CN104659282A - Organic electroluminescence device and preparation method thereof - Google Patents

Organic electroluminescence device and preparation method thereof Download PDF

Info

Publication number
CN104659282A
CN104659282A CN201310608402.5A CN201310608402A CN104659282A CN 104659282 A CN104659282 A CN 104659282A CN 201310608402 A CN201310608402 A CN 201310608402A CN 104659282 A CN104659282 A CN 104659282A
Authority
CN
China
Prior art keywords
layer
rhenium
compound
calcium
electroluminescence device
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201310608402.5A
Other languages
Chinese (zh)
Inventor
周明杰
黄辉
陈吉星
王平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
Original Assignee
Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Oceans King Lighting Science and Technology Co Ltd, Shenzhen Oceans King Lighting Engineering Co Ltd filed Critical Oceans King Lighting Science and Technology Co Ltd
Priority to CN201310608402.5A priority Critical patent/CN104659282A/en
Publication of CN104659282A publication Critical patent/CN104659282A/en
Pending legal-status Critical Current

Links

Classifications

    • 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

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

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 light emitting material layer and a binary doped layer; the light emitting material layer is made of a 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 binary doped layer comprises a calcium compound material and a rhenium compound material doped in the calcium compound material; the calcium compound material is selected from at least one of calcium oxide, calcium chloride, calcium carbonate and calcium fluoride; the rhenium compound material is selected from at least one of rhenium heptoxide, rhenium oxide, rhenium trioxide and rhenium chloride.

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 made up of luminous material layer and binary doped layer, the material of described luminous material 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, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl and oxine aluminium, described binary doped layer comprises the compound-material of calcium and is entrained in the compound-material of the rhenium in the compound-material of described calcium, the compound-material of described calcium is selected from calcium oxide, calcium chloride, at least one in calcium carbonate and calcirm-fluoride, the compound-material of described rhenium is selected from rhenium heptoxide, rhenium dioxide, at least one in rhenium trioxide and chlorination rhenium.
The thickness of described luminous material layer is 10nm ~ 50nm, and the thickness of described binary doped layer is 50nm ~ 300nm.
Described in described binary doped layer, the mass ratio of the compound-material of calcium and the compound-material of described rhenium is 4:1 ~ 15:1.
The refractive index of described substrate of glass is 1.8 ~ 2.2.
A preparation method for organic electroluminescence device, comprises the following steps:
Scattering layer is prepared at glass basic surface evaporation, described scattering layer is made up of luminous material layer and binary doped layer, thermal resistance evaporation is adopted to prepare luminous material layer at described glass basic surface, the material of described luminous material 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, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl and oxine aluminium, described binary doped layer is prepared by electron beam evaporation plating on described luminous material layer surface, described binary doped layer comprises the compound-material of calcium and is entrained in the compound-material of the rhenium in the compound-material of described calcium, the compound-material of described calcium is selected from calcium oxide, calcium chloride, at least one in calcium carbonate and calcirm-fluoride, the compound-material of described rhenium is selected from rhenium heptoxide, rhenium dioxide, at least one in rhenium trioxide and chlorination rhenium,
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 luminous material layer is 10nm ~ 50nm, and the thickness of described binary doped layer is 50nm ~ 300nm.
Described in described binary doped layer, the mass ratio of the compound-material of calcium and the compound-material of described rhenium is 4:1 ~ 15:1.
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.
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~ l00W/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 made up of luminous material layer and binary doped layer, luminescent material 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, binary doped layer is made up of the compound-material of calcium and the compound-material of rhenium, the compound-material of calcium is conducive to the scattering of photon, the homogeneous stable in properties of internal structure of the compound-material of calcium, after light carries out multiple reflections in crystal, incidence angle is changed, the HOMO energy level of the compound-material of rhenium is lower, the potential barrier between hole injection layer and anode can be reduced, improve Hole injection capacity, 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 made up of luminous material layer 201 and binary doped layer 202, the material of described luminous material layer 201 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'-two (9-ethyl-3-carbazole vinyl)-1,1'-biphenyl (BCzVBi) and oxine aluminium (Alq 3) middle at least one, described binary doped layer 202 comprises the compound-material of calcium and is entrained in the compound-material of the rhenium in the compound-material of described calcium, and the compound-material of described calcium is selected from calcium oxide (CaO), calcium chloride (CaCl 2), calcium carbonate (CaCO 3) and calcirm-fluoride (CaF 2) middle at least one, the compound-material of described rhenium is selected from rhenium heptoxide (Re 2o 7), rhenium dioxide (ReO 2) rhenium trioxide (ReO 3) and chlorination rhenium (ReCl 3) middle at least one.
The thickness of described luminous material layer 201 is 10nm ~ 50nm, and the thickness of described binary doped layer 202 is 50nm ~ 300nm.
Described in described binary doped layer 202, the mass ratio of the compound-material of calcium and the compound-material of described rhenium is 4:1 ~ 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''-tri-(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, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-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 150nm.
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 0.7nm.
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 100nm.
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 made up of luminous material layer and binary doped layer, luminescent material 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, binary doped layer is made up of the compound-material of calcium and the compound-material of rhenium, the compound-material of calcium is conducive to the scattering of photon, the homogeneous stable in properties of internal structure of the compound-material of calcium, after light carries out multiple reflections in crystal, incidence angle is changed, the HOMO energy level of the compound-material of rhenium is lower, the potential barrier between hole injection layer and anode can be reduced, improve Hole injection capacity, 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 luminous material layer 201 and binary doped layer 202, thermal resistance evaporation is adopted to prepare luminous material layer 201 on described substrate of glass 10 surface, the material of described luminous material layer 201 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, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-and oxine aluminium (Alq 3) middle at least one, described binary doped layer 202 is prepared by electron beam evaporation plating on described luminous material layer 201 surface, described binary doped layer 202 comprises the compound-material of calcium and is entrained in the compound-material of the rhenium in the compound-material of described calcium, and the compound-material of described calcium is selected from calcium oxide (CaO), calcium chloride (CaCl 2), calcium carbonate (CaCO 3) and calcirm-fluoride (CaF 2) middle at least one, the compound-material of described rhenium is selected from rhenium heptoxide (Re 2o 7), rhenium dioxide (ReO 2) rhenium trioxide (ReO 3) and chlorination rhenium (ReCl 3) middle at least one.
The thickness of described luminous material layer 201 is 10nm ~ 50nm, and the thickness of described binary doped layer 202 is 50nm ~ 300nm.
Described in described binary doped layer 202, the mass ratio of the compound-material of calcium and the compound-material of described rhenium is 4:1 ~ 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.
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~ l00W/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''-tri-(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, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-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 150nm.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 0.7nm.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 100nm.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/ CaO:Re 2o 7/ 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 luminous material layer and binary doped layer, and adopt thermal resistance evaporation to prepare luminous material layer at glass baseplate surface, material is Alq 3, thickness is 12nm, and adopt electron beam evaporation plating to prepare binary doped layer on luminous material layer surface, material is CaO:Re 2o 7, CaO and Re 2o 7mass ratio be 5:1, thickness 150nm.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 50W/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/ CaO:Re 2o 7/ 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 7.2lm/W, and comparative example be only 4.7lm/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 made up of luminous material layer and binary doped layer, luminescent material 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, binary doped layer is made up of the compound-material of calcium and the compound-material of rhenium, the compound-material of calcium is conducive to the scattering of photon, the homogeneous stable in properties of internal structure of the compound-material of calcium, after light carries out multiple reflections in crystal, incidence angle is changed, the HOMO energy level of the compound-material of rhenium is lower, the potential barrier between hole injection layer and anode can be reduced, improve Hole injection capacity, 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/CaCl that the present embodiment prepares structure 2: ReO 2/ IZO/MoO 3/ NPB/ADN/TAZ/Cs 2cO 3the organic electroluminescence device of/Au.
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 luminous material layer and binary doped layer, adopt thermal resistance evaporation to prepare luminous material layer at glass baseplate surface, material is DCJTB, and thickness is 50nm, adopt electron beam evaporation plating to prepare binary doped layer on luminous material layer surface, material is CaCl 2: ReO 2, CaCl 2with ReO 2mass ratio be 4:1, thickness 300nm.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 NPB, 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 Cs 2cO 3, thickness is 10nm; Evaporation negative electrode, material is Au, 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 10W/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/CaCO that the present embodiment prepares structure 3: ReO 3/ AZO/WO 3the organic electroluminescence device of/TCTA/DCJTB/Bphen/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 luminous material layer and binary doped layer, adopts thermal resistance evaporation to prepare luminous material layer at glass baseplate surface, material is ADN, thickness is 10nm, and adopt electron beam evaporation plating to prepare binary doped layer on luminous material layer surface, material is CaCO 3: ReO 3, CaCO 3with ReO 3mass ratio be 15:1, thickness 50nm.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 TCTA, 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 LiF, and thickness is 0.5nm; Evaporation negative electrode, material is Pt, 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 100W/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//ITO/V that the present embodiment prepares structure 2o 5/ TCTA/BCzVBi/TPBi/CsN 3the organic electroluminescence device of/Al.
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 luminous material layer and binary doped layer, adopt thermal resistance evaporation to prepare luminous material layer at glass baseplate surface, material is BCzVBi, and thickness is 35nm, adopt electron beam evaporation plating to prepare binary doped layer on luminous material layer surface, material is CaF 2: ReCl 3, CaF 2with ReCl 3mass ratio be 7:1, thickness 180nm.Then prepare ITO on the scattering layer, thickness is 150nm, 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 TCPA, 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 CsN 3, thickness is 1nm; Evaporation negative electrode, material is Al, 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 2.5A, 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 (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 made up of luminous material layer and binary doped layer, the material of described luminous material 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, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl and oxine aluminium, described binary doped layer comprises the compound-material of calcium and is entrained in the compound-material of the rhenium in the compound-material of described calcium, the compound-material of described calcium is selected from calcium oxide, calcium chloride, at least one in calcium carbonate and calcirm-fluoride, the compound-material of described rhenium is selected from rhenium heptoxide, rhenium dioxide, at least one in rhenium trioxide and chlorination rhenium.
2. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described luminous material layer is 10nm ~ 50nm, and the thickness of described binary doped layer is 50nm ~ 300nm.
3. organic electroluminescence device according to claim 1, is characterized in that, described in described binary doped layer, the mass ratio of the compound-material of calcium and the compound-material of described rhenium is 4:1 ~ 15:1.
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. 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 made up of luminous material layer and binary doped layer, thermal resistance evaporation is adopted to prepare luminous material layer at described glass basic surface, the material of described luminous material 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, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl and oxine aluminium, described binary doped layer is prepared by electron beam evaporation plating on described luminous material layer surface, described binary doped layer comprises the compound-material of calcium and is entrained in the compound-material of the rhenium in the compound-material of described calcium, the compound-material of described calcium is selected from calcium oxide, calcium chloride, at least one in calcium carbonate and calcirm-fluoride, the compound-material of described rhenium is selected from rhenium heptoxide, rhenium dioxide, at least one in rhenium trioxide and chlorination rhenium,
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, is characterized in that: the thickness of described luminous material layer is 10nm ~ 50nm, and the thickness of described binary doped layer is 50nm ~ 300nm.
7. the preparation method of organic electroluminescence device according to claim 5, is characterized in that: described in described binary doped layer, the mass ratio of the compound-material of calcium and the compound-material of described rhenium is 4:1 ~ 15:1.
8. the preparation method of organic electroluminescence device according to claim 5, is characterized in that: the refractive index of described substrate of glass is 1.8 ~ 2.2.
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.
10. the preparation method of organic electroluminescence device according to claim 5, is characterized in that: 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~ l00W/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.
CN201310608402.5A 2013-11-25 2013-11-25 Organic electroluminescence device and preparation method thereof Pending CN104659282A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310608402.5A CN104659282A (en) 2013-11-25 2013-11-25 Organic electroluminescence device and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310608402.5A CN104659282A (en) 2013-11-25 2013-11-25 Organic electroluminescence device and preparation method thereof

Publications (1)

Publication Number Publication Date
CN104659282A true CN104659282A (en) 2015-05-27

Family

ID=53250177

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310608402.5A Pending CN104659282A (en) 2013-11-25 2013-11-25 Organic electroluminescence device and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104659282A (en)

Similar Documents

Publication Publication Date Title
CN104124370A (en) Organic light-emitting device and preparation method thereof
CN104518145A (en) Organic electroluminescent device and method for preparing same
CN104659231A (en) Organic electroluminescence device and preparation method thereof
CN104659229A (en) Organic electroluminescence device and manufacturing method for organic electroluminescence device
CN104009161B (en) Organic electroluminescent device
CN104659282A (en) Organic electroluminescence device and preparation method thereof
CN104425724A (en) Organic electroluminescent device and preparation method thereof
CN104425723A (en) Organic electroluminescent device and preparation method thereof
CN104659265A (en) Organic electroluminescence device and preparation method thereof
CN104466001A (en) Organic electroluminescent device and manufacturing method thereof
CN104659239A (en) Organic electroluminescence device and preparation method thereof
CN104659230A (en) Organic electroluminescence device and manufacturing method for organic electroluminescence device
CN104659263A (en) Organic electroluminescence device and preparation method thereof
CN104659262A (en) Organic electroluminescence device and preparation method thereof
CN104425745A (en) Organic electroluminescent device and preparation method thereof
CN104518106A (en) Organic light-emitting device and making method thereof
CN104659232A (en) Organic electroluminescence device and preparation method thereof
CN104518140A (en) Organic electroluminescent device and preparation method thereof
CN104659236A (en) Organic electroluminescence device and preparation method thereof
CN104659233A (en) Organic electroluminescence device and preparation method thereof
CN104659264A (en) Organic electroluminescence device and preparation method thereof
CN104659238A (en) Organic electroluminescence device and preparation method thereof
CN104659261A (en) Organic electroluminescence device and preparation method thereof
CN104659266A (en) Organic electroluminescence device and preparation method thereof
CN104659234A (en) Organic electroluminescence device and preparation method thereof

Legal Events

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

Application publication date: 20150527