CN104183729A - Organic light emitting device and manufacturing method thereof - Google Patents

Organic light emitting device and manufacturing method thereof Download PDF

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Publication number
CN104183729A
CN104183729A CN201310196289.4A CN201310196289A CN104183729A CN 104183729 A CN104183729 A CN 104183729A CN 201310196289 A CN201310196289 A CN 201310196289A CN 104183729 A CN104183729 A CN 104183729A
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layer
evaporation
thickness
zinc oxide
oxide
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周明杰
王平
黄辉
陈吉星
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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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Publication of CN104183729A publication Critical patent/CN104183729A/en
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/865—Intermediate layers comprising a mixture of materials of the adjoining active layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H10K50/155—Hole transporting layers comprising dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H10K50/854—Arrangements for extracting light from the devices comprising scattering means
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition

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

Abstract

The invention discloses an organic light emitting device, which comprises an anode, a hole injection layer, a first hole transmission layer, a first light emitting layer, a first electron transmission layer, a charge generation layer, a second hole transmission layer, a second light emitting layer, a second electron transmission layer, an electron injection layer and a cathode stacked sequentially. The charge generation layer comprises an n-type layer, a middle layer, and a zinc oxide-doped layer, wherein the material of the n-type layer comprises bipolar metal oxide; the material of the middle layer is titanium dioxide; and material of the zinc oxide-doped layer is zinc oxide material doped with lanthanide oxide. The light emitting efficiency of the organic light emitting device is high. The invention also provides an organic light emitting device manufacturing method.

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
The principle of luminosity of organic electroluminescence device is based under the effect of extra electric field, and 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.Electronics and hole meet at luminescent layer, compound, form exciton, exciton moves under electric field action, and energy is passed to luminescent material, and excitation electron is from ground state transition to excitation state, excited energy, by Radiation-induced deactivation, produces photon, discharges luminous energy.Yet the luminous efficiency of organic electroluminescence device is lower at present.
Summary of the invention
Based on this, be necessary to provide organic electroluminescence device that a kind of luminous efficiency is higher and preparation method thereof.
A kind of organic electroluminescence device, comprise the anode stacking gradually, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode, described charge generation layer comprises N-shaped layer, intermediate layer and doped zinc oxide diamicton, described N-shaped layer material is selected from molybdenum trioxide, in tungstic acid and vanadic oxide at least one, intermediate layer material is titanium dioxide, Zinc oxide doped layer material is the zinc oxide material doped with lanthanide oxide, described lanthanide oxide is selected from titanium dioxide praseodymium, praseodymium sesquioxide, at least one in three ytterbium oxides and samarium oxide, wherein, the mass ratio of described lanthanide oxide and described zinc oxide is 1:20～1:5.
The thickness of described N-shaped layer is 10nm～60nm, and described intermediate layer thickness is 20nm～150nm, and the thickness of described doped zinc oxide diamicton is 10nm～40nm.
The particle diameter of described titanium dioxide is 100nm～200nm.
The material of described the first hole transmission layer and described the second hole transmission layer is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine and N; N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine.
The material of described the first electron transfer layer and described the second electron transfer layer is selected from 4,7-diphenyl-1,10-phenanthroline, 1,2, at least one in 4-triazole derivative and N-aryl benzimidazole.
A preparation method for organic electroluminescence device, comprises the following steps:
At anode surface successively evaporation, prepare hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer;
At described the first electron transfer layer surface evaporation, prepare charge generation layer, described charge generation layer comprises N-shaped layer, intermediate layer and doped zinc oxide diamicton, described N-shaped layer material is selected from molybdenum trioxide, in tungstic acid and vanadic oxide at least one, intermediate layer material is titanium dioxide, Zinc oxide doped layer material is the zinc oxide material doped with lanthanide oxide, described lanthanide oxide is selected from titanium dioxide praseodymium, praseodymium sesquioxide, at least one in three ytterbium oxides and samarium oxide, wherein, the mass ratio of described lanthanide oxide and described zinc oxide is 1:20～1:5, evaporation is 2 * 10 at vacuum pressure -3～5 * 10 -5under Pa, carry out, intermediate layer adopts electron beam evaporation plating mode, and the energy density of electron beam evaporation plating is 10W/cm 2～l00W/cm 2, the evaporation speed of organic material is 0.1～1nm/s, the evaporation speed of metal and metallic compound is 1～10nm/s, and
On described charge generation layer surface successively evaporation, form the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode.
The material of described the first luminescent layer and described the second luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, at least one in 4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl and oxine aluminium.
The material of described the first hole transmission layer and described the second hole transmission layer is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine and N; N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine.
The thickness of described N-shaped layer is 10nm～60nm, and described intermediate layer thickness is 20nm～150nm, and the thickness of described doped zinc oxide diamicton is 10nm～40nm.
Before described anode surface forms hole injection layer, first antianode carries out pre-treatment, pre-treatment comprises: anode is carried out to photoetching treatment, be cut into needed size, adopt liquid detergent, deionized water, acetone, ethanol, each Ultrasonic Cleaning of isopropyl acetone 15min, to remove the organic pollution of anode surface.
Above-mentioned organic electroluminescence device and preparation method thereof, charge generation layer is by comprising N-shaped layer, intermediate layer and doped zinc oxide diamicton form, wherein, N-shaped layer material is the transmission rate that bipolarity metal oxide can improve electronics, for luminescence unit provides regeneration electronics, titanium dioxide is intermediate layer, it has larger surface area, network configuration, can carry out scattering to light, doped with the zinc oxide of lanthanide oxide and the HOMO energy level of hole mobile material, mate, can reduce injection barrier, improve the regeneration injectability in hole, zinc oxide work function also approaches the HOMO energy level of hole mobile material, be conducive to the injection in hole, be conducive to the transmission of charge carrier, improve exciton recombination probability, this charge generation layer can effectively improve the luminous efficiency of organic electroluminescence device.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is preparation method's the flow chart of the organic electroluminescence device of an execution mode;
Fig. 3 is current density and the luminous efficiency graph of a relation of the organic electroluminescence device of embodiment 1 preparation.
Embodiment
Below in conjunction with the drawings and specific embodiments, organic electroluminescence device and preparation method thereof is further illustrated.
Refer to Fig. 1, the organic electroluminescence device 100 of one execution mode comprises anode 10, hole injection layer 20, the first hole transmission layer 32, the first luminescent layer 34, the first electron transfer layer 36, charge generation layer 40, the second hole transmission layer 52, the second luminescent layer 54, the second electron transfer layer 56, electron injecting layer 60 and the negative electrode 70 stacking gradually, charge generation layer 40 comprises N-shaped layer 401, intermediate layer 402 and doped zinc oxide diamicton 403.
Anode 10 is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), is preferably ITO.
Hole injection layer 20 is formed at anode 10 surfaces.The material of hole injection layer 20 is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) at least one, be preferably V 2o 5.The thickness of hole injection layer 20 is 20nm～80nm, is preferably 60nm.
The first hole transmission layer 32 is formed at the surface of hole injection layer 20.The material of the first hole transmission layer 32 is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4; at least one in 4 '-benzidine (NPB), is preferably TCTA.The thickness of the first hole transmission layer 32 is 20nm～60nm, is preferably 30nm.
The first luminescent layer 34 is formed at the surface of the first hole transmission layer 32.The material of the first luminescent layer 34 is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably BCzVBi.The thickness of luminescent layer 40 is 5nm～40nm, is preferably 20nm.
The first electron transfer layer 36 is formed at the surface of the first luminescent layer 32.The material of the first electron transfer layer 36 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and at least one in 4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TPBI.The thickness of the first electron transfer layer 36 is 40nm～300nm, is preferably 60nm.
Charge generation layer 40 is formed at the surface of the first electron transfer layer 36.Charge generation layer 40, charge generation layer 40 comprises N-shaped layer 401, intermediate layer 402 and doped zinc oxide diamicton 403, the material of N-shaped layer 401 is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) at least one.Intermediate layer 402 materials are titanium dioxide, and doped zinc oxide diamicton 403 materials are the zinc oxide material doped with lanthanide oxide, and described lanthanide oxide is selected from titanium dioxide praseodymium (PrO 2), praseodymium sesquioxide (Pr 2o 3), three ytterbium oxide (Yb 2o 3) and samarium oxide (Sm 2o 3) at least one, wherein, the mass ratio of described lanthanide oxide and described zinc oxide is 1:20～1:5.The thickness of described N-shaped layer 401 is 10nm～60nm, and described intermediate layer 402 thickness are 20nm～150nm, and the thickness of described doped zinc oxide diamicton 403 is 10nm～40nm.
Wherein, the particle diameter of titanium dioxide is 100nm～200nm.
The second hole transmission layer 52 is formed at the surface of doped zinc oxide diamicton 403.The material of the second hole transmission layer 52 is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4; at least one in 4 '-benzidine (NPB), is preferably TAPC.The thickness of the second hole transmission layer 52 is 20nm～60nm, is preferably 30nm.
The second luminescent layer 54 is formed at the surface of the second hole transmission layer 52.The material of the second luminescent layer 54 is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably BCzVBi.The thickness of luminescent layer 40 is 5nm～40nm, is preferably 20nm.
The second electron transfer layer 56 is formed at the surface of the second luminescent layer 52.The material of the second electron transfer layer 56 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and at least one in 4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TAZ.The thickness of the second electron transfer layer 56 is 40nm～300nm, is preferably 210nm.
Electron injecting layer 60 is formed at the second electron transfer layer 56 surfaces.The material of electron injecting layer 60 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 60 is 0.5nm～10nm, is preferably 1nm.
Negative electrode 70 is formed at electron injecting layer 60 surfaces.The material of negative electrode 70 is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au), is preferably Al.The thickness of negative electrode 70 is 60nm～300nm, is preferably 150nm.
Above-mentioned organic electroluminescence device 100, charge generation layer 40 is by comprising N-shaped layer 401, intermediate layer 402 and doped zinc oxide diamicton 403 form, wherein, N-shaped layer 401 material are the transmission rate that bipolarity metal oxide can improve electronics, for luminescence unit provides regeneration electronics, titanium dioxide is intermediate layer 402, it has larger surface area, network configuration, can carry out scattering to light, doped zinc oxide diamicton 403 is to mate doped with the zinc oxide of lanthanide oxide and the HOMO energy level of hole mobile material, can reduce injection barrier, improve the regeneration injectability in hole, zinc oxide work function also approaches the HOMO energy level of hole mobile material, be conducive to the injection in hole, improve exciton recombination probability, this charge generation layer can effectively improve the luminous efficiency of organic electroluminescence device 100, organic electroluminescence device 100 has two luminescence units simultaneously, thereby has brightness and luminous efficiency at double.
Be appreciated that in this organic electroluminescence device 100 and also other functional layers can be set as required.
Please refer to Fig. 2, the preparation method of the organic electroluminescence device 100 of an embodiment, it comprises the following steps:
Step S110, at anode surface successively evaporation, prepare hole injection layer 20, the first hole transmission layer 32, the first luminescent layer 34 and the first electron transfer layer 36.
Anode 10 is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), is preferably ITO.
In present embodiment, before anode 10 surfaces form hole injection layer 20, first antianode 10 carries out pre-treatment, pre-treatment comprises: anode 10 is carried out to photoetching treatment, be cut into needed size, adopt liquid detergent, deionized water, acetone, ethanol, each Ultrasonic Cleaning of isopropyl acetone 15min, to remove the organic pollution on anode 10 surfaces.
Hole injection layer 20 is formed at the surface of anode 10.Hole injection layer 20 is prepared by evaporation.The material of hole injection layer 20 is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) at least one, be preferably V 2o 5.The thickness of hole injection layer 20 is 20nm～80nm, is preferably 60nm.Evaporation is 2 * 10 at vacuum pressure -3pa～5 * 10 -5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
The first hole transmission layer 32 is formed at the surface of hole injection layer 20.The first hole transmission layer 32 is prepared by evaporation.The material of the first hole transmission layer 32 is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4; at least one in 4 '-benzidine (NPB), is preferably TCTA.The thickness of the first hole transmission layer 32 is 20nm～60nm, is preferably 30nm.Evaporation is 2 * 10 at vacuum pressure -3pa～5 * 10 -5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
The first luminescent layer 34 is formed at the surface of the first hole transmission layer 32.The first luminescent layer 34 is prepared by evaporation.The material of the first luminescent layer 34 is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably BCzVBi.The thickness of luminescent layer 40 is 5nm～40nm, is preferably 20nm.Evaporation is 2 * 10 at vacuum pressure -3pa～5 * 10 -5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
The first electron transfer layer 36 is formed at the surface of the first luminescent layer 32.The first electron transfer layer 36 is prepared by evaporation.The material of the first electron transfer layer 36 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and at least one in 4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TPBI.The thickness of the first electron transfer layer 36 is 40nm～300nm, is preferably 60nm.Evaporation is 2 * 10 at vacuum pressure -3pa～5 * 10 -5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
Step S120, at the surperficial evaporation of the first electron transfer layer 36, prepare charge generation layer 40.
Charge generation layer 40 is formed at the surface of the first electron transfer layer 36, and charge generation layer 40 comprises N-shaped layer 401, intermediate layer 402 and doped zinc oxide diamicton 403, and the material of N-shaped layer 401 is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) at least one.Intermediate layer 402 materials are titanium dioxide, and doped zinc oxide diamicton 403 materials are the zinc oxide material doped with lanthanide oxide, and described lanthanide oxide is selected from titanium dioxide praseodymium (PrO 2), praseodymium sesquioxide (Pr 2o 3), three ytterbium oxide (Yb 2o 3) and samarium oxide (Sm 2o 3) at least one, wherein, the mass ratio of described lanthanide oxide and described zinc oxide is 1:20～1:5.The thickness of described N-shaped layer 401 is 10nm～60nm, and described intermediate layer 402 thickness are 20nm～150nm, and the thickness of described doped zinc oxide diamicton 403 is 10nm～40nm.Evaporation is 2 * 10 at vacuum pressure -3～5 * 10 -5under Pa, carry out, intermediate layer adopts electron beam evaporation plating mode, and the energy density of electron beam evaporation plating is 10W/cm 2～l00W/cm 2, the evaporation speed of organic material is 0.1～1nm/s, the evaporation speed of metal and metallic compound is 1～10nm/s.
Step S130, on charge generation layer surface successively evaporation, prepare the second hole transmission layer 52, the second luminescent layer 54, the second electron transfer layer 56, electron injecting layer 60 and negative electrode 70.
The second hole transmission layer 52 is formed at the surface of doped zinc oxide diamicton 403.The material of the second hole transmission layer 52 is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4; at least one in 4 '-benzidine (NPB), is preferably TAPC.The thickness of the second hole transmission layer 52 is 20nm～60nm, is preferably 30nm.Evaporation is 2 * 10 at vacuum pressure -3～5 * 10 -5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
The second luminescent layer 54 is formed at the surface of the second hole transmission layer 52.The material of the second luminescent layer 54 is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably BCzVBi.The thickness of luminescent layer 40 is 5nm～40nm, is preferably 20nm.Evaporation is 2 * 10 at vacuum pressure -3～5 * 10 -5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
The second electron transfer layer 56 is formed at the surface of the second luminescent layer 52.The material of the second electron transfer layer 56 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and at least one in 4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TAZ.The thickness of the second electron transfer layer 56 is 40nm～300nm, is preferably 210nm.Evaporation is 2 * 10 at vacuum pressure -3～5 * 10 -5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
Electron injecting layer 60 is formed at the second electron transfer layer 56 surfaces.The material of electron injecting layer 60 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 60 is 0.5nm～10nm, is preferably 1nm.Evaporation is 2 * 10 at vacuum pressure -3～5 * 10 -5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
Negative electrode 70 is formed at electron injecting layer 60 surfaces.The material of negative electrode 70 is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au), is preferably Al.The thickness of negative electrode 70 is 60nm～300nm, is preferably 150nm.Evaporation is 2 * 10 at vacuum pressure -3～5 * 10 -5under Pa, carry out, evaporation speed is 1nm/s～10nm/s.
Above-mentioned organic electroluminescence device preparation method, technique is simple, and the luminous efficiency of the organic electroluminescence device of preparation is higher.
Below in conjunction with specific embodiment, the preparation method of organic electroluminescence device provided by the invention is elaborated.
The preparation used of the embodiment of the present invention and 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 test electric property of U.S. Keithley company, CS-100A colorimeter test brightness and the colourity of Japanese Konica Minolta company.
Embodiment 1
Structure prepared by the present embodiment is ITO/V 2o 5/ TCTA/BCzVBi/TPBI/MoO 3/ TiO 2/ PrO 2: the organic electroluminescence device of ZnO/TAPC/BCzVBi/TAZ/CsF/Al.Wherein, "/" presentation layer stack structure, ": " represents doping or mixes, following examples are identical.
First ITO is carried out to photoetching treatment, be cut into needed size, use successively liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface; Evaporation hole injection layer, material is V 2o 5, thickness is 60nm; Evaporation the first hole transmission layer, material is TCTA, thickness is 30nm; Evaporation the first luminescent layer, material is BCzVBi, thickness is 30nm; Evaporation the first electron transfer layer, material is TPBI, thickness is 60nm; Evaporation charge generation layer, N-shaped layer is MoO 3, thickness is 30nm, and intermediate layer titanium dioxide particle diameter is 50nm, and thickness is 120nm, and intermediate layer adopts electron beam evaporation plating, and doped zinc oxide diamicton is PrO 2: ZnO, wherein, ZnO particle diameter is 150nm, PrO 2with ZnO mass ratio be 1:10, thickness is 150nm; Evaporation the second hole transmission layer, material is TAPC, thickness is 30nm; Evaporation the second luminescent layer, material is BCzVBi, thickness is 20nm; Evaporation the second electron transfer layer, material is TAZ, thickness is 210nm; Evaporation electron injecting layer, material is CsF, thickness is 1nm; Evaporation negative electrode, material is Al, thickness is 150nm.Finally obtain needed electroluminescent device.Evaporation is 8 * 10 at vacuum pressure -5under Pa, carry out, the evaporation speed of organic material is 0.2nm/s, and the evaporation speed of metal and metallic compound is 3nm/s, and the energy density of electron beam evaporation plating is 20W/cm 2.
Refer to Fig. 3, the structure that is depicted as preparation in embodiment 1 is ITO/V 2o 5/ TCTA/BCzVBi/TPBI/MoO 3/ TiO 2/ PrO 2: the organic electroluminescence device of ZnO/TAPC/BCzVBi/TAZ/CsF/Al (curve 1) is ito glass/V with structure prepared by comparative example 2o 5/ TCTA/BCzVBi/TAZ/CsF/Al(curve 2) current density and the relation of luminous efficiency.In the organic electroluminescence device that in organic electroluminescence device prepared by comparative example, each layer thickness is prepared with embodiment 1, each layer thickness is identical.
As seen from Figure 3, under different current densities, the luminous efficiency of embodiment 1 is large than comparative example all, the maximum lumen efficiency of the organic electroluminescence device of embodiment 1 preparation is 3.8lm/W, and the luminous efficiency of organic electroluminescence device prepared by comparative example is only 2.5lm/W, and the luminous efficiency of comparative example along with the increase of brightness fast-descending, this explanation, charge generation layer is by comprising N-shaped layer, intermediate layer and doped zinc oxide diamicton form, wherein, N-shaped layer material is the transmission rate that bipolarity metal oxide can improve electronics, for luminescence unit provides regeneration electronics, titanium dioxide is intermediate layer, it has larger surface area, network configuration, can carry out scattering to light, doped with the zinc oxide of lanthanide oxide and the HOMO energy level of hole mobile material, mate, can reduce injection barrier, improve the regeneration injectability in hole, zinc oxide work function also approaches the HOMO energy level of hole mobile material, be conducive to the injection in hole, improve light extraction efficiency, this charge generation layer can effectively improve the luminous efficiency of organic electroluminescence device.
The luminous efficiency of the organic electroluminescence device that below prepared by each embodiment is all similar with embodiment 1, and each organic electroluminescence device also has similar luminous efficiency, repeats no more below.
Embodiment 2
Structure prepared by the present embodiment is AZO/MoO 3/ TAPC/ADN/Bphen/WO 3/ TiO 2/ Pr 2o 3: ZnO/TCTA/ADN/TAZ/CsN 3the organic electroluminescence device of/Pt.
First AZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface; Evaporation is prepared hole injection layer, and material is MoO 3, thickness is 80nm; Evaporation is prepared the first hole transmission layer, and material is TAPC, and thickness is 60nm; Evaporation is prepared the first luminescent layer, and material is ADN, and thickness is 5nm; Evaporation is prepared the first electron transfer layer, and material is Bphen, and thickness is 200nm; Evaporation charge generation layer, N-shaped layer is WO 3, thickness is 60nm, and intermediate layer titanium dioxide particle diameter is 200nm, and thickness is 150nm, and intermediate layer adopts electron beam evaporation plating, and doped zinc oxide diamicton is Pr 2o 3: ZnO, wherein, ZnO particle diameter is: 200nm, Pr 2o 3with ZnO mass ratio be 1:5, thickness is 40nm; Evaporation is prepared the second hole transmission layer, and material is TCTA, and thickness is 20nm, the second luminescent layer, and material is ADN, thickness is 7nm; Evaporation is prepared the second electron transfer layer, and material is TAZ, and thickness is 40nm; Evaporation is prepared electron injecting layer, and material is CsN 3, thickness is 0.5nm; Evaporation is prepared negative electrode, and material is Pt, and thickness is 60nm, finally obtains needed electroluminescent device.Evaporation is 2 * 10 at vacuum pressure -3under Pa, carry out, the evaporation speed of organic material is 0.1nm/s, and the evaporation speed of metal and metallic compound is 10nm/s, and the energy density of electron beam evaporation plating is 50W/cm 2.
Embodiment 3
Structure prepared by the present embodiment is IZO/WO 3/ NPB/Alq 3/ TAZ/V 2o 5/ TiO 2/ Yb 2o 3: ZnO/TAPC/Alq 3the organic electroluminescence device of/Bphen/LiF/Ag.
First IZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface; Evaporation is prepared hole injection layer, and material is WO 3, thickness is 20nm; Evaporation is prepared the first hole transmission layer, and material is NPB, and thickness is 30nm; Evaporation is prepared the first luminescent layer, and material is Alq 3, thickness is 40nm; Evaporation is prepared the first electron transfer layer, and material is TAZ, and thickness is 200nm; Evaporation is prepared charge generation layer, and N-shaped layer is V 2o 5, thickness is 10nm, and intermediate layer titanium dioxide particle diameter is 20nm, and thickness is 20nm, and intermediate layer adopts electron beam evaporation plating, and doped zinc oxide diamicton is Yb 2o 3: ZnO, wherein, ZnO particle diameter is 100nm, Yb 2o 3with ZnO mass ratio be 1:20, thickness is 10nm; Evaporation is prepared the second hole transmission layer, and material is TAPC, and thickness is 60nm; Evaporation is prepared the second luminescent layer, and material is Alq 3, thickness is 30nm; Evaporation is prepared the second electron transfer layer, and material is Bphen, and thickness is 40nm; Evaporation is prepared electron injecting layer, and material is LiF, and thickness is 0.5nm; Evaporation is prepared negative electrode, and material is Ag, and thickness is 300nm, finally obtains needed electroluminescent device.Evaporation is 5 * 10 at vacuum pressure -5under Pa, carry out, the evaporation speed of organic material is 1nm/s, and the evaporation speed of metal and metallic compound is 1nm/s, and the energy density of electron beam evaporation plating is 100W/cm 2.
Embodiment 4
Structure prepared by the present embodiment is IZO/V 2o 5/ TAPC/DCJTB/TPBi/WO 3/ TiO 2/ Sm 2o 3: ZnO/NPB/DCJTB/Bphen/Cs 2cO 3the organic electroluminescence device of/Au.
First IZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface; Evaporation is prepared hole injection layer, and material is V 2o 5, thickness is 30nm; Evaporation is prepared the first hole transmission layer, and material is TAPC, and thickness is 50nm; Evaporation is prepared the first luminescent layer, and material is DCJTB, and thickness is 5nm; Evaporation is prepared the first electron transfer layer, and material is TPBi, and thickness is 40nm; Evaporation is prepared charge generation layer, and N-shaped layer is WO 3, thickness is 50nm, and intermediate layer titanium dioxide particle diameter is 100nm, and thickness is 100nm, and intermediate layer adopts electron beam evaporation plating, and doped zinc oxide diamicton is Sm 2o 3: ZnO, wherein, ZnO particle diameter is 100nm, Sm 2o 3with ZnO mass ratio be 1:10, thickness is 15nm; Evaporation is prepared the second hole transmission layer, and material is NPB, and thickness is 50nm, the second luminescent layer, and material is DCJTB, thickness is 5nm; Evaporation is prepared the second electron transfer layer, and material is Bphen, and thickness is 80nm; Evaporation is prepared electron injecting layer, and material is Cs 2cO 3, thickness is 2nm; Evaporation is prepared negative electrode, and material is Au, and thickness is 100nm, finally obtains needed electroluminescent device.Evaporation is 5 * 10 at vacuum pressure -4under Pa, carry out, the evaporation speed of organic material is 0.2nm/s, and the evaporation speed of metal and metallic compound is 5nm/s, and the energy density of electron beam evaporation plating is 10W/cm 2.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore 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 anode stacking gradually, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode, described charge generation layer comprises N-shaped layer, intermediate layer and doped zinc oxide diamicton, described N-shaped layer material is selected from molybdenum trioxide, in tungstic acid and vanadic oxide at least one, intermediate layer material is titanium dioxide, Zinc oxide doped layer material is the zinc oxide material doped with lanthanide oxide, described lanthanide oxide is selected from titanium dioxide praseodymium, praseodymium sesquioxide, at least one in three ytterbium oxides and samarium oxide, wherein, the mass ratio of described lanthanide oxide and described zinc oxide is 1:20～1:5.
2. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described N-shaped layer is 10nm～60nm, and described intermediate layer thickness is 20nm～150nm, and the thickness of described doped zinc oxide diamicton is 10nm～40nm.
3. organic electroluminescence device according to claim 1, is characterized in that, the particle diameter of described titanium dioxide is 100nm～200nm.
4. organic electroluminescence device according to claim 1, it is characterized in that, the material of described the first hole transmission layer and described the second hole transmission layer is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine and N; N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine.
5. organic electroluminescence device according to claim 1, is characterized in that, the material of described the first electron transfer layer and described the second electron transfer layer is selected from 4,7-diphenyl-1,10-phenanthroline, 1,2, at least one in 4-triazole derivative and N-aryl benzimidazole.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
At anode surface successively evaporation, prepare hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer;
At described the first electron transfer layer surface evaporation, prepare charge generation layer, described charge generation layer comprises N-shaped layer, intermediate layer and doped zinc oxide diamicton, described N-shaped layer material is selected from molybdenum trioxide, in tungstic acid and vanadic oxide at least one, intermediate layer material is titanium dioxide, Zinc oxide doped layer material is the zinc oxide material doped with lanthanide oxide, described lanthanide oxide is selected from titanium dioxide praseodymium, praseodymium sesquioxide, at least one in three ytterbium oxides and samarium oxide, wherein, the mass ratio of described lanthanide oxide and described zinc oxide is 1:20～1:5, evaporation is 2 * 10 at vacuum pressure -3～5 * 10 -5under Pa, carry out, intermediate layer adopts electron beam evaporation plating mode, and the energy density of electron beam evaporation plating is 10W/cm 2～l00W/cm 2, the evaporation speed of organic material is 0.1～1nm/s, the evaporation speed of metal and metallic compound is 1～10nm/s, and
On described charge generation layer surface successively evaporation, form the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode.
7. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that, the material of described the first luminescent layer and described the second luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, at least one in 4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl and oxine aluminium.
8. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that, the material of described the first hole transmission layer and described the second hole transmission layer is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine and N; N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine.
9. the preparation method of organic electroluminescence device according to claim 6, is characterized in that, the thickness of described N-shaped layer is 10nm～60nm, and described intermediate layer thickness is 20nm～150nm, and the thickness of described doped zinc oxide diamicton is 10nm～40nm.
10. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that, before described anode surface forms hole injection layer, first antianode carries out pre-treatment, pre-treatment comprises: anode is carried out to photoetching treatment, be cut into needed size, adopt liquid detergent, deionized water, acetone, ethanol, each Ultrasonic Cleaning of isopropyl acetone 15min, to remove the organic pollution of anode surface.
CN201310196289.4A 2013-05-24 2013-05-24 Organic light emitting device and manufacturing method thereof Pending CN104183729A (en)

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Publication number Priority date Publication date Assignee Title
CN1961613A (en) * 2004-03-26 2007-05-09 松下电工株式会社 Organic light emitting element
CN1989787A (en) * 2002-12-11 2007-06-27 Lg化学株式会社 Electroluminescent devices with low work function anode
CN102208551A (en) * 2010-03-31 2011-10-05 株式会社半导体能源研究所 Light-emitting element, light-emitting device, electronic device and lighting device
JP2012146643A (en) * 2010-12-24 2012-08-02 Semiconductor Energy Lab Co Ltd Lighting system

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1989787A (en) * 2002-12-11 2007-06-27 Lg化学株式会社 Electroluminescent devices with low work function anode
CN1961613A (en) * 2004-03-26 2007-05-09 松下电工株式会社 Organic light emitting element
CN102208551A (en) * 2010-03-31 2011-10-05 株式会社半导体能源研究所 Light-emitting element, light-emitting device, electronic device and lighting device
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Application publication date: 20141203