron injecting layer 80 and the negative electrode 90 stacking gradually, wherein light removing layer 10 comprises scattering layer 101,, polymeric layer 102.
Fig. 2 is the graph of a relation of the organic electroluminescence device of the present embodiment and the current density of existing luminescent device and luminous efficiency.Wherein, curve 1 is the present embodiment the current density of organic electroluminescence device and the graph of a relation of current efficiency; The current density that curve 2 is existing luminescent device and the graph of a relation of current efficiency.
As can see from Figure 2, under different current densities, the luminous efficiency of the present embodiment organic electroluminescence device is large than existing luminescent device all, maximum luminous efficiency is 6.3lm/W, and that existing luminescent device is only 4.9lm/W, and the luminous efficiency of existing luminescent device along with the increase of current density fast-descending, this explanation, adopt refractive index to be greater than 1.8, visible light transmissivity is greater than to 90% optical glass as the substrate of device, eliminate the total reflection between glass and anode, more light is incided in substrate; In substrate of glass, first prepare polymeric layer, can reduce the refringence between glass substrate and air, the ratio that makes light arrive air from glass increases.On polymeric layer, prepare again scattering layer, can make the light that arrives polymer produce scattering, in the middle of making can get back to the light of both sides transmitting, thereby improve light extraction efficiency, simultaneously, the transmission wide waveband of Si oxide, does not absorb in very wide scope interior focusing, has stronger anti-reflection effect, and light scattering layer is doped with low-index material, also can further dwindle the refringence between polymeric layer and air, reduce total reflection probability, more light is shone in air.
Embodiment 2
A preparation method for organic electroluminescence device, comprises the following steps:
(1) after N-LAF36 distilled water for glass, alcohol flushing is clean, be placed in isopropyl alcohol and soak an evening, obtain clean substrate of glass;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), rotating speed with 6000rpm is arranged on PEDOT:PSS aqueous solution spin coating 30s in clean substrate of glass, at 200 ℃, dry 10min afterwards, obtain the polymeric layer that thickness is 20nm, wherein, in the PEDOT:PSS aqueous solution, the mass fraction of PEDOT is that the weight ratio of 1%, PEDOT and PSS is 2:1;
By Nb
2o
5: SiO mixture is arranged on polymeric layer by electron beam evaporation plating, obtains the scattering layer that thickness is 50nm, wherein Nb
2o
5: SiO mixture is by Nb
2o
5according to mass fraction 50%, be doped to the mixture forming in SiO, the condition of electron beam evaporation plating is energy density 10W/cm
2;
(3) by magnetron sputtering IZO, prepare anode, thickness is 80nm, and condition is accelerating voltage 300V, magnetic field 50G, power density 40W/cm
2;
(4) at pressure, be then 2 * 10
-3under the condition of Pa, with the evaporation speed of 1nm/s thermal resistance evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer successively on anode, with the evaporation speed of 10nm/s in electron injecting layer surface resistance of heat transfer evaporation silvery for negative electrode, obtain organic electroluminescence device.
Particularly, in the present embodiment, the material of hole injection layer is MoO
3, thickness is 40nm; The material of hole transmission layer is TAPC, and thickness is 45nm; The material of luminescent layer is DCJTB, and thickness is 5nm; The material of electron transfer layer is TAZ, and thickness is 65nm; The material of electron injecting layer is Cs
2cO
3, thickness is 10nm; The material of negative electrode is Pt, and thickness is 80nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: Nb
2o
5: SiO/PEDOT:PSS/N-LAF36 glass/IZO/MoO
3/ TAPC/DCJTB/TAZ/Cs
2cO
3/ Pt.
Embodiment 3
A preparation method for organic electroluminescence device, comprises the following steps:
(1) after N-LASF31A distilled water for glass, alcohol flushing is clean, be placed in isopropyl alcohol and soak an evening, obtain clean substrate of glass;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), rotating speed with 2000rpm is arranged on PEDOT:PSS aqueous solution spin coating 10s in clean substrate of glass, at 50 ℃, dry 30min afterwards, obtain the polymeric layer that thickness is 80nm, wherein, in the PEDOT:PSS aqueous solution, the mass fraction of PEDOT is that the weight ratio of 10%, PEDOT and PSS is 6:1;
By Ta
2o
5: SiO mixture is arranged on polymeric layer by electron beam evaporation plating, obtains the scattering layer that thickness is 500nm, wherein Ta
2o
5: SiO mixture is by Ta
2o
5according to mass fraction 10%, be doped to the mixture forming in SiO, the condition of electron beam evaporation plating is energy density 100W/cm
2;
(3) by magnetron sputtering AZO, prepare anode, thickness is 300nm, and condition is accelerating voltage 800V, magnetic field 200G, power density 1W/cm
2;
(4) at pressure, be then 5 * 10
-5under the condition of Pa, with the evaporation speed of 0.1nm/s thermal resistance evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer successively on anode, with the evaporation speed of 1nm/s in electron injecting layer surface resistance of heat transfer evaporation silvery for negative electrode, obtain organic electroluminescence device.
Particularly, in the present embodiment, the material of hole injection layer is V
2o
5, thickness is 20nm; The material of hole transmission layer is TCTA, and thickness is 60nm; The material of luminescent layer is ADN, and thickness is 10nm; The material of electron transfer layer is Bphen, and thickness is 250nm; The material of electron injecting layer is LiF, and thickness is 0.5nm; The material of negative electrode is Al, and thickness is 100nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: Ta
2o
5: SiO/PEDOT:PSS/N-LASF31A glass/AZO/V
2o
5/ TCTA/ADN/Bphen/LiF/Al.
Embodiment 4
A preparation method for organic electroluminescence device, comprises the following steps:
(1) after N-LASF41 distilled water for glass, alcohol flushing is clean, be placed in isopropyl alcohol and soak an evening, obtain clean substrate of glass;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), rotating speed with 5000rpm is arranged on PEDOT:PSS aqueous solution spin coating 20s in clean substrate of glass, at 50 ℃, dry 20min afterwards, obtain the polymeric layer that thickness is 70nm, wherein, in the PEDOT:PSS aqueous solution, the mass fraction of PEDOT is that the weight ratio of 1.5%, PEDOT and PSS is 5:1;
By HfO
2: SiO mixture is arranged on polymeric layer by electron beam evaporation plating, obtains the scattering layer that thickness is 300nm, wherein HfO
2: SiO mixture is by HfO
2according to mass fraction 25%, be doped to the mixture forming in SiO, the condition of electron beam evaporation plating is energy density 80W/cm
2;
(3) by magnetron sputtering ITO, prepare anode, thickness is 180nm, and condition is accelerating voltage 600V, magnetic field 100G, power density 30W/cm
2;
(4) at pressure, be then 2 * 10
-4under the condition of Pa, with the evaporation speed of 0.5nm/s thermal resistance evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer successively on anode, with the evaporation speed of 5nm/s in electron injecting layer surface resistance of heat transfer evaporation silvery for negative electrode, obtain organic electroluminescence device.
Particularly, in the present embodiment, the material of hole injection layer is MoO
3, thickness is 80nm; The material of hole transmission layer is NPB, and thickness is 20nm; The material of luminescent layer is BCzVBi, and thickness is 40nm; The material of electron transfer layer is Bphen, and thickness is 40nm; The material of electron injecting layer is CsN
3, thickness is 3nm; The material of negative electrode is Au, and thickness is 250nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: HfO
2: SiO/PEDOT:PSS/N-LASF41 glass/ITO/MoO
3/ NPB/BCzVBi/Bphen/CsN
3/ Au.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. an organic electroluminescence device, it is characterized in that, comprise the light removing layer, substrate of glass, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, described smooth removing layer comprises polymeric layer and scattering layer, the material of described polymeric layer comprises poly-3,4-dioxy ethene thiophene and polyphenyl sulfonate, the material of described scattering layer is that refractive index is greater than 2.0 metal oxide and according to mass fraction 10 ~ 50%, is doped to the mixture forming in Si oxide.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, the weight ratio of described poly-3,4-dioxy ethene thiophene and described polyphenyl sulfonate is 2:1 ~ 6:1.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, described refractive index is greater than 2.0 metal oxide the transmitance of light is greater than to 70%.
4. organic electroluminescence device as claimed in claim 1, is characterized in that, it is hafnium oxide, niobium pentaoxide or tantalum pentoxide that described refractive index is greater than 2.0 metal oxide.
5. organic electroluminescence device as claimed in claim 1, is characterized in that, described Si oxide is silicon dioxide or silicon monoxide.
6. organic electroluminescence device as claimed in claim 1, is characterized in that, described substrate of glass is refractive index higher than 1.8 optical glass, and the transmitance of the visible ray that described optical glass is 400 ~ 700nm to wavelength is greater than 90%.
7. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
Clean substrate of glass is provided;
In the one side of described substrate of glass, prepare light removing layer, described smooth removing layer comprises polymeric layer and scattering layer:
The preparation process of described polymeric layer is, will gather 3,4-dioxy ethene thiophene and the polyphenyl sulfonate aqueous solution is spin-coated on described glass basic surface, then under 50 ~ 200 ℃ of conditions, dries 10 ~ 30min; In described poly-3,4-dioxy ethene thiophene and the polyphenyl sulfonate aqueous solution, the mass fraction of poly-3,4-dioxy ethene thiophene is 1% ~ 5%, and the weight ratio of described poly-3,4-dioxy ethene thiophene and described polyphenyl sulfonate is 2:1 ~ 6:1;
The preparation process of described scattering layer is, refractive index is greater than to 2.0 metal oxide and according to mass fraction 10 ~ 50%, is doped to the mixture forming in Si oxide and arrives described polymeric layer surface by electron beam evaporation plating;
At described substrate of glass another side magnetron sputtering, prepare anode again, the condition of described magnetron sputtering is accelerating voltage 300 ~ 800V, magnetic field 50 ~ 200G, power density 1 ~ 40W/cm
2;
On anode, thermal resistance evaporation is prepared hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively, and described thermal resistance evaporation condition is pressure 5 * 10
-5~ 2 * 10
-3pa, speed 0.1 ~ 1nm/s;
On described electron injecting layer, thermal resistance evaporation is prepared negative electrode, and described thermal resistance evaporation condition is pressure 5 * 10
-5~ 2 * 10
-3pa, speed 1 ~ 10nm/s.
8. the preparation method of a kind of organic electroluminescence device as claimed in claim 7, is characterized in that, described spin coating condition is rotating speed 2000 ~ 6000rpm, time 10 ~ 30s.
9. the preparation method of a kind of organic electroluminescence device as claimed in claim 7, is characterized in that, it is hafnium oxide, niobium pentaoxide or tantalum pentoxide that described refractive index is greater than 2.0 metal oxide.
10. the preparation method of a kind of organic electroluminescence device as claimed in claim 7, is characterized in that, described Si oxide is silicon dioxide or silicon monoxide.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108091770A (en) * | 2016-12-28 | 2018-05-29 | 南京第壹有机光电有限公司 | A kind of OLED device containing light extraction film adhesion promoting layer |
| CN113707813A (en) * | 2021-08-26 | 2021-11-26 | 电子科技大学 | Transparent top electrode composite film material for organic photoelectric device and preparation method thereof |
| CN114695780A (en) * | 2020-12-30 | 2022-07-01 | Tcl科技集团股份有限公司 | Top-emission quantum dot light-emitting diode and preparation method thereof |
| CN114695691A (en) * | 2020-12-30 | 2022-07-01 | Tcl科技集团股份有限公司 | Bottom emission quantum dot light-emitting diode and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101599536A (en) * | 2008-06-05 | 2009-12-09 | 三星移动显示器株式会社 | Organic light emitting diode display device |
| CN101682001A (en) * | 2007-05-10 | 2010-03-24 | 伊斯曼柯达公司 | Electroluminescent device having improved light output |
| CN101882666A (en) * | 2010-06-01 | 2010-11-10 | 昆山维信诺显示技术有限公司 | An organic electroluminescent device |
| CN101978779A (en) * | 2008-03-26 | 2011-02-16 | 住友化学株式会社 | Organic electroluminescence element, lighting device, and display device |
-
2013
- 2013-02-26 CN CN201310059582.6A patent/CN104009178A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101682001A (en) * | 2007-05-10 | 2010-03-24 | 伊斯曼柯达公司 | Electroluminescent device having improved light output |
| CN101978779A (en) * | 2008-03-26 | 2011-02-16 | 住友化学株式会社 | Organic electroluminescence element, lighting device, and display device |
| CN101599536A (en) * | 2008-06-05 | 2009-12-09 | 三星移动显示器株式会社 | Organic light emitting diode display device |
| CN101882666A (en) * | 2010-06-01 | 2010-11-10 | 昆山维信诺显示技术有限公司 | An organic electroluminescent device |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108091770A (en) * | 2016-12-28 | 2018-05-29 | 南京第壹有机光电有限公司 | A kind of OLED device containing light extraction film adhesion promoting layer |
| CN114695780A (en) * | 2020-12-30 | 2022-07-01 | Tcl科技集团股份有限公司 | Top-emission quantum dot light-emitting diode and preparation method thereof |
| CN114695691A (en) * | 2020-12-30 | 2022-07-01 | Tcl科技集团股份有限公司 | Bottom emission quantum dot light-emitting diode and preparation method thereof |
| CN113707813A (en) * | 2021-08-26 | 2021-11-26 | 电子科技大学 | Transparent top electrode composite film material for organic photoelectric device and preparation method thereof |
| CN113707813B (en) * | 2021-08-26 | 2023-05-16 | 电子科技大学 | Transparent top electrode composite film material for organic photoelectric device and preparation method thereof |
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Application publication date: 20140827 |