CN104659229A - Organic electroluminescence device and manufacturing method for organic electroluminescence device - Google Patents

Organic electroluminescence device and manufacturing method for organic electroluminescence device Download PDF

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CN104659229A
CN104659229A CN201310601918.7A CN201310601918A CN104659229A CN 104659229 A CN104659229 A CN 104659229A CN 201310601918 A CN201310601918 A CN 201310601918A CN 104659229 A CN104659229 A CN 104659229A
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organic electroluminescence
electroluminescence device
metal oxide
thickness
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周明杰
黄辉
张振华
王平
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/865—Intermediate layers comprising a mixture of materials of the adjoining active layers
    • 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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/302—Details of OLEDs of OLED structures

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  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Electromagnetism (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention discloses an organic electroluminescence device. The organic electroluminescence device comprises a glass substrate, a scattering layer, a positive pole, a hole-injection layer, a hole-transmission layer, a light-emitting layer, an electronic transmission layer, an electronic injection layer and a negative pole which are sequentially overlapped, wherein the scattering layer comprises a metal oxide layer, a light-emitting material layer and an iron salt layer; the HOMO energy level of the material of the metal oxide layer is between -5.2 eV and -6.0 eV; the material of the light-emitting layer is selected from one and more of 4-(dicyanomethyl)-2-butyl-6-(1,1,7,7-tetramethyljulolidine-9-ethenyl)-4H-pyran, 9,10-di-beta-naphthyl anthracene, 4,4'-di(9-ethyl-3-vinylcarbazole)-1-1'-biphenyl and 8-hydroxyquinoline aluminum; the material of the iron salt layer is selected from one and more of iron chloride, iron bromide and iron sulfide. The organic electroluminescence device is relatively high in light-emitting efficiency. The invention also provides a manufacturing method for the organic electroluminescence device.

Description

Organic electroluminescence device and preparation method thereof
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 metal oxide layer, luminous material layer and molysite layer composition, the HOMO energy level of described metal oxide layer material is-5.2eV ~-6.0eV, described luminescent material layer material 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, 4 '-bis-(9-ethyl-3-carbazole vinyl)-1, at least one in 1 '-biphenyl and oxine aluminium, described molysite layer material is selected from iron chloride, at least one in ferric bromide and iron sulfide.
Described metal oxide layer material is selected from least one in molybdenum trioxide, tungstic acid and vanadic oxide.
The thickness of described metal oxide layer is 10nm ~ 30nm, and the thickness of described luminous material layer is 20nm ~ 80nm, and the thickness of described molysite layer is 50nm ~ 100nm.
The refractive index of described substrate of glass is 1.8 ~ 2.2.
The material of described luminescent layer 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, the material of described hole transmission layer is selected from 1, 1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, 4, 4 ', 4 "-three (carbazole-9-base) triphenylamine and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine.
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 metal oxide layer, luminous material layer and molysite layer composition, thermal resistance evaporation is adopted to prepare metal oxide layer at described glass basic surface, the HOMO energy level of described metal oxide layer material is-5.2eV ~-6.0eV, described luminous material layer is prepared by thermal resistance evaporation on described metal oxide layer surface, described luminescent material layer material 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, 4 '-bis-(9-ethyl-3-carbazole vinyl)-1, at least one in 1 '-biphenyl and oxine aluminium, then molysite layer is prepared on described luminous material layer surface by thermal resistance evaporation, described molysite layer material is selected from iron chloride, at least one in ferric bromide and iron sulfide,
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.
The thickness of described metal oxide layer is 10nm ~ 30nm, and the thickness of described luminous material layer is 20nm ~ 80nm, and the thickness of described molysite layer is 50nm ~ 100nm.
Described metal oxide layer material is selected from least one in molybdenum trioxide, tungstic acid and vanadic oxide.
The refractive index of described substrate of glass is 1.8 ~ 2.2.
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.
Above-mentioned organic electroluminescence device and preparation method thereof, scattering layer is prepared between anode and substrate of glass, scattering layer is by metal oxide layer, luminous material layer and molysite layer composition, metal oxide layer has Hole injection capacity, the injection efficiency in hole can be improved, potential barrier between anode and hole injection layer is reduced, avoid energy loss, luminous material layer is that fluorescence luminescent material 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, molysite layer is made up of molysite material, the carrier concentration of molysite material is higher, the conductivity of device can be improved, potential barrier between lower layer, the potential barrier that hole is injected reduces, 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 brightness 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 made up of metal oxide layer 201, luminous material layer 202 and molysite layer 203, the HOMO energy level of described metal oxide layer 201 material is-5.2eV ~-6.0eV, described luminous material layer 202 material 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 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq 3) middle at least one, described molysite layer 203 material is selected from iron chloride (FeCl 3) ferric bromide (FeBr 3) and iron sulfide (Fe 2s 3) middle at least one.
Described metal oxide layer material is selected from molybdenum trioxide (MoO 3).Also can adopt tungstic acid (WO 3) and vanadic oxide (V 2o 5) middle at least one.
The thickness of described metal oxide layer is 10nm ~ 30nm, and the thickness of described luminous material layer is 20nm ~ 80nm, and the thickness of described molysite layer is 50nm ~ 100nm.
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 30nm.
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 50nm.
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 18nm.
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 90nm.
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 (C sn 3) and lithium fluoride (LiF) at least one, be preferably CsF.The thickness of electron injecting layer 80 is 0.5nm ~ 10nm, is preferably 1nm.
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 Au.The thickness of negative electrode 90 is 80nm ~ 250nm, is preferably 200nm.
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 metal oxide layer, luminous material layer and molysite layer composition, metal oxide layer has Hole injection capacity, the injection efficiency in hole can be improved, potential barrier between anode and hole injection layer is reduced, avoid energy loss, luminous material layer is that fluorescence luminescent material 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, molysite layer is made up of molysite material, the carrier concentration of molysite material is higher, the conductivity of device can be improved, potential barrier between lower layer, the potential barrier that hole is injected reduces, 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 by metal oxide layer 201, luminous material layer 202 and molysite layer 203 form, thermal resistance evaporation is adopted to prepare metal oxide layer 201 on described substrate of glass 10 surface, the HOMO energy level of described metal oxide layer 201 material is-5.2eV ~-6.0eV, described luminous material layer is prepared by thermal resistance evaporation on described metal oxide layer 201 surface, described luminous material layer 202 material 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 '-bis-(9-ethyl-3-carbazole vinyl)-1, 1 '-biphenyl (BCzVBi) and the middle at least one of oxine aluminium (Alq3), then molysite layer 203 is prepared on described luminous material layer 202 surface by thermal resistance evaporation, described molysite layer material is selected from iron chloride (FeCl 3) ferric bromide (FeBr 3) and iron sulfide (Fe 2s 3) middle at least one.
The thickness of described metal oxide layer is 10nm ~ 30nm, and the thickness of described luminous material layer is 20nm ~ 80nm, and the thickness of described molysite layer is 50nm ~ 100nm.
Described metal oxide layer material is selected from molybdenum trioxide (MoO 3).Also can adopt tungstic acid (WO 3) and vanadic oxide (V 2o 5) middle at least one.
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.
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 30nm.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 50nm.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 18nm.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 90nm.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 1nm.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 Au.The thickness of negative electrode 90 is 80nm ~ 250nm, is preferably 200nm.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/MoO that the present embodiment prepares structure 3/ Alq 3/ FeCl 3/ ITO/MoO 3/ NPB/Alq 3the organic electroluminescence device of/TAZ/CsF/Au, "/" 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 metal oxide layer, luminous material layer and molysite layer, and adopt thermal resistance evaporation to prepare metal oxide layer at glass baseplate surface, material is MoO 3, thickness is 12nm, and adopt thermal resistance evaporation to prepare luminescent layer on metal oxide layer surface, material is Alq 3, thickness is 70nm, and adopt thermal resistance evaporation to prepare molysite layer on luminescent layer surface, material is FeCl 3, thickness is 80nm.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 30nm; Evaporation prepares hole transmission layer: material is NPB, and thickness is 50nm; Evaporation prepares luminescent layer: selected materials is Alq 3, thickness is 18nm; Evaporation prepares electron transfer layer, and material is TAZ, and thickness is 90nm; Evaporation prepares electron injecting layer, material is CsF, and thickness is 1nm; Evaporation prepares negative electrode, and material is Au, and thickness is 200nm; 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: 400V, magnetic field about: 100G, power density: 25W/cm 2.
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 8 × 10 -5pa, operating current is 2A, and the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 3nm/s.
Refer to Fig. 3, the structure being depicted as preparation in embodiment 1 is substrate of glass/MoO 3/ Alq 3/ FeCl 3/ ITO/MoO 3/ NPB/Alq 3structure prepared by organic electroluminescence device (curve 1) and the comparative example of/TAZ/CsF/Au is ito glass/MoO 3/ NPB/Alq 3the brightness 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 8.0lm/W, and comparative example be only 5.5lm/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 metal oxide layer, luminous material layer and molysite layer composition, metal oxide layer has Hole injection capacity, the injection efficiency in hole can be improved, potential barrier between anode and hole injection layer is reduced, avoid energy loss, luminous material layer is that fluorescence luminescent material 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, molysite layer is made up of molysite material, the carrier concentration of molysite material is higher, the conductivity of device can be improved, potential barrier between lower layer, the potential barrier that hole is injected reduces, 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/WO that the present embodiment prepares structure 3/ DCJTB/FeBr 3/ IZO/WO 3/ TCTA/ADN/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 metal oxide layer, luminous material layer and molysite layer, adopt thermal resistance evaporation to prepare metal oxide layer at glass baseplate surface, material is WO 3, thickness is 10nm, and adopt thermal resistance evaporation to prepare luminescent layer on metal oxide layer surface, material is DCJTB, and thickness is 80nm, and adopt thermal resistance evaporation to prepare molysite layer on luminescent layer surface, material is FeBr 3, thickness is 50nm.Then prepare IZO on the scattering layer, thickness is 80nm, adopts the method preparation of magnetron sputtering; Evaporation hole injection layer, material is WO 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 TAZ, 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.
Embodiment 3
It is substrate of glass/V that the present embodiment prepares structure 2o 5/ ADN/Fe 2s 3/ AZO/V 2o 5/ NPB/DCJTB/Bphen/Cs 2cO 3the organic electroluminescence device of/Au.
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 metal oxide layer, luminous material layer and molysite layer, adopt thermal resistance evaporation to prepare metal oxide layer at glass baseplate surface, material is V 2o 5, thickness is 30nm, and adopt thermal resistance evaporation to prepare luminescent layer on metal oxide layer surface, material is ADN, and thickness is 20nm, and adopt thermal resistance evaporation to prepare molysite layer on luminescent layer surface, material is Fe 2s 3, thickness is 80nm.Then prepare AZO on the scattering layer, thickness is 300nm, adopts the method preparation of magnetron sputtering; Evaporation hole injection layer, material is V 2o 5, thickness is 20nm; Evaporation hole transmission layer: material is NPB, thickness is 60nm; Evaporation luminescent layer: selected materials is DCJTB, thickness is 10nm; Evaporation electron transfer layer, material is Bphen, and thickness is 200nm; Evaporation electron injecting layer, material are Cs 2cO 3, 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 2 × 10 -4pa, the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of metallic compound is 0.6nm/s, and the evaporation rate of metal is 1nm/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 5A, and the evaporation rate of organic material is 0.5nm/s, and the evaporation rate of metal and metallic compound is 6nm/s.
Embodiment 4
It is substrate of glass/WO that the present embodiment prepares structure 3/ BCzVBi/Fe 2s 3/ ITO/MoO 3the organic electroluminescence device of/TCTA/BCzVBi/TPBi/LiF/Pt.
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 metal oxide layer, luminous material layer and molysite layer, and adopt thermal resistance evaporation to prepare metal oxide layer at glass baseplate surface, material is WO 3, thickness is 19nm, and adopt thermal resistance evaporation to prepare luminescent layer on metal oxide layer surface, material is BCzVBi, and thickness is 55nm, and adopt thermal resistance evaporation to prepare molysite layer on luminescent layer surface, material is Fe 2s 3, thickness is 60nm.Then prepare IZO on the scattering layer, thickness is 180nm, adopts the method preparation of magnetron sputtering.Evaporation hole injection layer, material is MoO 3, thickness is 20nm; Evaporation hole transmission layer: material is TCTA, thickness is 60nm; Evaporation luminescent layer: selected materials is BCzVBi, thickness is 40nm; Evaporation electron transfer layer, material is TPBi, and thickness is 35nm; Evaporation electron injecting layer, material are LiF, and 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 5 × 10 -5pa, the evaporation rate of organic material is 0.5nm/s, and the evaporation rate of metal is 6nm/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 2.5A, and the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s.
The 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, 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 metal oxide layer, luminous material layer and molysite layer composition, the HOMO energy level of described metal oxide layer material is-5.2eV ~-6.0eV, described luminescent material layer material 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, 4 '-bis-(9-ethyl-3-carbazole vinyl)-1, at least one in 1 '-biphenyl and oxine aluminium, described molysite layer material is selected from iron chloride, at least one in ferric bromide and iron sulfide.
2. organic electroluminescence device according to claim 1, is characterized in that, described metal oxide layer material is selected from least one in molybdenum trioxide, tungstic acid and vanadic oxide.
3. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described metal oxide layer is 10nm ~ 30nm, and the thickness of described luminous material layer is 20nm ~ 80nm, and the thickness of described molysite layer is 50nm ~ 100nm.
4. organic electroluminescence device according to claim 1, is characterized in that, the refractive index of described substrate of glass is 1.8 ~ 2.2.
5. organic electroluminescence device according to claim 1, it is characterized in that, the material of described luminescent layer 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, the material of described hole transmission layer is selected from 1, 1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, 4, 4 ', 4 "-three (carbazole-9-base) triphenylamine and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine.
6. 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 metal oxide layer, luminous material layer and molysite layer composition, thermal resistance evaporation is adopted to prepare metal oxide layer at described glass basic surface, the HOMO energy level of described metal oxide layer material is-5.2eV ~-6.0eV, described luminous material layer is prepared by thermal resistance evaporation on described metal oxide layer surface, described luminescent material layer material 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, 4 '-bis-(9-ethyl-3-carbazole vinyl)-1, at least one in 1 '-biphenyl and oxine aluminium, then molysite layer is prepared on described luminous material layer surface by thermal resistance evaporation, described molysite layer material is selected from iron chloride, at least one in ferric bromide and iron sulfide,
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.
7. the preparation method of organic electroluminescence device according to claim 6, is characterized in that: the thickness of described metal oxide layer is 10nm ~ 30nm, and the thickness of described luminous material layer is 20nm ~ 80nm, and the thickness of described molysite layer is 50nm ~ 100nm.
8. the preparation method of organic electroluminescence device according to claim 6, is characterized in that: described metal oxide layer material is selected from least one in molybdenum trioxide, tungstic acid and vanadic oxide.
9. the preparation method of organic electroluminescence device according to claim 6, is characterized in that: the refractive index of described substrate of glass is 1.8 ~ 2.2.
10. the preparation method of organic electroluminescence device according to claim 6, 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.
CN201310601918.7A 2013-11-25 2013-11-25 Organic electroluminescence device and manufacturing method for organic electroluminescence device Pending CN104659229A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107251258A (en) * 2014-10-24 2017-10-13 德山新勒克斯有限公司 Utilize the display and organic electronic element of organic electronic element constituent

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107251258A (en) * 2014-10-24 2017-10-13 德山新勒克斯有限公司 Utilize the display and organic electronic element of organic electronic element constituent
CN107251258B (en) * 2014-10-24 2019-04-26 德山新勒克斯有限公司 Display and organic electronic device using composition for organic electronic device

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