CN104466016A - Organic electroluminescent device and manufacturing method thereof - Google Patents

Organic electroluminescent device and manufacturing method thereof Download PDF

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Publication number
CN104466016A
CN104466016A CN201310438727.3A CN201310438727A CN104466016A CN 104466016 A CN104466016 A CN 104466016A CN 201310438727 A CN201310438727 A CN 201310438727A CN 104466016 A CN104466016 A CN 104466016A
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layer
molysite
organic electroluminescence
metal
doped layer
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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
    • 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

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention relates to an organic electroluminescent device and a manufacturing method of the organic electroluminescent device. The organic electroluminescent device is of a laminated structure. According to the laminated structure, a glass substrate, an anode layer, a scattering layer, a hole injection layer, a hole transmission layer, a light-emitting layer, an electron transfer layer, an electron injection layer and a cathode layer are sequentially stacked in a laminated mode, the scattering layer comprises a metal doping layer and a molysite doping layer, the metal doping layer is made of high-work-function metal materials and fluorescent materials, and the molysite doping layer is made of molysite materials and hole doping materials. According to the organic electroluminescent device and the manufacturing method, the scattering layer of the organic electroluminescent device improves the hole injection capacity, improves the light color purity, improves the electrical conductivity of the device and lowers the hole injection potential energy barrier, so that the hole injection efficiency is improved, and the light-extraction efficiency can be improved beneficially.

Description

Organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to field of optoelectronic devices, particularly relate to a kind of organic electroluminescence device.The invention still further relates to the preparation method of this organic electroluminescence device.
Background technology
1987, C.W.Tang and VanSlyke of Eastman Kodak company of the U.S. reported the breakthrough in organic electroluminescent research.Ultrathin film technology is utilized to prepare high brightness, high efficiency double-deck organic electroluminescence device (OLED).Under 10V, brightness reaches 1000cd/m 2, its luminous efficiency is 1.51lm/W, the life-span is greater than 100 hours.
In existing 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, there is the difference (specific refractivity as between glass and ITO) of refractive index between interface.Specifically, be 1.8 when the glass refraction of existing luminescent device is 1.5, ITO, light arrives glass from ITO, total reflection will occur, and cause the loss of total reflection, thus it is lower to cause entirety to go out optical property.
Summary of the invention
The object of the invention is to solve above-mentioned prior art Problems existing and deficiency, provide a kind of organic electroluminescence device and preparation method thereof to improve the light extraction efficiency of organic electroluminescence device.
The present invention is directed to above-mentioned technical problem and the technical scheme proposed is: a kind of organic electroluminescence device, this organic electroluminescence device is layer structure, and this layer structure is: the substrate of glass stacked gradually, anode layer, scattering layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer; Described scattering layer comprises metal-doped layer and molysite doped layer; Wherein,
The material of described metal-doped layer comprises high-work-function metal and fluorescence luminescent material that work function is-4.0 ~-5.5eV, and the material of described molysite doped layer comprises molysite and hole doping material;
Described fluorescence luminescent 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) or oxine aluminium (Alq 3);
Described hole doping material is 2,3,5,6-tetra-fluoro-7,7,8,8 ,-four cyano-benzoquinone's bismethane (F4-TCNQ), 4,4,4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine (1T-NATA) and dinaphthyl-N, N '-diphenyl-4,4 '-benzidine (2T-NATA).
Further, described high-work-function metal and the described fluorescence luminescent material mass ratio that adulterates is 0.5:1 ~ 2:1; The doping mass ratio of described molysite and described hole doping material is 0.1:1 ~ 0.4:1.
Further, described high-work-function metal is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au); Described molysite is iron chloride (FeCl 3) ferric bromide (FeBr 3) or iron sulfide (Fe 2s 3).
Further, the refractive index of described substrate of glass is more than 1.8, and visible light transmissivity is more than 90%.The wavelength of described visible ray is preferably 400nm.
Further, the thickness of described metal-doped layer is 50 ~ 200nm, and the thickness of described molysite doped layer is 40 ~ 100nm.
Further, the material of described anode layer is indium tin oxide, aluminium zinc oxide or indium-zinc oxide;
The material of described hole injection layer is molybdenum trioxide (MoO 3), tungstic acid (WO 3) or vanadic oxide (V 2o 5);
The material of described hole transmission layer is 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4 ', 4 "-three (carbazole-9-base) triphenylamine (TCTA), N; N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB);
The material of described luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) or oxine aluminium (Alq 3);
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBI);
The material of described electron injecting layer is cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), nitrine caesium (CsN 3) or lithium fluoride (LiF).
The material of described cathode layer is silver (Ag), aluminium (Al), platinum (Pt) or gold (Au).
The present invention also proposes a kind of preparation method of organic electroluminescence device, and it comprises the steps:
A () prepares anode layer by magnetron sputtering apparatus on the glass substrate;
B () uses thermal resistance evaporated device to prepare metal-doped layer on the anode layer that step (a) is obtained, then on described metal-doped layer, prepare molysite doped layer, thus obtain described heat dissipating layer; Wherein,
It is 0.5:1 ~ 2:1 high-work-function metal and fluorescence luminescent material that the material of described metal-doped layer comprises doping mass ratio, and it is 0.1:1 ~ 0.4:1 molysite and hole doping material that the material of described molysite doped layer comprises doping mass ratio;
Described fluorescence luminescent 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)-1,1 '-biphenyl or oxine aluminium;
Described hole doping material is 2,3,5,6-tetra-fluoro-7,7,8,8 ,-four cyano-benzoquinone's bismethane, 4,4,4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine or dinaphthyl-N, N '-diphenyl-4,4 '-benzidines;
(c) evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer successively on the scattering layer that step (b) is obtained, thus obtain described organic electroluminescence device.
Further, in described step (a), the accelerating voltage of described magnetron sputtering apparatus is 300 ~ 800V, and magnetic field is 50 ~ 200G, and power density is 1 ~ 40W/cm 2.
Further, in described step (b), the evaporation rate of described thermal resistance evaporated device is 0.1 ~ 1nm/s, and the thickness of described metal-doped layer is 50 ~ 200nm, and the thickness of described molysite doped layer is 40 ~ 100nm.
Further, in described step (c), the evaporation rate of described hole transmission layer, luminescent layer and electron transfer layer is 0.1 ~ 1nm/s, and the evaporation rate of described cathode layer is 1 ~ 10nm/s.
The performance of each component of described scattering layer is as follows: the hole doping material of described scattering layer can improve the transmission rate in hole, and meanwhile, its HOMO energy level is lower, can further improve the injectability in hole; The work function of the metal of described scattering layer is higher, can improve the injectability in hole; The fluorescence luminescent material of described scattering layer and the consistent of luminescent layer, can supplement luminescence is photochromic, improve photochromic purity, effectively improve luminous efficiency, and glow color is stablized, and the rate of decay reduces; The molysite doped layer of described scattering layer is made up of molysite and hole-injecting material, and the carrier concentration of molysite is higher, can improve the conductivity of device, and molysite layer can potential barrier between lower layer, and the potential barrier that hole is injected reduces, thus improves hole injection efficiency; Hole doping material can improve injectability and the transmission rate in hole, thus is conducive to improving light extraction efficiency.Above-mentioned HOMO energy level is the saying being derived from frontier orbital theory, and referring to the track that the energy level that occupies electronics is the highest, is the sign of the ability giving electronics.
Generally speaking, compared with prior art, organic electroluminescence devices of the present invention and preparation method thereof, there is following advantage: the scattering layer of organic electroluminescence device of the present invention improves the injectability in hole, improve photochromic purity, improve the conductivity of device, the potential barrier that hole is injected reduces, thus raising hole injection efficiency, thus be conducive to improving light extraction efficiency.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of the embodiment of the present invention 1.
Fig. 2 is the graph of a relation of the organic electroluminescence device of embodiment 1 and the current density of comparative example and current efficiency.
Embodiment
Below in conjunction with embodiment, elaboration is further given to the present invention.
Embodiment 1
As shown in Figure 1, the organic electroluminescence device in the present embodiment is layer structure, and every layer is followed successively by:
Substrate of glass 101, anode layer 102, metal-doped layer 103, molysite doped layer 104, hole injection layer 105, hole transmission layer 106, luminescent layer 107, electron transfer layer 108, electron injecting layer 109 and cathode layer 110.Described metal-doped layer 103 and described molysite doped layer 104 form described heat dissipating layer.The structure of this organic electroluminescence device is substrate of glass/ITO/Ag:BCzVBi/FeCl 3: F4-TCNQ/MoO 3/ NPB/BCzVBi/TAZ/CsF/Ag, wherein brace "/" represents layer structure, and colon ": " expression is adulterated mutually.）
Above-mentioned organic electroluminescence device is prepared successively as follows:
(1) preliminary treatment of plated film
Take out the substrate of glass 101 that the glass trade mark is N-LASF44, after clean with distilled water, alcohol flushing, be placed in isopropyl alcohol and soak an evening.
(2) preparation of anode layer
By prepare through step () substrate of glass 101 be placed in magnetron sputtering apparatus under, the technological parameter of magnetron sputtering apparatus is set to the accelerating voltage of 700V, the magnetic field of 120G and 250W/cm 2power density, use magnetron sputtering apparatus in substrate of glass 101, prepare anode layer 102, anode layer 102 material is indium tin oxide (ITO) and thickness is 80nm.
(3) preparation of scattering layer
Under the substrate of glass 101 prepared through step (two) is placed in thermal resistance evaporated device, the technological parameter of thermal resistance evaporated device is set to the evaporation rate and 8 × 10 of 0.2nm/s -4the operating pressure of Pa, target is set as silver and 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl, use thermal resistance evaporated device evaporation metal doped layer 103 on anode layer 102, make the thickness of metal-doped layer 103 be 120nm, silver and 4 in metal-doped layer 103, the doping mass ratio of 4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl is 1.2:1;
The target of thermal resistance evaporated device is set as iron chloride and 2,3,5,6-tetra-fluoro-7,7,8,8,-four cyano-benzoquinone's bismethane, uses thermal resistance evaporated device evaporation molysite doped layer 104 on metal-doped layer 103, makes the thickness of molysite doped layer 104 be 60nm, iron chloride and 2 in molysite doped layer 104,3,5,6-tetra-fluoro-7,7,8,8, the doping mass ratio of-four cyano-benzoquinone's bismethane is 0.2:1, thus obtained heat dissipating layer.
(4) preparation of organic electroluminescence device
Thermal resistance evaporation is used to be prepared on molysite doped layer 104 deposition material successively for molybdenum trioxide and the thickness hole injection layer 105 that is 30nm, material is N, N '-(1-naphthyl)-N, N '-diphenyl-4, 4 '-benzidine and thickness are the hole transmission layer 106 of 50nm, material is 4, 4 '-bis-(9-ethyl-3-carbazole vinyl)-1, 1 '-biphenyl and thickness are the luminescent layer 107 of 22nm, material is 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, 2, 4-triazole and thickness are the electron transfer layer 108 of 110nm, material is cesium fluoride and thickness is the electron injecting layer 109 of 1nm, then evaporation rate prepared by thermal resistance evaporation is adjusted to 2nm/s, uses thermal resistance evaporation to be prepared in electron injecting layer 109 steams and cross material for silver and the thickness cathode layer 110 that is 120nm, thus obtain required electroluminescent device.
Fig. 2 is the luminous efficiency of the present embodiment 1 organic electroluminescence device and general device and the graph of a relation of current density.The structure of described general device is substrate of glass/ITO/WO 3/ NPB/BCzVBi/TAZ/CsF/Ag.In Fig. 2, abscissa is the size of current density, ordinate is the size of luminous efficiency, and curve 1 is the current density of embodiment 1 organic electroluminescence device and the relation curve of luminous efficiency, and curve 2 is the current density of comparative example device and the relation curve of luminous efficiency.As seen from Figure 2, under different current density, the luminous efficiency of embodiment 1 is all larger than comparative example, maximum luminous efficiency is 10.5lm/W, and comparative example be only 7.1lm/W, and the luminous efficiency of comparative example declines fast along with the increase of current density, this illustrates that the scattering layer prepared by the present invention can improve the injectability in hole, supplement luminescence is photochromic, improve photochromic purity, effectively improve luminous efficiency, improve the conductivity of device, improve injectability and the transmission rate in hole, thus be conducive to improving light extraction efficiency.
Embodiment 2
Organic electroluminescence device in the present embodiment is layer structure, and every layer is followed successively by: substrate of glass, anode layer, metal-doped layer, molysite doped layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer.
Described metal-doped layer and described molysite doped layer form described heat dissipating layer.The structure of described organic electroluminescence device is substrate of glass/IZO/Al:ADN/FeBr 3: 1T-NATA/WO 3/ NPB/ADN/TAZ/CsN 3/ Al, wherein brace "/" represents layer structure, and colon ": " expression is adulterated mutually.Above-mentioned organic electroluminescence device is prepared successively as follows:
(1) preliminary treatment of plated film
Taking out the glass trade mark is the substrate of glass of N-LAF36, after clean with distilled water, alcohol flushing, be placed in isopropyl alcohol and soak an evening.
(2) preparation of anode layer
Under the substrate of glass prepared through step () is placed in magnetron sputtering apparatus, the technological parameter of magnetron sputtering apparatus is set to the accelerating voltage of 300V, the magnetic field of 50G and 40W/cm 2power density, use magnetron sputtering apparatus to prepare material on the glass substrate for indium-zinc oxide (IZO) and thickness is the anode layer of 80nm.
(3) preparation of scattering layer
Under the substrate of glass prepared through step (two) is placed in thermal resistance evaporated device, technological parameter prepared by thermal resistance evaporation is set to the evaporation rate and 2 × 10 of 1nm/s -3the operating pressure of Pa, target prepared by thermal resistance evaporation is set as aluminium and 9,10-bis--β-naphthylene anthracene, use thermal resistance evaporated device evaporation metal doped layer on the anode layer, the thickness of metal-doped layer is made to be 200nm, in metal-doped layer, the doping mass ratio of aluminium and 9,10-bis--β-naphthylene anthracene is 0.5:1;
Target prepared by thermal resistance evaporation is set as ferric bromide and 4,4,4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine, use electron-beam coating equipment evaporation molysite doped layer on metal-doped layer, the thickness of molysite doped layer is made to be 100nm, ferric bromide and 4 in molysite doped layer, 4, the doping mass ratio of 4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine is 0.1:1, thus obtained heat dissipating layer.
(4) preparation of organic electroluminescence device
Thermal resistance evaporation is used to be prepared on molysite doped layer deposition material successively for tungstic acid and the thickness hole injection layer that is 40nm, material are N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine and thickness are the hole transmission layer of 45nm, material is 9,10-bis--β-naphthylene anthracene and thickness are the luminescent layer of 8nm, material is 1,2,4-triazole derivative and thickness be 65nm electron transfer layer, material is nitrine caesium and thickness is the electron injecting layer of 10nm; Then evaporation rate prepared by thermal resistance evaporation is adjusted to 10nm/s again, uses thermal resistance evaporation to be prepared in electron injecting layer steams and cross material for aluminium and the thickness cathode layer that is 80nm, thus obtain required electroluminescent device.
Embodiment 3
Organic electroluminescence device in the present embodiment is layer structure, and every layer is followed successively by:
Substrate of glass, anode layer, metal-doped layer, molysite doped layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer.Described metal-doped layer and described molysite doped layer form described heat dissipating layer.The structure of this organic electroluminescence device is substrate of glass/AZO/Pt:DCJTB/Fe 2s 3: 2T-NATA/V 2o 5/ TCTA/DCJTB/Bphen/Cs 2cO 3/ Au, wherein brace "/" represents layer structure, and colon ": " expression is adulterated mutually.Above-mentioned organic electroluminescence device is prepared successively as follows:
(1) preliminary treatment of plated film
Taking out the glass trade mark is the substrate of glass of N-LASF31A, after clean with distilled water, alcohol flushing, be placed in isopropyl alcohol and soak an evening.
(2) preparation of anode layer
Under the substrate of glass prepared through step () is placed in magnetron sputtering apparatus, the technological parameter of magnetron sputtering apparatus is set to the accelerating voltage of 800V, the magnetic field of 200G, and 1W/cm 2power density, use described magnetron sputtering apparatus to prepare material on the glass substrate for aluminium zinc oxide and the thickness anode layer that is 300nm.
(3) preparation of scattering layer
Under the substrate of glass prepared through step (two) is placed in thermal resistance evaporated device; The evaporation rate of thermal resistance evaporated device is set as 0.1nm/s, the target of thermal resistance evaporated device is set as platinum and 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, use thermal resistance evaporated device evaporation metal doped layer on the anode layer, the thickness of metal-doped layer is made to be 50nm, platinum and 4-(dintrile methyl in metal-doped layer)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl) the doping mass ratio of-4H-pyrans is 2:1;
The target of thermal resistance evaporated device is set as iron sulfide and dinaphthyl-N, N '-diphenyl-4,4 '-benzidine, use thermal resistance evaporated device evaporation molysite doped layer on metal-doped layer, the thickness of molysite doped layer is made to be 40nm, iron sulfide and dinaphthyl-N, N '-diphenyl-4 in molysite doped layer, the doping mass ratio of 4 '-benzidine is 0.4:1, thus obtained heat dissipating layer.
(4) preparation of organic electroluminescence device
To use on thermal resistance evaporation preparation molysite doped layer on the glass substrate deposition material successively for vanadic oxide and the thickness hole injection layer that is 20nm, material are 4,4 ', 4 "-three (carbazole-9-base) triphenylamines and thickness are the hole transmission layer of 60nm, material is 4-(dintrile methyl)-2-butyl-6-(1; 1; 7; 7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans and thickness are the luminescent layer of 10nm, material is 4; 7-diphenyl-1,10-phenanthroline and thickness be 200nm electron transfer layer, material is cesium carbonate and thickness is the electron injecting layer of 0.5nm; Then evaporation rate prepared by thermal resistance evaporation is adjusted to 1nm/s again, uses thermal resistance evaporation to be prepared in electron injecting layer steams and cross material for gold and the thickness cathode layer that is 100nm, thus obtain required electroluminescent device.
Embodiment 4
Organic electroluminescence device in the present embodiment is layer structure, and every layer is followed successively by:
Substrate of glass, anode layer, metal-doped layer, hole doping layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer.Described metal-doped layer and described molysite doped layer form described heat dissipating layer.The structure of this organic electroluminescence device is substrate of glass ITO/Au:Alq 3/ Fe 2s 3: F4-TCNQ/MoO 3/ NPB/Alq 3//TPBi/LiF/Pt, wherein brace "/" represents layer structure, and colon ": " expression is adulterated mutually.Above-mentioned organic electroluminescence device is prepared successively as follows:
(1) preliminary treatment of plated film
Taking out the glass trade mark is the substrate of glass of N-LASF41A, after clean with distilled water, alcohol flushing, be placed in isopropyl alcohol and soak an evening.
(2) preparation of anode layer
Under the substrate of glass prepared through step () is placed in magnetron sputtering apparatus, the technological parameter of magnetron sputtering apparatus is set to the accelerating voltage of 600V, the magnetic field of 100G, and 30W/cm 2power density, use magnetron sputtering apparatus to prepare material on the glass substrate for indium tin oxide and the thickness anode layer that is 180nm.
(3) preparation of scattering layer
Under the substrate of glass prepared through step (two) is placed in thermal resistance evaporated device, the technological parameter of thermal resistance evaporated device is set to the evaporation rate and 2 × 10 of 0.5nm/s -4the operating pressure of Pa, the target of thermal resistance evaporated device is set as gold and oxine aluminium, use evaporation metal doped layer on thermal resistance evaporated device anode layer on the glass substrate, the thickness making metal-doped layer is 80nm, and in metal-doped layer, the doping mass ratio of gold and oxine aluminium is 1:1;
Thermal resistance evaporated device is set as iron sulfide and 2,3,5,6-tetra-fluoro-7,7,8,8,-four cyano-benzoquinone's bismethane, uses electron-beam coating equipment evaporation molysite doped layer on metal-doped layer, makes the thickness of molysite doped layer be 60nm, iron sulfide and 2 in molysite doped layer, 3,5,6-tetra-fluoro-7,7,8,8, the doping mass ratio of-four cyano-benzoquinone's bismethane is 0.3:1, thus obtained heat dissipating layer.
(4) preparation of organic electroluminescence device
Thermal resistance evaporation is used to be prepared on metal-doped layer deposition material successively for molybdenum trioxide and the thickness hole injection layer that is 80nm, material are N, N '-(1-naphthyl)-N, the electron transfer layer that N '-diphenyl-4,4 '-benzidine and thickness are the hole transmission layer of 60nm, material is oxine aluminium and thickness is the luminescent layer of 40nm, N-aryl benzimidazole and thickness are 35nm, material is lithium fluoride and thickness is the electron injecting layer of 1nm; Then evaporation rate prepared by thermal resistance evaporation is adjusted to 6nm/s again, uses thermal resistance evaporated device to steam on electron injecting layer to cross material for platinum and the thickness cathode layer that is 100nm, thus obtain required electroluminescent device.
Compared with prior art, organic electroluminescence devices of the present invention and preparation method thereof, there is following advantage: the scattering layer of organic electroluminescence device of the present invention improves the injectability in hole, improve photochromic purity, improve the conductivity of device, the potential barrier that hole is injected reduces, thus improves hole injection efficiency, thus is conducive to improving light extraction efficiency.
Above-mentioned test and Preparation equipment are high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), the USB4000 fiber spectrometer testing electroluminescent spectrum of U.S. marine optics Ocean Optics, the Keithley2400 of Keithley company of the U.S. tests electric property, the CS-100A colorimeter test brightness of Japanese Konica Minolta company and colourity.
Foregoing; be only preferred embodiment of the present invention; not for limiting embodiment of the present invention; those of ordinary skill in the art are according to central scope of the present invention and spirit; can carry out corresponding flexible or amendment very easily, therefore protection scope of the present invention should be as the criterion with the protection range required by claims.

Claims (10)

1. an organic electroluminescence device, this organic electroluminescence device is layer structure, it is characterized in that, this layer structure is: the substrate of glass stacked gradually, anode layer, scattering layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer, and described scattering layer comprises metal-doped layer and molysite doped layer; Wherein,
The material of described metal-doped layer comprises high-work-function metal and fluorescence luminescent material, and the material of described molysite doped layer comprises molysite and hole doping material;
Described fluorescence luminescent 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'-two (9-ethyl-3-carbazole vinyl)-1,1'-biphenyl or oxine aluminium;
Described hole doping material is 2,3,5,6-tetra-fluoro-7,7,8,8 ,-four cyano-benzoquinone's bismethane, 4,4,4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine or dinaphthyl-N, N '-diphenyl-4,4 '-benzidines.
2. organic electroluminescence device according to claim 1, is characterized in that, described high-work-function metal and the described fluorescence luminescent material mass ratio that adulterates is 0.5:1 ~ 2:1; The doping mass ratio of described molysite and described hole doping material is 0.1:1 ~ 0.4:1.
3. organic electroluminescence device according to claim 1, is characterized in that, described high-work-function metal is silver, aluminium, platinum or gold; Described molysite is iron chloride, ferric bromide and iron sulfide.
4. organic electroluminescence device according to claim 1, is characterized in that, the refractive index of described substrate of glass is more than 1.8, and visible light transmissivity is more than 90%.
5. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described metal-doped layer is 50 ~ 200nm, and the thickness of described molysite doped layer is 40 ~ 100nm.
6. organic electroluminescence device according to claim 1, is characterized in that,
The material of described anode layer is indium tin oxide, aluminium zinc oxide or indium-zinc oxide;
The material of described hole injection layer is molybdenum trioxide, tungstic acid or vanadic oxide;
The material of described hole transmission layer is 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-base) triphenylamine or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine;
The material of described luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4,4'-two (9-ethyl-3-carbazole vinyl)-1,1'-biphenyl or oxine aluminium;
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole;
The material of described electron injecting layer is cesium carbonate, cesium fluoride, nitrine caesium or lithium fluoride.
7. a preparation method for organic electroluminescence device, is characterized in that, comprises the steps:
A () prepares anode layer by magnetron sputtering apparatus on the glass substrate;
B () uses thermal resistance evaporated device to prepare metal-doped layer on the anode layer that step (a) is obtained, then on described metal-doped layer, prepare molysite doped layer, thus obtain described heat dissipating layer; Wherein,
It is 0.5:1 ~ 2:1 high-work-function metal and fluorescence luminescent material that the material of described metal-doped layer comprises doping mass ratio, and it is 0.1:1 ~ 0.4:1 molysite and hole doping material that the material of described molysite doped layer comprises doping mass ratio;
Described fluorescence luminescent 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'-two (9-ethyl-3-carbazole vinyl)-1,1'-biphenyl or oxine aluminium;
Described hole doping material is 2,3,5,6-tetra-fluoro-7,7,8,8 ,-four cyano-benzoquinone's bismethane, 4,4,4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine or dinaphthyl-N, N '-diphenyl-4,4 '-benzidines;
(c) evaporation hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer successively on the scattering layer that step (b) is obtained, thus obtain described organic electroluminescence device.
8. preparation method according to claim 7, is characterized in that, in described step (a), the accelerating voltage of described magnetron sputtering apparatus is 300 ~ 800V, and magnetic field is 50 ~ 200G, and power density is 1 ~ 40W/cm 2.
9. preparation method according to claim 7, it is characterized in that, in described step (b), the evaporation rate of described thermal resistance evaporated device is 0.1 ~ 1nm/s, the thickness of described metal-doped layer is 50 ~ 200nm, and the thickness of described molysite doped layer is 40 ~ 100nm.
10. preparation method according to claim 7, is characterized in that, in described step (c), the evaporation rate of described hole transmission layer, luminescent layer and electron transfer layer is 0.1 ~ 1nm/s, and the evaporation rate of described cathode layer is 1 ~ 10nm/s.
CN201310438727.3A 2013-09-24 2013-09-24 Organic electroluminescent device and manufacturing method thereof Pending CN104466016A (en)

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Application publication date: 20150325