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CN104733636A - Organic electroluminescence device and preparing method thereof - Google Patents

Organic electroluminescence device and preparing method thereof Download PDF

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Publication number
CN104733636A
CN104733636A CN201310706147.8A CN201310706147A CN104733636A CN 104733636 A CN104733636 A CN 104733636A CN 201310706147 A CN201310706147 A CN 201310706147A CN 104733636 A CN104733636 A CN 104733636A
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layer
organic electroluminescence
electroluminescence device
thickness
hole
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周明杰
黄辉
陈吉星
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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Priority to CN201310706147.8A priority Critical patent/CN104733636A/en
Publication of CN104733636A publication Critical patent/CN104733636A/en
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/10OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17Carrier injection layers
    • H10K50/171Electron injection layers
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/649Aromatic compounds comprising a hetero atom
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/649Aromatic compounds comprising a hetero atom
    • H10K85/657Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60Organic compounds having low molecular weight
    • H10K85/649Aromatic compounds comprising a hetero atom
    • H10K85/656Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
    • H10K85/6565Oxadiazole compounds

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Manufacturing & Machinery (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention discloses an organic electroluminescence device. The device comprises a substrate, an anode, a hole injection layer, a hole transmission layer, a light emitting layer, an electron transmission layer, an electron injection layer and a cathode which are overlapped in sequence. The electron injection layer of the organic electroluminescence device is made of mixtures of electron transmission materials, thiophene compounds and hole doping object materials. The electron transmission materials can be subjected to crystallization easily under the vitrification converting temperature of 50-100 DEG C, electron transmission speed can be improved, crystallization can happen easily, after crystallization, crystal arraying is in order, light scattering can be enhanced, light emitted to the two sides is scattered back to the middle to be emitted out, and light-out efficiency is improved. Compared with a traditional organic electroluminescence device, the organic electroluminescence device is high in light-emitting efficiency. The invention further discloses a preparing method of the organic electroluminescence device.

Description

Organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to field of organic electroluminescence, particularly relate to a kind of organic electroluminescence device and preparation method thereof.
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/m2, and its luminous efficiency is 1.51lm/W, the life-span is greater than 100 hours.
In traditional field of organic electroluminescence, all low than hole transport speed two or three orders of magnitude of electron transfer rate, thus very easily cause the low of exciton recombination probability, and make the region of its compound not at light-emitting zone, thus cause luminous efficiency to reduce.
Summary of the invention
Based on this, be necessary the organic electroluminescence device providing a kind of luminous efficiency higher.
A kind of organic electroluminescence device, comprise stack gradually substrate, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode;
The mixture of the electron transport material of the material of described electron injecting layer to be mass ratio be 15 ~ 30:0.3 ~ 1.5:0.1, thiophenes and hole doping guest materials;
Described electron transport material is 4,7-diphenyl-1,10-phenanthroline, 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1,3,4-oxadiazoles, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene or 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles];
Described thiophenes is 3 methyl thiophene, 3 methyl thiophene, 3-octyl thiophene or 3-dodecylthiophene;
Described hole doping guest materials 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.
In one embodiment, the thickness of described electron injecting layer is 15nm ~ 70nm.
In one embodiment, described anode is indium and tin oxide film, mix the zinc-oxide film of aluminium or mix the zinc-oxide film of indium, and the thickness of described anode is 50nm ~ 300nm.
In one embodiment, the material of described hole injection layer is molybdenum trioxide, tungstic acid or vanadic oxide, and the thickness of described hole injection layer is 20nm ~ 80nm.
In one embodiment, 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 thickness of described hole transmission layer is 20nm ~ 60nm
In one embodiment, 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 thickness of described luminescent layer is 5nm ~ 40nm.
In one embodiment, the material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole, and the thickness of described electron transfer layer is 40nm ~ 250nm.
In one embodiment, the material of described negative electrode is Ag, Al, Pt or Au, and the thickness of described negative electrode is 80nm ~ 250nm.
A preparation method for organic electroluminescence device, comprises the steps:
Surface preparation is carried out to substrate;
Magnetron sputtering prepares anode on the substrate;
On described anode, evaporation forms hole injection layer successively, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer, the electron transport material of the material of described electron injecting layer to be mass ratio be 15 ~ 30:0.3 ~ 1.5:0.1, the mixture of thiophenes and hole doping guest materials, described electron transport material is 4, 7-diphenyl-1, 10-phenanthroline, 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1, 3, 4-oxadiazoles, 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene or 2, 2'-(1, 3-phenyl) two [5-(4-tert-butyl-phenyl)-1, 3, 4-oxadiazoles], described thiophenes is 3 methyl thiophene, 3 methyl thiophene, 3-octyl thiophene or 3-dodecylthiophene, described hole doping guest materials 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 '-benzidine, and
On described electron injecting layer, evaporation forms negative electrode, obtains described organic electroluminescence device.
In one embodiment, the accelerating voltage of magnetron sputtering is 300V ~ 800V, and magnetic field is 50G ~ 200G, and power density is 1W/cm 2~ 40W/cm 2;
In evaporate process, operating pressure is 2 × 10 -3~ 5 × 10 -5pa, the evaporation rate of organic material is 0.1 ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1 ~ 10nm/s.
The mixture of the electron transport material of the material of the electron injecting layer of this organic electroluminescence device to be mass ratio be 15 ~ 30:0.3 ~ 1.5:0.1, thiophenes and hole doping guest materials, electron transport material selects the electron transport material of the easy crystallization of glass transition temperature between 50 DEG C ~ 100 DEG C, the transmission rate of electronics can be improved and easily crystallization, after crystallization, crystal arrangement is orderly, the scattering of high light can be added, make the light scattering of launching to both sides get back to middle outgoing, improve light extraction efficiency; Thiophene compound segment is regular, orderly, is conducive to the transmission of charge carrier, meanwhile, can improve the segment regularity of molecules, be conducive to the scattering of light after adding; The HOMO energy level of hole doping guest materials is very low, can traverse to negative electrode one end and electronics generation compound and cancellation occurs by blocking hole, is conducive to improving luminous efficiency.
Relative to traditional organic electroluminescence device, this organic electroluminescence device luminous efficiency is higher.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is the flow chart of the preparation method of the organic electroluminescence device of an execution mode;
Fig. 3 is the brightness of organic electroluminescence device for preparing of embodiment 1 and comparative example and the graph of a relation of luminous efficiency.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
The organic electroluminescence device of an execution mode as shown in Figure 1, comprises the following structure stacked gradually: substrate 10, anode 20, hole injection layer 30, hole transmission layer 40, luminescent layer 50, electron transfer layer 60, electron injecting layer 70 and negative electrode 80.
Substrate 10 is glass.Generally speaking, simple glass.In special application, the special glass of special process processing and fabricating also can be selected.
Anode 20 can be indium and tin oxide film (ITO), mixes the zinc-oxide film (AZO) of aluminium or mix the zinc-oxide film (IZO) of indium, and the thickness of anode 20 is 50nm ~ 300nm.In one preferably embodiment, anode 20 is indium and tin oxide film (ITO), and the thickness of anode 20 is 120nm.
The material of hole injection layer 30 can be molybdenum trioxide (MoO 3), tungstic acid (WO 3) or vanadic oxide (V 2o 5).The thickness of hole injection layer 30 can be 20nm ~ 80nm.In one preferably embodiment, the material of hole injection layer 30 is molybdenum trioxide (MoO 3), the thickness of hole injection layer 30 is 24nm.
The material of hole transmission layer 40 can be 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB), the material of hole transmission layer 40 can be 20nm ~ 60nm.In one preferably embodiment, the material of hole transmission layer 40 is NPB, and the material of hole transmission layer 40 is 37nm.
The material of luminescent layer 50 can be 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'-or oxine aluminium (Alq 3), the thickness of luminescent layer 50 can be 5nm ~ 40nm.In one preferably embodiment, the material of luminescent layer 50 is BCzVBi, and the thickness of luminescent layer 50 is 21nm.
The material of electron transfer layer 60 can be electron transport material.The thickness of electron transfer layer 60 can be 40nm ~ 250nm.Electron transport layer materials can be 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (TAZ) or N-aryl benzimidazole (TPBI).In one preferably embodiment, the material of electron transfer layer 60 is TPBI, and the thickness of electron transfer layer 60 is 80nm.
The mixture of the electron transport material of the material of electron injecting layer 70 to be mass ratio be 15 ~ 30:0.3 ~ 1.5:0.1, thiophenes and hole doping guest materials.The thickness of electron injecting layer 70 is 15nm ~ 70nm.
Electron transport material selects the electron transport material of the easy crystallization of glass transition temperature between 50 DEG C ~ 100 DEG C, be specially 4,7-diphenyl-1,10-phenanthroline (Bphen), 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1,3,4-oxadiazoles (PBD), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP) or 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles] (OXD-7).
Thiophenes is 3 methyl thiophene (3HT), 3 methyl thiophene (3AT), 3-octyl thiophene (3OT) or 3-dodecylthiophene (3DDT).These compounds, easily prepare, and can obtain on the market, and meanwhile, the ability of transporting holes is comparatively strong, and segment is in order regular, is common polymer monomer material.
Hole doping guest materials 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) or dinaphthyl-N, N '-diphenyl-4,4 '-benzidine (2T-NATA).The HOMO energy level of these materials is higher, between-6.7eV ~-7.8eV, effectively can improve the injection efficiency in hole after doping, easily forms p doping.
The material of negative electrode 80 is Ag, Al, Pt or Au, and the thickness of negative electrode 80 is 80nm ~ 250nm.In one preferably embodiment, the material of negative electrode 80 is Ag, and the thickness of negative electrode 80 is 200nm.
The mixture of the electron transport material of the material of the electron injecting layer 70 of this organic electroluminescence device to be mass ratio be 15 ~ 30:0.3 ~ 1.5:0.1, thiophenes and hole doping guest materials, electron transport material selects the electron transport material of the easy crystallization of glass transition temperature between 50 DEG C ~ 100 DEG C, the transmission rate of electronics can be improved and easily crystallization, after crystallization, crystal arrangement is orderly, the scattering of high light can be added, make the light scattering of launching to both sides get back to middle outgoing, improve light extraction efficiency; Thiophene compound segment is regular, orderly, is conducive to the transmission of charge carrier, meanwhile, can improve the segment regularity of molecules, be conducive to the scattering of light after adding; The HOMO energy level of hole doping guest materials is very low, can traverse to negative electrode one end and electronics generation compound and cancellation occurs by blocking hole, is conducive to improving luminous efficiency.
Relative to traditional organic electroluminescence device, this organic electroluminescence device luminous efficiency is higher.
The preparation method of above-mentioned organic electroluminescence device as shown in Figure 2, comprises the steps:
S10, surface preparation is carried out to substrate 10.
Substrate 10 is glass.Generally speaking, simple glass.In special application, the special glass of special process processing and fabricating also can be selected.
The process of surface preparation is specially: after substrate 10 being rinsed well successively with distilled water and ethanol, be placed in isopropyl alcohol soaked overnight.
S20, on the substrate 10 magnetron sputtering prepare anode 20.
Anode 20 can be indium and tin oxide film (ITO), mixes the zinc-oxide film (AZO) of aluminium or mix the zinc-oxide film (IZO) of indium, and the thickness of anode 20 is 50nm ~ 300nm.In one preferably embodiment, anode 20 is indium and tin oxide film (ITO), and the thickness of anode 20 is 120nm.
The accelerating voltage of magnetron sputtering is 300V ~ 800V, and magnetic field is 50G ~ 200G, and power density is 1W/cm 2~ 40W/cm 2.
S30, on anode 20 successively evaporation formed hole injection layer 30, hole transmission layer 40, luminescent layer 50, electron transfer layer 60 and electron injecting layer 70.
In evaporate process, operating pressure is 2 × 10 -3~ 5 × 10 -5pa, the evaporation rate of organic material is 0.1 ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1 ~ 10nm/s.
The material of hole injection layer 30 can be molybdenum trioxide (MoO 3), tungstic acid (WO 3) or vanadic oxide (V 2o 5).The thickness of hole injection layer 30 can be 20nm ~ 80nm.In one preferably embodiment, the material of hole injection layer 30 is molybdenum trioxide (MoO 3), the thickness of hole injection layer 30 is 24nm.
The material of hole transmission layer 40 can be 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB), the material of hole transmission layer 40 can be 20nm ~ 60nm.In one preferably embodiment, the material of hole transmission layer 40 is NPB, and the material of hole transmission layer 40 is 37nm.
The material of luminescent layer 50 can be 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'-or oxine aluminium (Alq 3), the thickness of luminescent layer 50 can be 5nm ~ 40nm.In one preferably embodiment, the material of luminescent layer 50 is BCzVBi, and the thickness of luminescent layer 50 is 21nm.
The material of electron transfer layer 60 can be electron transport material.The thickness of electron transfer layer 60 can be 40nm ~ 250nm.Electron transport layer materials can be 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (TAZ) or N-aryl benzimidazole (TPBI).In one preferably embodiment, the material of electron transfer layer 60 is TPBI, and the thickness of electron transfer layer 60 is 80nm.
The mixture of the electron transport material of the material of electron injecting layer 70 to be mass ratio be 15 ~ 30:0.3 ~ 1.5:0.1, thiophenes and hole doping guest materials.The thickness of electron injecting layer 70 is 15nm ~ 70nm.
Electron transport material selects the electron transport material of the easy crystallization of glass transition temperature between 50 DEG C ~ 100 DEG C, be specially 4,7-diphenyl-1,10-phenanthroline (Bphen), 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1,3,4-oxadiazoles (PBD), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP) or 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles] (OXD-7).
Thiophenes is 3 methyl thiophene (3HT), 3 methyl thiophene (3AT), 3-octyl thiophene (3OT) or 3-dodecylthiophene (3DDT).
Hole doping guest materials 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) or dinaphthyl-N, N '-diphenyl-4,4 '-benzidine (2T-NATA).
S40, on electron injecting layer 70 evaporation formed negative electrode 80, obtain organic electroluminescence device.
The evaporation rate of negative electrode 80 is 1nm/s ~ 10nm/s.
The material of negative electrode 80 is Ag, Al, Pt or Au, and the thickness of negative electrode 80 is 80nm ~ 250nm.In one preferably embodiment, the material of negative electrode 80 is Ag, and the thickness of negative electrode 80 is 200nm.
Preparation method's step of this organic electroluminescence device is simple, and simple and easy to do, the organic electroluminescence device luminous efficiency prepared is higher.
It is below specific embodiment, the test used in embodiment and Preparation equipment comprise: the high vacuum coating system (evaporation) of 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 and colourity) of Japanese Konica Minolta company.
Embodiment 1
A kind of organic electroluminescence device, comprise stack gradually substrate, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, concrete structure is expressed as: glass/ITO/MoO 3/ NPB/BCzVBi/TPBI/BCP:3HT:F4-TCNQ/Ag.Preparation process is:
Commercially available simple glass is provided, after glass distilled water and ethanol being rinsed well successively, is placed in isopropyl alcohol soaked overnight.
Anode is prepared at surface-treated glass surface magnetron sputtering.The material of anode is ITO, and thickness is 120nm.The accelerating voltage of magnetron sputtering is 700V, and magnetic field is 120G, and power density is 25W/cm 2.
Be 8 × 10 in operating pressure -4under the condition of Pa, be 0.2nm/s according to the evaporation rate of organic material, the evaporation rate of metal and metallic compound is 2nm/s, and on anode, evaporation prepares hole injection layer, hole transmission layer, luminescent layer and electron transfer layer successively.The material of hole injection layer is MoO 3, thickness is 24nm.The material of hole transmission layer is NPB, and thickness is 37nm.The material of luminescent layer is BCzVBi, and thickness is 21nm.The material of electron transfer layer is TPBI, and thickness is 80nm.The mixture of the material of electron injecting layer to be mass ratio be BCP, 3HT and F4-TCNQ of 20:0.8:0.1, thickness is 50nm.
Be 8 × 10 in operating pressure -4under the condition of Pa, be 2nm/s according to the evaporation rate of metallic cathode, on electron injecting layer, evaporation forms negative electrode, obtains organic electroluminescence device.The material of negative electrode is Ag, and thickness is 200nm.
Organic electroluminescence device (simple glass/the ITO/MoO of organic electroluminescence device prepared by embodiment 1 as shown in Figure 3 and ordinary construction 3/ NPB/BCzVBi/TPBi/Cs 2cO 3/ Ag) brightness and the graph of a relation of luminous efficiency.
Curve 1 is the brightness of organic electroluminescence device and the relation curve of luminous efficiency of embodiment 1 preparation, and curve 2 is the brightness of the organic electroluminescence device of ordinary construction and the graph of a relation of luminous efficiency.
As seen from Figure 3, under same brightness, the luminous efficiency of organic electroluminescence device prepared by embodiment 1 is significantly higher than the luminous efficiency of the organic electroluminescence device of ordinary construction.The maximum luminous efficiency of organic electroluminescence device prepared by embodiment 1 is 5.35lm/W, and the maximum lumen efficiency of the organic electroluminescence device of ordinary construction is only 4.76lm/W, and the luminous efficiency of the organic electroluminescence device of ordinary construction declines fast along with the increase of brightness.This explanation, the electron injecting layer of organic electroluminescence device prepared by embodiment 1 can improve the transmission rate of electronics, add the scattering of high light, blocking hole traverses to negative electrode one end and electronics generation compound and cancellation occurs, and improves the luminous efficiency of organic electroluminescence device.
Embodiment 2
A kind of organic electroluminescence device, comprise stack gradually substrate, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, concrete structure is expressed as: glass/IZO/V 2o 5/ TAPC/AND/TAZ/Bphen:3AT:1T-NATA/Al.Preparation process is:
Commercially available simple glass is provided, after glass distilled water and ethanol being rinsed well successively, is placed in isopropyl alcohol soaked overnight.
Anode is prepared at surface-treated glass surface magnetron sputtering.The material of anode is IZO, and thickness is 300nm.The accelerating voltage of magnetron sputtering is 300V, and magnetic field is 50G, and power density is 40W/cm 2.
Be 2 × 10 in operating pressure -3under the condition of Pa, be 1nm/s according to the evaporation rate of organic material, the evaporation rate of metal and metallic compound is 10nm/s, and on anode, evaporation prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively.The material of hole injection layer is V 2o 5, thickness is 20nm.The material of hole transmission layer is TAPC, and thickness is 45nm.The material of luminescent layer is ADN, and thickness is 5nm.The material of electron transfer layer is TAZ, and thickness is 65nm.The mixture of the material of electron injecting layer to be mass ratio be Bphen, 3AT and 1T-NATA of 15:0.3:0.1, thickness is 70nm.
Be 2 × 10 in operating pressure -3under the condition of Pa, be 10nm/s according to the evaporation rate of metallic cathode, on electron injecting layer, evaporation forms negative electrode, obtains organic electroluminescence device.The material of negative electrode is Al, and thickness is 80nm.
Embodiment 3
A kind of organic electroluminescence device, comprise stack gradually substrate, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, concrete structure is expressed as: glass/AZO/WO 3/ TCTA/Alq 3/ TAZ/PBD:3OT:2T-NATA/Au.Preparation process is:
Commercially available simple glass is provided, after glass distilled water and ethanol being rinsed well successively, is placed in isopropyl alcohol soaked overnight.
Anode is prepared at surface-treated glass surface magnetron sputtering.The material of anode is AZO, and thickness is 150nm.The accelerating voltage of magnetron sputtering is 800V, and magnetic field is 200G, and power density is 1W/cm 2.
Be 5 × 10 in operating pressure -5under the condition of Pa, be 0.1nm/s according to the evaporation rate of organic material, the evaporation rate of metal and metallic compound is 1nm/s, and on anode, evaporation prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively.The material of hole injection layer is WO 3, thickness is 55nm.The material of hole transmission layer is TCTA, and thickness is 60nm.The material of luminescent layer is Alq 3, thickness is 40nm.The material of electron transfer layer is TAZ, and thickness is 50nm.The mixture of the material of electron injecting layer to be mass ratio be PBD, 3OT and 2T-NATA of 30:1.5:0.1, thickness is 15nm.
Be 5 × 10 in operating pressure -5under the condition of Pa, be 1nm/s according to the evaporation rate of metallic cathode, on electron injecting layer, evaporation forms negative electrode, obtains organic electroluminescence device.The material of negative electrode is Au, and thickness is 250nm.
Embodiment 4
A kind of organic electroluminescence device, comprise stack gradually substrate, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, concrete structure is expressed as: glass/ITO/MoO 3/ TCTA/DCJTB/Bphen/OXD-7:3DDT:2T-NATA/Pt.Preparation process is:
Commercially available simple glass is provided, after glass distilled water and ethanol being rinsed well successively, is placed in isopropyl alcohol soaked overnight.
Anode is prepared at surface-treated glass surface magnetron sputtering.The material of anode is ITO, and thickness is 50nm.The accelerating voltage of magnetron sputtering is 600V, and magnetic field is 100G, and power density is 30W/cm 2.
Be 2 × 10 in operating pressure -4under the condition of Pa, be 0.5nm/s according to the evaporation rate of organic material, the evaporation rate of metal and metallic compound is 6nm/s, and on anode, evaporation prepares hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively.The material of hole injection layer is MoO 3, thickness is 80nm.The material of hole transmission layer is TCTA, and thickness is 60nm.The material of luminescent layer is DCJTB, and thickness is 8nm.The material of electron transfer layer is Bphen, and thickness is 200nm.The mixture of the material of electron injecting layer to be mass ratio be OXD-7,3DDT and 2T-NATA of 25:0.4:0.1, thickness is 65nm.
Be 8 × 10 in operating pressure -4under the condition of Pa, be 6nm/s according to the evaporation rate of metallic cathode, on electron injecting layer, evaporation forms negative electrode, obtains organic electroluminescence device.The material of negative electrode is Pt, and thickness is 160nm.
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, is characterized in that, comprise stack gradually substrate, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode;
The mixture of the electron transport material of the material of described electron injecting layer to be mass ratio be 15 ~ 30:0.3 ~ 1.5:0.1, thiophenes and hole doping guest materials;
Described electron transport material is 4,7-diphenyl-1,10-phenanthroline, 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1,3,4-oxadiazoles, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene or 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles];
Described thiophenes is 3 methyl thiophene, 3 methyl thiophene, 3-octyl thiophene or 3-dodecylthiophene;
Described hole doping guest materials 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 as claimed in claim 1, it is characterized in that, the thickness of described electron injecting layer is 15nm ~ 70nm.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, described anode is indium and tin oxide film, mix the zinc-oxide film of aluminium or mix the zinc-oxide film of indium, and the thickness of described anode is 50nm ~ 300nm.
4. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described hole injection layer is molybdenum trioxide, tungstic acid or vanadic oxide, and the thickness of described hole injection layer is 20nm ~ 80nm.
5. organic electroluminescence device as claimed in claim 1, it is characterized in that, 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 thickness of described hole transmission layer is 20nm ~ 60nm.
6. organic electroluminescence device as claimed in claim 1, it is characterized in that, 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, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl of 4'-or oxine aluminium, the thickness of described luminescent layer is 5nm ~ 40nm.
7. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative or N-aryl benzimidazole, the thickness of described electron transfer layer is 40nm ~ 250nm.
8. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described negative electrode is Ag, Al, Pt or Au, and the thickness of described negative electrode is 80nm ~ 250nm.
9. a preparation method for organic electroluminescence device, is characterized in that, comprises the steps:
Surface preparation is carried out to substrate;
Magnetron sputtering prepares anode on the substrate;
On described anode, evaporation forms hole injection layer successively, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer, the electron transport material of the material of described electron injecting layer to be mass ratio be 15 ~ 30:0.3 ~ 1.5:0.1, the mixture of thiophenes and hole doping guest materials, described electron transport material is 4, 7-diphenyl-1, 10-phenanthroline, 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1, 3, 4-oxadiazoles, 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene or 2, 2'-(1, 3-phenyl) two [5-(4-tert-butyl-phenyl)-1, 3, 4-oxadiazoles], described thiophenes is 3 methyl thiophene, 3 methyl thiophene, 3-octyl thiophene or 3-dodecylthiophene, described hole doping guest materials 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 '-benzidine, and
On described electron injecting layer, evaporation forms negative electrode, obtains described organic electroluminescence device.
10. the preparation method of organic electroluminescence device as claimed in claim 9, it is characterized in that, the accelerating voltage of magnetron sputtering is 300V ~ 800V, and magnetic field is 50G ~ 200G, and power density is 1W/cm 2~ 40W/cm 2;
In evaporate process, operating pressure is 2 × 10 -3~ 5 × 10 -5pa, the evaporation rate of organic material is 0.1 ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1 ~ 10nm/s.
CN201310706147.8A 2013-12-19 2013-12-19 Organic electroluminescence device and preparing method thereof Pending CN104733636A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108461640A (en) * 2018-03-16 2018-08-28 中国科学院长春应用化学研究所 Crystalline state organic electroluminescent LED and its application
WO2024208197A1 (en) * 2023-04-03 2024-10-10 Tcl科技集团股份有限公司 Light-emitting device, manufacturing method therefor, and display apparatus

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108461640A (en) * 2018-03-16 2018-08-28 中国科学院长春应用化学研究所 Crystalline state organic electroluminescent LED and its application
WO2024208197A1 (en) * 2023-04-03 2024-10-10 Tcl科技集团股份有限公司 Light-emitting device, manufacturing method therefor, and display apparatus

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