CN104659231A - Organic electroluminescence device and preparation method thereof - Google Patents
Organic electroluminescence device and preparation method thereof Download PDFInfo
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- CN104659231A CN104659231A CN201310603526.4A CN201310603526A CN104659231A CN 104659231 A CN104659231 A CN 104659231A CN 201310603526 A CN201310603526 A CN 201310603526A CN 104659231 A CN104659231 A CN 104659231A
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Abstract
The invention discloses an organic electroluminescence device which comprises a glass substrate, a scattering layer, an anode, a hole injection layer, a hole transmission layer, a light emitting layer, an electron transfer layer, an electron injection layer and a cathode which are overlapped in sequence, wherein the scattering layer consists of a first light emitting material layer, a metallic oxide doped layer and a second light emitting material layer; the first light emitting material layer and the second light emitting material layer are made of a same material selected from at least one of 4-(dinitrile methyl)-2-butyl-6-(1,1,7,7-tetramethyljulolidine-9-vinyl)-4H-pyran, 9,10-di-beta-naphthylene anthracene, 4,4'-di(9-ethyl-3-carbazole vinyl)-1,1'-biphenyl and 8-hydroxyquinoline aluminum; the metallic oxide doped layer comprises a first metallic oxide and a second metallic oxide doped in the first metallic oxide. The organic electroluminescence device disclosed by the invention is relatively high in light emission efficiency. The invention further provides a preparation method of the organic electroluminescence device.
Description
Technical field
The present invention relates to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Under the principle of luminosity of organic electroluminescence device is based on the effect of extra electric field, electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Meet at luminescent layer in electronics and hole, compound, formation exciton, and exciton moves under electric field action, and by energy transferring to luminescent material, and excitation electron is from ground state transition to excitation state, and excited energy, by Radiation-induced deactivation, produces photon, release luminous energy.
In traditional luminescent device, the light of device inside only has about 18% can be transmitted into outside to go, and other part can consume at device exterior with other forms, (as the specific refractivity between glass and ITO, glass refraction is 1.5, ITO is 1.8 to there is the difference of refractive index between interface, light arrives glass from ITO, will total reflection be there is), cause the loss of total reflection, thus it is lower to cause entirety to go out optical property.
Summary of the invention
Based on this, be necessary to provide organic electroluminescence device that a kind of light extraction efficiency is higher and preparation method thereof.
A kind of organic electroluminescence device, comprise the substrate of glass stacked gradually, scattering layer, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described scattering layer is by the first luminous material layer, doped metallic oxide layer and the second luminous material layer composition, described first luminous material layer is identical with described second luminescent material layer material is selected from 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, 4 '-bis-(9-ethyl-3-carbazole vinyl)-1, at least one in 1 '-biphenyl and oxine aluminium, described doped metallic oxide layer comprises the first metal oxide and is entrained in described second metal oxide in described first metal oxide, the HOMO energy level of described first metal oxide is-5.2eV ~-6.0eV, described second metal oxide refractive index is 1.8 ~ 2.0.
Described first metal oxide materials is selected from least one in molybdenum trioxide, tungstic acid and vanadic oxide, and described second metal oxide layer material is selected from least one in zirconia, magnesium oxide and calcium oxide.
The thickness of described first luminous material layer is 20nm ~ 60nm, and the thickness of described doped metallic oxide layer is 100nm ~ 300nm, and the thickness of described second luminous material layer is 2nm ~ 10nm.
Described in described doped metallic oxide layer, the mass ratio of the first metal oxide and described second metal oxide is 10:1 ~ 15:1.
A preparation method for organic electroluminescence device, comprises the following steps:
Scattering layer is prepared at glass basic surface evaporation, described scattering layer is by the first luminous material layer, doped metallic oxide layer and the second luminous material layer composition, thermal resistance evaporation is adopted to prepare the first luminous material layer at described glass basic surface, described doped metallic oxide layer is prepared by electron beam evaporation plating on described first luminous material layer surface, described doped metallic oxide layer comprises the first metal oxide and is entrained in described second metal oxide in described first metal oxide, the HOMO energy level of described first metal oxide is-5.2eV ~-6.0eV, described second metal oxide refractive index is 1.8 ~ 2.0, then the second luminous material layer is prepared on described doped metallic oxide layer surface by thermal resistance evaporation, described first luminous material layer is identical with described second luminescent material layer material is selected from 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, 4 '-bis-(9-ethyl-3-carbazole vinyl)-1, at least one in 1 '-biphenyl and oxine aluminium,
Prepare anode at described scattering layer surface magnetic control sputtering, the material of described anode is indium tin oxide, aluminium zinc oxide or indium-zinc oxide; And
Cave implanted layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode is prepared on the surface of described anode successively evaporation.
Described first metal oxide materials is selected from least one in molybdenum trioxide, tungstic acid and vanadic oxide, and described second metal oxide layer material is selected from least one in zirconia, magnesium oxide and calcium oxide.
The thickness of described first luminous material layer is 20nm ~ 60nm, and the thickness of described doped metallic oxide layer is 100nm ~ 300nm, and the thickness of described second luminous material layer is 2nm ~ 10nm.
Described in described doped metallic oxide layer, the mass ratio of the first metal oxide and described second metal oxide is 10:1 ~ 15:1.
The technique of described thermal resistance evaporation mode is specially: operating pressure is 2 × 10
-3~ 5 × 10
-5pa, operating current is 1A ~ 5A, and the evaporation rate of organic material is 0.1 ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s, and the technique of described electron beam evaporation plating mode is specially: operating pressure is 2 × 10
-3~ 5 × 10
-5pa, the energy density of electron beam evaporation plating is 10W/cm
2~ 100W/cm
2, the evaporation rate of organic material is 0.1 ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s.
Above-mentioned organic electroluminescence device and preparation method thereof, scattering layer is prepared between anode and substrate of glass, scattering layer is by the first luminous material layer, doped metallic oxide layer and the second luminous material layer composition, the luminescent material of the first luminous material layer is fluorescence luminescent material, and it is consistent with the material of luminescent layer, can supplement luminescence is photochromic, improve photochromic purity, effective raising luminous efficiency, glow color is stablized, the rate of decay reduces, and doped metallic oxide layer is made up of with second metal oxide with high index of refraction first metal oxide with Hole injection capacity, hole injection efficiency can be improved, second metal oxide of high index of refraction can reduce the refringence between scattering layer and anode, thus effectively avoid the generation of total reflection, improve light extraction efficiency, second luminous material layer can spread to organic material place by the metal ion in the oxide-doped layer of barrier metal, avoid cancellation occurs, supplement photochromic further, improve luminous efficiency, thus the life-span of organic electroluminescence device is longer.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is scattering layer structural representation in the structure of the organic electroluminescence device of an execution mode;
Fig. 3 is current density and the luminous efficiency graph of a relation of organic electroluminescence device prepared by embodiment 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, organic electroluminescence device and preparation method thereof is illustrated further.
Refer to Fig. 1, the organic electroluminescence device 100 of an execution mode comprises the substrate of glass 10, scattering layer 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 that stack gradually.
Substrate of glass 10 for refractive index be the glass of 1.8 ~ 2.2, in 400nm transmitance higher than 90%.Substrate of glass 10 is preferably the glass that the trade mark is N-LAF36, N-LASF31A, N-LASF41A or N-LASF44.
A side surface of substrate of glass 10 is formed at reference to scattering layer 20 shown in figure 2.Scattering layer 20 is by the first luminous material layer 201, doped metallic oxide layer 202 and the second luminous material layer 203 form, described first luminous material layer 201 is identical with described second luminous material layer 203 material is selected from 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 '-bis-(9-ethyl-3-carbazole vinyl)-1, 1 '-biphenyl (BCzVBi), at least one in oxine aluminium (Alq3), described doped metallic oxide layer 202 comprises the first metal oxide and is entrained in described second metal oxide in described first metal oxide, the HOMO energy level of described first metal oxide is-5.2eV ~-6.0eV, described second metal oxide refractive index is 1.8 ~ 2.0.
Described first metal oxide materials is selected from tungstic acid (WO
3) and vanadic oxide (V
2o
5) middle at least one, described second metal oxide layer material is selected from zirconia (ZrO
2), at least one in magnesium oxide (MgO) and calcium oxide (CaO).
The thickness of described first luminous material layer 201 is 20nm ~ 60nm, and the thickness of described doped metallic oxide layer 202 is 100nm ~ 300nm, and the thickness of described second luminous material layer 203 is 2nm ~ 10nm.
Described in described doped metallic oxide layer 202, the mass ratio of the first metal oxide and described second metal oxide is 10:1 ~ 15:1.
Anode 30 is formed at the surface of scattering layer 20.The material of anode 30 is indium tin oxide (ITO), aluminium zinc oxide (AZO) or indium-zinc oxide (IZO), is preferably ITO.The thickness of anode 30 is 80nm ~ 300nm, and thickness is preferably 100nm.
Hole injection layer 40 is formed at the surface of anode 30.The material of hole injection layer 40 is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) at least one, be preferably MoO
3.The thickness of hole injection layer 40 is 20nm ~ 80nm, is preferably 40nm.
Hole transmission layer 50 is formed at the surface of hole injection layer 40.The material of hole transmission layer 50 is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4 ', 4 "-three (carbazole-9-base) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4; at least one in 4 '-benzidine (NPB), is preferably NPB.The thickness of hole transmission layer 50 is 20nm ~ 60nm, is preferably 40nm.
Luminescent layer 60 is formed at the surface of hole transmission layer 50.The material of luminescent layer 60 is selected from 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 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq
3) at least one, be preferably Alq
3.The thickness of luminescent layer 60 is 5nm ~ 40nm, is preferably 10nm.
Electron transfer layer 70 is formed at the surface of luminescent layer 60.The material of electron transfer layer 70 is selected from least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TAZ.The thickness of electron transfer layer 70 is 40nm ~ 250nm, is preferably 100nm.
Electron injecting layer 80 is formed at the surface of electron transfer layer 70.The material of electron injecting layer 80 is selected from cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) and lithium fluoride (LiF) at least one, be preferably CsF.The thickness of electron injecting layer 80 is 0.5nm ~ 10nm, is preferably 1.5nm.
Negative electrode 90 is formed at the surface of electron injecting layer 80.The material of negative electrode 90 is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au), is preferably Ag.The thickness of negative electrode 90 is 80nm ~ 250nm, is preferably 140nm.
Above-mentioned organic electroluminescence device 100, adopt refractive index more than 1.8, visible light transmissivity be the glass of more than 90% as the substrate of glass 10 of organic electroluminescence device, eliminate the total reflection between substrate of glass 10 and anode 30, make more light incide in substrate of glass 10, scattering layer 20 is prepared between anode 30 and substrate of glass 10, scattering layer is by the first luminous material layer, doped metallic oxide layer and the second luminous material layer composition, the luminescent material of the first luminous material layer is fluorescence luminescent material, and it is consistent with the material of luminescent layer, can supplement luminescence is photochromic, improve photochromic purity, effective raising luminous efficiency, glow color is stablized, the rate of decay reduces, and doped metallic oxide layer is made up of with second metal oxide with high index of refraction first metal oxide with Hole injection capacity, hole injection efficiency can be improved, second metal oxide of high index of refraction can reduce the refringence between scattering layer and anode, thus effectively avoid the generation of total reflection, improve light extraction efficiency, second luminous material layer can spread to organic material place by the metal ion in the oxide-doped layer of barrier metal, avoid cancellation occurs, supplement photochromic further, improve luminous efficiency, thus the life-span of organic electroluminescence device is longer.
Be appreciated that in this organic electroluminescence device 100 and also can other functional layers be set as required.
The preparation method of the organic electroluminescence device 100 of one embodiment, it comprises the following steps:
Step S110, prepare scattering layer 20 at substrate of glass 10 surface electronic bundle evaporation.
Scattering layer 20 is formed at a side surface of substrate of glass 10.Scattering layer 20 is made up of the first luminous material layer 201, doped metallic oxide layer 202 and the second luminous material layer 203.Thermal resistance evaporation is adopted to prepare the first luminous material layer 201 on described substrate of glass 10 surface, described doped metallic oxide layer 202 is prepared by electron beam evaporation plating on described first luminous material layer 201 surface, described doped metallic oxide layer 202 comprises the first metal oxide and is entrained in described second metal oxide in described first metal oxide, the HOMO energy level of described first metal oxide is-5.2eV ~-6.0eV, described second metal oxide refractive index is 1.8 ~ 2.0, then the second luminous material layer 203 is prepared on described doped metallic oxide layer 202 surface by thermal resistance evaporation, described first luminous material layer 201 is identical with described second luminous material layer 203 material is selected from 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 '-bis-(9-ethyl-3-carbazole vinyl)-1, 1 '-biphenyl (BCzVBi), oxine aluminium (Alq
3) middle at least one.
Described first metal oxide materials is selected from tungstic acid (WO
3) and vanadic oxide (V
2o
5) middle at least one, described second metal oxide layer material is selected from zirconia (ZrO
2), at least one in magnesium oxide (MgO) and calcium oxide (CaO).
The thickness of described first luminous material layer 201 is 20nm ~ 60nm, and the thickness of described doped metallic oxide layer 202 is 100nm ~ 300nm, and the thickness of described second luminous material layer 203 is 2nm ~ 10nm.
Described in described doped metallic oxide layer 202, the mass ratio of the first metal oxide and described second metal oxide is 10:1 ~ 15:1.
In the present embodiment, substrate of glass 10 is placed in isopropyl alcohol and soaks 1 hour ~ 10 hours after using distilled water, alcohol flushing clean before use.
In the present embodiment, the technique of described thermal resistance evaporation mode is specially: operating pressure is 2 × 10
-3~ 5 × 10
-5pa, operating current is 1A ~ 5A, and the evaporation rate of organic material is 0.1 ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s, and the technique of described electron beam evaporation plating mode is specially: operating pressure is 2 × 10
-3~ 5 × 10
-5pa, the energy density of electron beam evaporation plating is 10W/cm
2~ 100W/cm
2, the evaporation rate of organic material is 0.1 ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s.
Step S120, prepare anode 30 at scattering layer 20 surface magnetic control sputtering.
Anode 30 is formed at the surface of scattering layer 20.The material of anode 30 is indium tin oxide (ITO), aluminium zinc oxide (AZO) or indium-zinc oxide (IZO), is preferably ITO.The thickness of anode 30 is 80nm ~ 300nm, and thickness is preferably 100nm.
In present embodiment, the accelerating voltage of magnetron sputtering: 300V ~ 800V, magnetic field about: 50G ~ 200G, power density: 1W/cm
2~ 40W/cm
2, the evaporation rate of organic material is 0.1nm/s ~ 1nm/s, and the evaporation rate of metallic cathode is 1nm/s ~ 10nm/s.
Step S130, the surface of anode 30 successively evaporation formed hole injection layer 40, hole transmission layer 50, luminescent layer 60, electron transfer layer 70, electron injecting layer 80 and negative electrode 90.
Hole injection layer 40 is formed at the surface of anode 30.The material of hole injection layer 40 is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) at least one, be preferably MoO
3.The thickness of hole injection layer 40 is 20nm ~ 80nm, is preferably 40nm.Evaporation is 2 × 10 at vacuum pressure
-3pa ~ 5 × 10
-5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Hole transmission layer 50 is formed at the surface of hole injection layer 40.The material of hole transmission layer 50 is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4 ', 4 "-three (carbazole-9-base) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4; at least one in 4 '-benzidine (NPB), is preferably NPB.The thickness of hole transmission layer 50 is 20nm ~ 60nm, is preferably 40nm.Evaporation is 2 × 10 at vacuum pressure
-3pa ~ 5 × 10
-5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Luminescent layer 60 is formed at the surface of hole transmission layer 50.The material of luminescent layer 60 is selected from 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 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq
3) at least one, be preferably Alq
3.The thickness of luminescent layer 60 is 5nm ~ 40nm, is preferably 10nm.Evaporation is 2 × 10 at vacuum pressure
-3pa ~ 5 × 10
-5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Electron transfer layer 70 is formed at the surface of luminescent layer 60.The material of electron transfer layer 70 is selected from least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TAZ.The thickness of electron transfer layer 70 is 40nm ~ 250nm, is preferably 100nm.Evaporation is 2 × 10 at vacuum pressure
-3pa ~ 5 × 10
-5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Electron injecting layer 80 is formed at the surface of electron transfer layer 70.The material of electron injecting layer 80 is selected from cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) and lithium fluoride (LiF) at least one, be preferably CsF.The thickness of electron injecting layer 80 is 0.5nm ~ 10nm, is preferably 1.5nm.Evaporation is 2 × 10 at vacuum pressure
-3pa ~ 5 × 10
-5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Negative electrode 90 is formed at the surface of electron injecting layer 80.The material of negative electrode 90 is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au), is preferably Ag.The thickness of negative electrode 90 is 80nm ~ 250nm, is preferably 140nm.Evaporation is 2 × 10 at vacuum pressure
-3pa ~ 5 × 10
-5carry out under Pa, evaporation rate is 1nm/s ~ 10nm/s.
Above-mentioned organic electroluminescence device preparation method, preparation technology is simple; The light extraction efficiency of the organic electroluminescence device of preparation is higher.
Below in conjunction with specific embodiment, the preparation method to organic electroluminescence device is described in detail.
The embodiment of the present invention and the preparation used by comparative example and tester 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 measuring current density of Japanese Konica Minolta company and colourity.
Embodiment 1
It is substrate of glass/Alq that the present embodiment prepares structure
3/ MoO
3: ZrO
2/ Alq
3/ ITO/MoO
3/ NPB/Alq
3the organic electroluminescence device of/TAZ/CsF/Ag, "/" presentation layer in the present embodiment and following examples, ": " represents doping.
Substrate of glass is N-LASF44, after substrate of glass distilled water, alcohol flushing is clean, be placed in isopropyl alcohol and soak an evening.Prepare scattering layer on the glass substrate, scattering layer is made up of the first luminous material layer, doped metallic oxide layer and the second luminous material layer, and adopt thermal resistance evaporation to prepare the first luminous material layer at glass baseplate surface, material is Alq
3, thickness is 45nm, and adopt electron beam evaporation plating to prepare doped metallic oxide layer on the first luminous material layer surface, material is MoO
3: ZrO
2, MoO
3with ZrO
2mass ratio be 12:1, thickness is 200nm, and adopt thermal resistance evaporation to prepare the second luminous material layer on doped metallic oxide layer surface, material is Alq
3, thickness is 5nm.Then prepare ITO on the scattering layer, thickness is 100nm, adopts the method preparation of magnetron sputtering; Evaporation prepares hole injection layer: material is MoO
3, thickness is 40nm; Evaporation prepares hole transmission layer: material is NPB, and thickness is 40nm; Evaporation prepares luminescent layer: selected materials is Alq
3, thickness is 10nm; Evaporation prepares electron transfer layer, and material is TAZ, and thickness is 100nm; Evaporation prepares electron injecting layer, material is CsF, and thickness is 1.5nm; Evaporation prepares negative electrode, and material is Ag, and thickness is 140nm; Finally obtain required electroluminescent device.
Operating pressure prepared by magnetron sputtering is 8 × 10
-4pa, the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metallic compound is 0.3nm/s, and the evaporation rate of metal is 2nm/s.The accelerating voltage of magnetron sputtering: 700V, magnetic field about: 120G, power density: 250W/cm
2.
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 8 × 10
-5pa, operating current is 1.5A, and the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 2nm/s.
The concrete technology condition of electron beam evaporation plating mode is: operating pressure is 8 × 10
-5pa, the energy density of electron beam evaporation plating is 40W/cm
2, the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 2nm/s.
Refer to Fig. 3, the structure being depicted as preparation in embodiment 1 is substrate of glass/Alq
3/ MoO
3: ZrO
2/ Alq
3/ ITO/MoO
3/ NPB/Alq
3structure prepared by organic electroluminescence device (curve 1) and the comparative example of/TAZ/CsF/Ag is ito glass/MoO
3/ NPB/Alq
3the current density of organic electroluminescence device (curve 2) of/TAZ/CsF/Ag and the relation of luminous efficiency.Comparative example prepare the step of organic electroluminescence device and each layer thickness all identical with embodiment 1.
Can see from figure, the luminous efficiency of embodiment 1 is all larger than comparative example, the luminous efficiency of embodiment 1 is 8.21m/W, and comparative example be only 5.71m/W, and the luminous efficiency of comparative example declines fast along with the increase of current density, this explanation, the scattering layer prepared between anode and glass of high refractive index substrate, scattering layer is by the first luminous material layer, doped metallic oxide layer and the second luminous material layer composition, the luminescent material of the first luminous material layer is fluorescence luminescent material, and it is consistent with the material of luminescent layer, can supplement luminescence is photochromic, improve photochromic purity, effective raising luminous efficiency, glow color is stablized, the rate of decay reduces, and doped metallic oxide layer is made up of with second metal oxide with high index of refraction first metal oxide with Hole injection capacity, hole injection efficiency can be improved, second metal oxide of high index of refraction can reduce the refringence between scattering layer and anode, thus effectively avoid the generation of total reflection, improve light extraction efficiency, second luminous material layer can spread to organic material place by the metal ion in the oxide-doped layer of barrier metal, avoid cancellation occurs, supplement photochromic further, improve luminous efficiency, thus the life-span of organic electroluminescence device is longer.
The luminous efficiency of organic electroluminescence device prepared of each embodiment is all similar with embodiment 1 below, and each organic electroluminescence device also has similar luminous efficiency, repeats no more below.
Embodiment 2
It is substrate of glass/DCJTB/WO that the present embodiment prepares structure
3: MgO/ADN/IZO/MoO
3/ TCTA/ADN/Bphen/CsN
3the organic electroluminescence device of/Al.
Substrate of glass is N-LAF36, after substrate of glass distilled water, alcohol flushing is clean, be placed in isopropyl alcohol to soak and prepare scattering layer on the glass substrate an evening, scattering layer is made up of the first luminous material layer, doped metallic oxide layer and the second luminous material layer, adopt thermal resistance evaporation to prepare the first luminous material layer at glass baseplate surface, material is DCJTB, and thickness is 20nm, adopt electron beam evaporation plating to prepare doped metallic oxide layer on the first luminous material layer surface, material is WO
3: MgO, WO
3be 10:1 with the mass ratio of MgO, thickness is 300nm, and adopt thermal resistance evaporation to prepare the second luminous material layer on doped metallic oxide layer surface, material is ADN, and thickness is 2nm.Then prepare IZO on the scattering layer, thickness is 80nm, adopts the method preparation of magnetron sputtering; Evaporation hole injection layer, material is MoO
3, thickness is 40nm; Evaporation hole transmission layer: material is TCTA, thickness is 45nm; Evaporation luminescent layer: selected materials is ADN, thickness is 8nm; Evaporation electron transfer layer, material is Bphen, and thickness is 65nm; Evaporation electron injecting layer, material are CsN
3, thickness is 10nm; Evaporation negative electrode, material is Al, and thickness is 80nm; Finally obtain required electroluminescent device.
Operating pressure prepared by magnetron sputtering is 2 × 10
-3pa, the evaporation rate of organic material is 1nm/s, and the evaporation rate of metallic compound is 0.1nm/s, and the evaporation rate of metal is 10nm/s.The accelerating voltage of magnetron sputtering: 300V, magnetic field about: 50G, power density: 40W/cm
2.
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 2 × 10
-3pa, operating current is 1A, and the evaporation rate of organic material is 1nm/s, and the evaporation rate of metal and metallic compound is 10nm/s.
The concrete technology condition of electron beam evaporation plating mode is: operating pressure is 2 × 10
-3pa, the energy density of electron beam evaporation plating is 100W/cm
2, the evaporation rate of organic material is 1nm/s, and the evaporation rate of metal and metallic compound is 10nm/s.
Embodiment 3
It is substrate of glass/ADN/V that the present embodiment prepares structure
2o
5: CaO/DCJTB/AZO/WO
3/ TAPC/DCJTB/TPBi/Cs
2cO
3the organic electroluminescence device of/Au.
Substrate of glass is N-LASF31A, after substrate of glass distilled water, alcohol flushing is clean, be placed in isopropyl alcohol and soak an evening; Prepare scattering layer on the glass substrate, scattering layer is made up of the first luminous material layer, doped metallic oxide layer and the second luminous material layer, thermal resistance evaporation is adopted to prepare the first luminous material layer at glass baseplate surface, material is ADN, thickness is 60nm, adopt electron beam evaporation plating to prepare doped metallic oxide layer on the first luminous material layer surface, material is V
2o
5: CaO, V
2o
5be 15:1 with the mass ratio of CaO, thickness is 100nm, and adopt thermal resistance evaporation to prepare the second luminous material layer on doped metallic oxide layer surface, material is DCJTB, and thickness is 10nm.Then prepare AZO on the scattering layer, thickness is 300nm, adopts the method preparation of magnetron sputtering.Evaporation hole injection layer, material is WO
3, thickness is 20nm; Evaporation hole transmission layer: material is TAPC, thickness is 60nm; Evaporation luminescent layer: selected materials is DCJTB, thickness is 10nm; Evaporation electron transfer layer, material is TPBi, and thickness is 200nm; Evaporation electron injecting layer, material are CsF, and thickness is 0.5nm; Evaporation negative electrode, material is Au, and thickness is 100nm; Finally obtain required electroluminescent device.
Operating pressure prepared by magnetron sputtering is 5 × 10
-5pa, the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of metal is 1nm/s.The accelerating voltage of magnetron sputtering: 800V, magnetic field about: 200G, power density: 1W/cm
2.
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 5 × 10
-5pa, operating current is 5A, and the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s.
The concrete technology condition of electron beam evaporation plating mode is: operating pressure is 5 × 10
-5pa, the energy density of electron beam evaporation plating is 10W/cm
2, the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s.
Embodiment 4
It is substrate of glass/BCzVBi/V that the present embodiment prepares structure
2o
5: ZrO
2/ BCzVBi/ITO/V
2o
5the organic electroluminescence device of/NPB/BCzVBi/TAZ/LiF/Pt.
Substrate of glass is N-LASF41A, after substrate of glass distilled water, alcohol flushing is clean, be placed in isopropyl alcohol to soak and prepare scattering layer on the glass substrate an evening, scattering layer is made up of the first luminous material layer, doped metallic oxide layer and the second luminous material layer, adopt thermal resistance evaporation to prepare the first luminous material layer at glass baseplate surface, material is BCzVBi, and thickness is 25nm, adopt electron beam evaporation plating to prepare doped metallic oxide layer on the first luminous material layer surface, material is V
2o
5: ZrO
2, V
2o
5with ZrO
2mass ratio be 14:1, thickness is 180nm, and adopt thermal resistance evaporation to prepare the second luminous material layer on doped metallic oxide layer surface, material is BCzVBi, and thickness is 8nm.Then prepare ITO on the scattering layer, thickness is 180nm, adopts the method preparation of magnetron sputtering; Evaporation hole injection layer, material is V
2o
5, thickness is 80nm; Evaporation hole transmission layer: material is NPB, thickness is 60nm; Evaporation luminescent layer: selected materials is BCzVBi, thickness is 40nm; Evaporation electron transfer layer, material is TAZ, and thickness is 35nm; Evaporation electron injecting layer, material are CsN
3, thickness is 1nm; Evaporation negative electrode, material is Pt, and thickness is 250nm; Finally obtain required electroluminescent device.
Operating pressure prepared by magnetron sputtering is 2 × 10
-4pa, the evaporation rate of organic material is 0.5nm/s, and the evaporation rate of metallic compound is 0.6nm/s, and the evaporation rate of metal is 6nm/s.The accelerating voltage of magnetron sputtering: 600V, magnetic field about: 100G, power density: 30W/cm
2.
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 2 × 10
-4pa, operating current is 1.5A, and the evaporation rate of organic material is 0.5nm/s, and the evaporation rate of metal and metallic compound is 6nm/s.
The concrete technology condition of electron beam evaporation plating mode is: operating pressure is 2 × 10
-4pa, the energy density of electron beam evaporation plating is 25W/cm
2, the evaporation rate of organic material is 0.5nm/s, and the evaporation rate of metal and metallic compound is 6nm/s.
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 (9)
1. an organic electroluminescence device, it is characterized in that, comprise the substrate of glass stacked gradually, scattering layer, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described scattering layer is by the first luminous material layer, doped metallic oxide layer and the second luminous material layer composition, described first luminous material layer is identical with described second luminescent material layer material is selected from 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, 4 '-bis-(9-ethyl-3-carbazole vinyl)-1, at least one in 1 '-biphenyl and oxine aluminium, described doped metallic oxide layer comprises the first metal oxide and is entrained in described second metal oxide in described first metal oxide, the HOMO energy level of described first metal oxide is-5.2eV ~-6.0eV, described second metal oxide refractive index is 1.8 ~ 2.0.
2. organic electroluminescence device according to claim 1, it is characterized in that, described first metal oxide materials is selected from least one in molybdenum trioxide, tungstic acid and vanadic oxide, and described second metal oxide layer material is selected from least one in zirconia, magnesium oxide and calcium oxide.
3. organic electroluminescence device according to claim 1, it is characterized in that, the thickness of described first luminous material layer is 20nm ~ 60nm, and the thickness of described doped metallic oxide layer is 100nm ~ 300nm, and the thickness of described second luminous material layer is 2nm ~ 10nm.
4. organic electroluminescence device according to claim 1, is characterized in that, described in described doped metallic oxide layer, the mass ratio of the first metal oxide and described second metal oxide is 10:1 ~ 15:1.
5. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
Scattering layer is prepared at glass basic surface evaporation, described scattering layer is by the first luminous material layer, doped metallic oxide layer and the second luminous material layer composition, thermal resistance evaporation is adopted to prepare the first luminous material layer at described glass basic surface, described doped metallic oxide layer is prepared by electron beam evaporation plating on described first luminous material layer surface, described doped metallic oxide layer comprises the first metal oxide and is entrained in described second metal oxide in described first metal oxide, the HOMO energy level of described first metal oxide is-5.2eV ~-6.0eV, described second metal oxide refractive index is 1.8 ~ 2.0, then the second luminous material layer is prepared on described doped metallic oxide layer surface by thermal resistance evaporation, described first luminous material layer is identical with described second luminescent material layer material is selected from 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, 4 '-bis-(9-ethyl-3-carbazole vinyl)-1, at least one in 1 '-biphenyl and oxine aluminium,
Prepare anode at described scattering layer surface magnetic control sputtering, the material of described anode is indium tin oxide, aluminium zinc oxide or indium-zinc oxide; And
Cave implanted layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode is prepared on the surface of described anode successively evaporation.
6. the preparation method of organic electroluminescence device according to claim 5, it is characterized in that: described first metal oxide materials is selected from least one in molybdenum trioxide, tungstic acid and vanadic oxide, described second metal oxide layer material is selected from least one in zirconia, magnesium oxide and calcium oxide.
7. the preparation method of organic electroluminescence device according to claim 5, it is characterized in that: the thickness of described first luminous material layer is 20nm ~ 60nm, the thickness of described doped metallic oxide layer is 100nm ~ 300nm, and the thickness of described second luminous material layer is 2nm ~ 10nm.
8. the preparation method of organic electroluminescence device according to claim 5, is characterized in that: described in described doped metallic oxide layer, the mass ratio of the first metal oxide and described second metal oxide is 10:1 ~ 15:1.
9. the preparation method of organic electroluminescence device according to claim 5, is characterized in that: the technique of described thermal resistance evaporation mode is specially: operating pressure is 2 × 10
-3~ 5 × 10
-5pa, operating current is 1A ~ 5A, and the evaporation rate of organic material is 0.1 ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s, and the technique of described electron beam evaporation plating mode is specially: operating pressure is 2 × 10
-3~ 5 × 10
-5pa, the energy density of electron beam evaporation plating is 10W/cm
2~ 100W/cm
2, the evaporation rate of organic material is 0.1 ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s.
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| CN113363395B (en) * | 2020-03-02 | 2022-11-18 | 海信视像科技股份有限公司 | Display device |
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