CN104253226A - An organic light-emitting device and a preparation method thereof - Google Patents

An organic light-emitting device and a preparation method thereof Download PDF

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Publication number
CN104253226A
CN104253226A CN201310259867.4A CN201310259867A CN104253226A CN 104253226 A CN104253226 A CN 104253226A CN 201310259867 A CN201310259867 A CN 201310259867A CN 104253226 A CN104253226 A CN 104253226A
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layer
evaporation
thickness
electroluminescence device
organic electroluminescence
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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
    • 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
    • H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
    • H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
    • H10K50/131—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit with spacer layers between the electroluminescent layers
    • 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
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass

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

Abstract

The invention describes an organic light-emitting device, which comprises: a anode, a hole injection layer, a first hole transporting layer, a first light-emitting layer, a first electron transfer layer, a charge generation layer, a second hole transporting layer, a second light-emitting layer, a second electron transfer layer, an electron injection layer and a cathode, which are configured to be sequentially stacked. The charge generation layer comprises an n-type layer, an intermediate layer and a p-type layer, wherein the n-type layer material is a metallic oxide, the intermediate layer material is - metal and a molysite doped in the metal, and the p-type layer is a bipolar metallic oxide. The organic light-emitting device described above has a higher luminous efficiency. The invention also provides a preparation method of the organic light-emitting device.

Description

Organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Under the principle of luminosity of organic electroluminescence device is based on the effect of extra electric field, electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Meet at luminescent layer in electronics and hole, compound, formation exciton, and exciton moves under electric field action, and by energy transferring to luminescent material, and excitation electron is from ground state transition to excitation state, and excited energy, by Radiation-induced deactivation, produces photon, release luminous energy.But the luminous efficiency of current organic electroluminescence device is lower.
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 stacked gradually, hole injection layer, first hole transmission layer, first luminescent layer, first electron transfer layer, charge generation layer, second hole transmission layer, second luminescent layer, second electron transfer layer, electron injecting layer and negative electrode, described charge generation layer comprises n-layer, intermediate layer and p-type layer, described n-layer material is metal oxide, the molysite that intermediate layer material is metal and is entrained in described metal, p-type layer is bipolarity metal oxide, described metal oxide is selected from titanium dioxide, zinc oxide, at least one in hafnium oxide or zirconia, described metal is selected from silver, aluminium, at least one in platinum or gold, described molysite is selected from iron chloride, at least one in ferric bromide or iron sulfide, described bipolarity metal oxide is selected from molybdenum trioxide, at least one in tungstic acid or vanadic oxide, wherein, the mass ratio of described molysite and described metal is 1:10 ~ 1:2.
In a preferred embodiment, the thickness of described n-layer is 10nm ~ 100nm, and described intermediate layer thickness is 5nm ~ 20nm, and the thickness of described p-type layer is 5nm ~ 30nm.
In a preferred embodiment, the material of described first luminescent layer and described second luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, 9, at least one in 10-bis--β-naphthylene anthracene, 4,4'-two (9-ethyl-3-carbazole vinyl)-1,1'-biphenyl and oxine aluminium.
In a preferred embodiment, the material of described first hole transmission layer and described second hole transmission layer is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-base) triphenylamine and N, N '-(1-naphthyl)-N, at least one in N '-diphenyl-4,4 '-benzidine.
In a preferred embodiment, the material of described first electron transfer layer and described second electron transfer layer is selected from least one in 4,7-diphenyl-1,10-phenanthroline, 1,2,4-triazole derivative and N-aryl benzimidazole.
A preparation method for organic electroluminescence device, comprises the following steps:
Hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer is prepared at anode surface successively evaporation;
Charge generation layer is prepared on described first electron transfer layer surface, described charge generation layer comprises n-layer, intermediate layer and p-type layer, intermediate layer and p-type layer adopt evaporation mode to prepare, n-layer adopts the preparation of electron beam mode evaporation, described n-layer material is metal oxide, the molysite that intermediate layer material is metal and is entrained in described metal, p-type layer is bipolarity metal oxide, wherein, described metal oxide is selected from titanium dioxide, zinc oxide, at least one in hafnium oxide or zirconia, described metal is selected from silver, aluminium, at least one in platinum or gold, described molysite is selected from iron chloride, at least one in ferric bromide or iron sulfide, described bipolarity metal oxide is selected from molybdenum trioxide, at least one in tungstic acid or vanadic oxide, wherein, the mass ratio of described molysite and described metal is 1:10 ~ 1:2, evaporation is 2 × 10 at vacuum pressure -3~ 5 × 10 -5carry out under Pa, the evaporation rate of organic material is 0.1 ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1 ~ 10nm/s, and the energy density of electron beam evaporation plating is 10-l00W/cm 2, and
In a preferred embodiment, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode is formed on described charge generation layer surface successively evaporation.
In a preferred embodiment, the material of described first luminescent layer and described second luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, 9, at least one in 10-bis--β-naphthylene anthracene, 4,4'-two (9-ethyl-3-carbazole vinyl)-1,1'-biphenyl and oxine aluminium.
In a preferred embodiment, the material of described first hole transmission layer and described second hole transmission layer is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-base) triphenylamine and N, N '-(1-naphthyl)-N, at least one in N '-diphenyl-4,4 '-benzidine.
In a preferred embodiment, the thickness of described n-layer is 10nm ~ 100nm, and described intermediate layer thickness is 5nm ~ 20nm, and the thickness of described p-type layer is 5nm ~ 30nm.
Before described anode surface forms hole injection layer, first antianode carries out pre-treatment, pre-treatment comprises: anode is carried out photoetching treatment, be cut into required size, adopt liquid detergent, deionized water, acetone, ethanol, each Ultrasonic Cleaning 15min of isopropyl acetone, to remove the organic pollution of anode surface.
Above-mentioned organic electroluminescence device and preparation method thereof, charge generation layer is by comprising n-layer, intermediate layer and p-type layer are formed, wherein, n-layer material is the injectability that metal oxide can improve electronics, the molysite that intermediate layer is metal and is entrained in described metal, the scattering of light can be conducive to by this doping and improve the conductivity in intermediate layer, metal has a large amount of free electrons and forms a large amount of hole-electron pairs, p-type layer material is bipolarity metal oxide, the conductivity that electric charge produces can be increased, improve the injectability in hole, be conducive to the injection in hole, be conducive to the transmission of charge carrier, improve exciton recombination probability, this charge generation layer effectively can 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 the flow chart of the preparation method of the organic electroluminescence device of an execution mode;
Fig. 3 is brightness and the luminous efficiency graph of a relation of organic electroluminescence device prepared by embodiment 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, organic electroluminescence device and preparation method thereof is illustrated further.
Refer to Fig. 1, the organic electroluminescence device 100 of one execution mode comprises the anode 10, hole injection layer 20, first hole transmission layer 32, first luminescent layer 34, first electron transfer layer 36, charge generation layer 40, second hole transmission layer 52, second luminescent layer 54, second electron transfer layer 56, electron injecting layer 60 and the negative electrode 70 that stack gradually, charge generation layer 40 comprises n-layer 401, intermediate layer 402 and p-type layer 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 surface.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 40nm.
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 '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine (NPB), is preferably NPB.The thickness of the first hole transmission layer 32 is 20nm ~ 60nm, is preferably 40nm.
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 pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-and 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably Alq 3.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 20nm.
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 least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably Bphen.The thickness of the first electron transfer layer 36 is 40nm ~ 300nm, is preferably 200nm.
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-layer 401, intermediate layer 402 and p-type layer 403, N-shaped 401 material is metal oxide, the molysite that intermediate layer 402 material is metal and is entrained in described metal, p-type layer 403 is bipolarity metal oxide, and described metal oxide is selected from titanium dioxide (TiO 2), zinc oxide (ZnO), hafnium oxide (HfO 2) or zirconia (ZrO 2) middle at least one, described metal is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) or gold (Au), and described molysite is selected from iron chloride (FeCl 3), ferric bromide (FeBr 3) or iron sulfide (Fe 2s 3) middle at least one, described bipolarity metal oxide is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3) or vanadic oxide (V 2o 5) middle at least one, wherein, the mass ratio of described molysite and described metal is 1:10 ~ 1:2.The thickness of n-layer 401 is 10nm ~ 100nm, and intermediate layer 402 thickness is 5nm ~ 20nm, and the thickness of p-type layer 403 is 5nm ~ 30nm.
Second hole transmission layer 52 is formed at the surface of charge generation layer 40.The material of the second hole transmission layer 52 is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine (NPB), is preferably NPB.The thickness of the second hole transmission layer 52 is 20nm ~ 60nm, is preferably 40nm.
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 pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-and 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably Alq 3.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 25nm.
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 least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TAZ.The thickness of the second electron transfer layer 56 is 40nm ~ 300nm, is preferably 60nm.
Electron injecting layer 60 is formed at the second electron transfer layer 56 surface.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 LiF.The thickness of electron injecting layer 60 is 0.5nm ~ 10nm, is preferably 0.7nm.
Negative electrode 70 is formed at electron injecting layer 60 surface.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-layer 401, intermediate layer 402 and p-type layer 403 are formed, wherein, n-layer material is the injectability that metal oxide can improve electronics, the molysite that intermediate layer is metal and is entrained in described metal, the scattering of light can be conducive to by this doping and improve the conductivity in intermediate layer, metal has a large amount of free electrons and forms a large amount of hole-electron pairs, p-type layer material is bipolarity metal oxide, the conductivity that electric charge produces can be increased, improve the injectability in hole, be conducive to the injection in hole, be conducive to the transmission of charge carrier, improve exciton recombination probability, this charge generation layer effectively can improve the luminous efficiency of organic electroluminescence device.
Be appreciated that in this organic electroluminescence device 100 and also can other functional layers 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, prepare hole injection layer 20, first hole transmission layer 32, first luminescent layer 34 and the first electron transfer layer 36 at anode surface successively evaporation.
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 surface forms hole injection layer 20, first antianode 10 carries out pre-treatment, pre-treatment comprises: anode 10 is carried out photoetching treatment, be cut into required size, adopt liquid detergent, deionized water, acetone, ethanol, each Ultrasonic Cleaning 15min of isopropyl acetone, to remove the organic pollution on anode 10 surface.
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 40nm.Evaporation is 2 × 10 at vacuum pressure -3pa ~ 5 × 10 -5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
First hole transmission layer 32 is formed at the surface of hole injection layer 20.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 '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine (NPB), is preferably NPB.The thickness of the first hole transmission layer 32 is 20nm ~ 60nm, is preferably 40nm.Evaporation is 2 × 10 at vacuum pressure -3pa ~ 5 × 10 -5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
First luminescent layer 34 is formed at the surface of the first hole transmission layer 32.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 pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-and 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably Alq 3.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 20nm.Evaporation is 2 × 10 at vacuum pressure -3pa ~ 5 × 10 -5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
First electron transfer layer 36 is formed at the surface of the first luminescent layer 32.First electron transfer layer 36 is prepared by evaporation.The material of the first electron transfer layer 36 is selected from least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably Bphen.The thickness of the first electron transfer layer 36 is 40nm ~ 300nm, is preferably 200nm.Evaporation is 2 × 10 at vacuum pressure -3pa ~ 5 × 10 -5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Step S120, prepare charge generation layer 40 on the first electron transfer layer 36 surface.
Charge generation layer 40 is formed at the surface of the first electron transfer layer 36, charge generation layer 40 comprises n-layer 401, intermediate layer 402 and p-type layer 403, intermediate layer 402 and p-type layer 403 adopt evaporation mode to prepare, n-layer 401 adopts electron beam mode evaporation to prepare, and N-shaped 401 material is metal oxide, the molysite that intermediate layer 402 material is metal and is entrained in described metal, p-type layer 403 is bipolarity metal oxide, and described metal oxide is selected from titanium dioxide (TiO 2), zinc oxide (ZnO), hafnium oxide (HfO 2) or zirconia (ZrO 2) middle at least one, described metal is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) or gold (Au), and described molysite is selected from iron chloride (FeCl 3), ferric bromide (FeBr 3) or iron sulfide (Fe 2s 3) middle at least one, described bipolarity metal oxide is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3) or vanadic oxide (V 2o 5) middle at least one, wherein, the mass ratio of described molysite and described metal is 1:10 ~ 1:2.The thickness of n-layer 401 is 10nm ~ 100nm, and intermediate layer 402 thickness is 5nm ~ 20nm, and the thickness of p-type layer 403 is 5nm ~ 30nm.Evaporation is 2 × 10 at vacuum pressure -3~ 5 × 10 -5carry out under Pa, the evaporation rate of organic material is 0.1 ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1 ~ 10nm/s, and the energy density of electron beam evaporation plating is 10-l00W/cm 2.
Step S130, prepare the second hole transmission layer 52, second luminescent layer 54, second electron transfer layer 56, electron injecting layer 60 and negative electrode 70 on charge generation layer surface successively evaporation.
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 '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine (NPB), is preferably NPB.The thickness of the second hole transmission layer 52 is 20nm ~ 60nm, is preferably 40nm.Evaporation is 2 × 10 at vacuum pressure -3~ 5 × 10 -5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
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 pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-and 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably Alq 3.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 25nm.Evaporation is 2 × 10 at vacuum pressure -3~ 5 × 10 -5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
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 least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TAZ.The thickness of the second electron transfer layer 56 is 40nm ~ 300nm, is preferably 60nm.Evaporation is 2 × 10 at vacuum pressure -3~ 5 × 10 -5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Electron injecting layer 60 is formed at the second electron transfer layer 56 surface.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 LiF.The thickness of electron injecting layer 60 is 0.5nm ~ 10nm, is preferably 1nm.Evaporation is 2 × 10 at vacuum pressure -3~ 5 × 10 -5carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Negative electrode 70 is formed at electron injecting layer 60 surface.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 -5carry out under Pa, evaporation rate 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 to organic electroluminescence device provided by the invention is described in detail.
The embodiment of the present invention and the preparation used by comparative example and tester are: high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), the USB4000 fiber spectrometer testing electroluminescent spectrum of U.S. marine optics Ocean Optics, the Keithley2400 of Keithley company of the U.S. tests electric property, the CS-100A colorimeter test brightness of Japanese Konica Minolta company and colourity.
Embodiment 1
Structure prepared by the present embodiment is ITO/V 2o 5/ NPB/Alq 3/ Bphen/ZnO/FeCl 3: Ag/MoO 3/ NPB/Alq 3the organic electroluminescence device of/TAZ/LiF/Al.Wherein, "/" presentation layer stack structure, ": " represents doping or mixing, and following examples are identical.
First ITO is carried out photoetching treatment, be cut into required size, use liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface; Evaporation hole injection layer, material is V 2o 5, thickness is 40nm; Evaporation first hole transmission layer, material is NPB, and thickness is 40nm; Evaporation first luminescent layer, material is Alq 3, thickness is 20nm; Evaporation first electron transfer layer, material is Bphen, and thickness is 200nm; Prepare charge generation layer, it is ZnO that electron beam evaporation plating prepares n-layer, and thickness is 20nm, and it is FeCl that evaporation prepares intermediate layer material 3: Ag, FeCl 3be 3:7 with the mass ratio of Ag, thickness is 10nm, and it is MoO that evaporation prepares p-type layer material 3, thickness is 20nm; Evaporation second hole transmission layer, material is NPB, and thickness is 40nm; Evaporation second luminescent layer, material is Alq 3, thickness is 25nm; Evaporation second electron transfer layer, material is TAZ, and thickness is 60nm; Evaporation electron injecting layer, material is LiF, and thickness is 0.7nm; Evaporation negative electrode, material is Al, and thickness is 150nm.Finally obtain required electroluminescent device.Evaporation is 8 × 10 at vacuum pressure -5carry out under Pa, the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 3nm/s, and the energy density of electron beam evaporation plating is 50W/cm 2.
Refer to Fig. 3, the structure being depicted as preparation in embodiment 1 is ITO/V 2o 5/ NPB/Alq 3/ Bphen/ZnO/FeCl 3: Ag/MoO 3/ NPB/Alq 3structure prepared by organic electroluminescence device (curve 1) and the comparative example of/TAZ/LiF/Al is ito glass/V 2o 5/ NPB/Alq 3/ TAZ/LiF/Al(curve 2) brightness and the relation of luminous efficiency.In organic electroluminescence device prepared by comparative example, each layer thickness is identical with each layer thickness in organic electroluminescence device prepared by embodiment 1.
Can see from figure, under different brightness, the current efficiency of embodiment 1 is all larger than comparative example, the maximum lumen efficiency of organic electroluminescence device prepared by embodiment 1 is 4.0cd/A, and the luminous efficiency of organic electroluminescence device prepared by comparative example is 2.6cd/A, and the luminous efficiency of comparative example declines fast along with the increase of brightness, this explanation, charge generation layer 40 is by comprising n-layer 401, intermediate layer 402 and p-type layer 403 are formed, wherein, n-layer material is the injectability that metal oxide can improve electronics, the molysite that intermediate layer is metal and is entrained in described metal, the scattering of light can be conducive to by this doping and improve the conductivity in intermediate layer, metal has a large amount of free electrons and forms a large amount of hole-electron pairs, p-type layer material is bipolarity metal oxide, the conductivity that electric charge produces can be increased, improve the injectability in hole, be conducive to the injection in hole, be conducive to the transmission of charge carrier, improve exciton recombination probability, this charge generation layer effectively can improve the luminous efficiency of organic electroluminescence device.
The luminous efficiency of organic electroluminescence device prepared of each embodiment is all similar with embodiment 1 below, and each organic electroluminescence device also has similar current efficiency, repeats no more below.
Embodiment 2
Structure prepared by the present embodiment is AZO/WO 3/ TCTA/ADN/TAZ/TiO 2/ FeBr 3: Al/WO 3/ NPB/ADN/TPBi/CsN 3the organic electroluminescence device of/Pt.
First AZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface; Evaporation prepares hole injection layer, and material is WO 3, thickness is 80nm; Evaporation prepares the first hole transmission layer, and material is TCTA, and thickness is 60nm; Evaporation prepares the first luminescent layer, and material is ADN, and thickness is 5nm; Evaporation prepares the first electron transfer layer, and material is TAZ, and thickness is 200nm; Prepare charge generation layer, it is TiO that electron beam evaporation plating prepares n-layer 2, thickness is 100nm, and it is FeBr that evaporation prepares intermediate layer material 3: Al, FeBr 3be 1:10 with the mass ratio of Al, thickness is 10nm, and it is WO that evaporation prepares p-type layer 3, thickness is 30nm; Evaporation prepares the second hole transmission layer, and material is NPB, and thickness is 20nm, the second luminescent layer, and material is ADN, and thickness is 7nm; Evaporation prepares the second electron transfer layer, and material is TPBi, and thickness is 40nm; Evaporation prepares electron injecting layer, and material is CsN 3, thickness is 10nm; Evaporation prepares negative electrode, and material is Pt, and thickness is 60nm, finally obtains required electroluminescent device.Evaporation is 2 × 10 at vacuum pressure -3carry out under Pa, the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of metal and metallic compound is 10nm/s, and the energy density of electron beam evaporation plating is 10W/cm 2.
Embodiment 3
Structure prepared by the present embodiment is IZO/V 2o 5/ TCTA/BCzVBi/TAZ/HfO 2/ Fe 2s 3: Pt/V 2o 5the organic electroluminescence device of/TCTA/BCzVBi/Bphen/CsF/Al.
First IZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface; Evaporation prepares hole injection layer, and material is V 2o 5, thickness is 20nm; Evaporation prepares the first hole transmission layer, and material is TCTA, and thickness is 30nm; Evaporation prepares the first luminescent layer, and material is BCzVBi, and thickness is 40nm; Evaporation prepares the first electron transfer layer, and material is TAZ, and thickness is 60nm; Prepare charge generation layer, it is HfO that electron beam evaporation plating prepares n-layer 2, thickness is 50nm, and it is Fe that evaporation prepares intermediate layer material 2s 3: Pt, Fe 2s 3be 1:2 with the mass ratio of Pt, thickness is 5nm, and p-type layer is V 2o 5, thickness is 5nm; Evaporation prepares the second hole transmission layer, and material is TCTA, and thickness is 200nm; Evaporation prepares the second luminescent layer, and material is BCzVBi, and thickness is 30nm; Evaporation prepares the second electron transfer layer, and material is Bphen, and thickness is 40nm; Evaporation prepares electron injecting layer, and material is CsF, and thickness is 0.5nm; Evaporation prepares negative electrode, and material is Al, and thickness is 300nm, finally obtains required electroluminescent device.Evaporation is 5 × 10 at vacuum pressure -5carry out under Pa, the evaporation rate of organic material is 1nm/s, and the evaporation rate 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/MoO 3/ TAPC/DCJTB/Bphen/ZrO 2/ FeCl 3: Au/MoO 3/ TCTA/DCJTB/TPBi/Cs 2cO 3the organic electroluminescence device of/Au.
First IZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface; Evaporation prepares hole injection layer, and material is MoO 3, thickness is 30nm; Evaporation prepares the first hole transmission layer, and material is TAPC, and thickness is 50nm; Evaporation prepares the first luminescent layer, and material is DCJTB, and thickness is 5nm; Evaporation prepares the first electron transfer layer, and material is Bphen, and thickness is 40nm; Prepare charge generation layer, it is ZrO that evaporation prepares n-layer 2, thickness is 50nm, and it is FeCl that electron beam evaporation plating prepares intermediate layer material 3: Au, FeCl 3be 1:5 with the mass ratio of Au, thickness is 15nm, and it is MoO that evaporation prepares p-type layer 3, thickness is 20nm; Evaporation prepares the second hole transmission layer, and material is TCTA, and thickness is 50nm, the second luminescent layer, and material is DCJTB, and thickness is 5nm; Evaporation prepares the second electron transfer layer, and material is TPBi, and thickness is 80nm; Evaporation prepares electron injecting layer, and material is Cs 2cO 3, thickness is 2nm; Evaporation prepares negative electrode, and material is Au, and thickness is 100nm, finally obtains required electroluminescent device.Evaporation is 5 × 10 at vacuum pressure -4carry out under Pa, the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 5nm/s, and the energy density of electron beam evaporation plating is 20W/cm 2.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.

Claims (10)

1. an organic electroluminescence device, it is characterized in that, comprise the anode stacked gradually, hole injection layer, first hole transmission layer, first luminescent layer, first electron transfer layer, charge generation layer, second hole transmission layer, second luminescent layer, second electron transfer layer, electron injecting layer and negative electrode, described charge generation layer comprises n-layer, intermediate layer and p-type layer, described n-layer material is metal oxide, the molysite that intermediate layer material is metal and is entrained in described metal, p-type layer is bipolarity metal oxide, described metal oxide is selected from titanium dioxide, zinc oxide, at least one in hafnium oxide or zirconia, described metal is selected from silver, aluminium, at least one in platinum or gold, described molysite is selected from iron chloride, at least one in ferric bromide or iron sulfide, described bipolarity metal oxide is selected from molybdenum trioxide, at least one in tungstic acid or vanadic oxide, wherein, the mass ratio of described molysite and described metal is 1:10 ~ 1:2.
2. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described n-layer is 10nm ~ 100nm, and described intermediate layer thickness is 5nm ~ 20nm, and the thickness of described p-type layer is 5nm ~ 30nm.
3. organic electroluminescence device according to claim 1, it is characterized in that, the material of described first luminescent layer and described second luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, at least one in two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl of 4'-and oxine aluminium.
4. organic electroluminescence device according to claim 1, it is characterized in that, the material of described first hole transmission layer and described second hole transmission layer is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-base) triphenylamine and N, at least one in N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine.
5. organic electroluminescence device according to claim 1, is characterized in that, the material of described first electron transfer layer and described second electron transfer layer is selected from 4,7-diphenyl-1, at least one in 10-phenanthroline, 1,2,4-triazole derivative and N-aryl benzimidazole.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
Hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer is prepared at anode surface successively evaporation;
Charge generation layer is prepared on described first electron transfer layer surface, described charge generation layer comprises n-layer, intermediate layer and p-type layer, intermediate layer and p-type layer adopt evaporation mode to prepare, n-layer adopts the preparation of electron beam mode evaporation, described n-layer material is metal oxide, the molysite that intermediate layer material is metal and is entrained in described metal, p-type layer is bipolarity metal oxide, wherein, described metal oxide is selected from titanium dioxide, zinc oxide, at least one in hafnium oxide or zirconia, described metal is selected from silver, aluminium, at least one in platinum or gold, described molysite is selected from iron chloride, at least one in ferric bromide or iron sulfide, described bipolarity metal oxide is selected from molybdenum trioxide, at least one in tungstic acid or vanadic oxide, wherein, the mass ratio of described molysite and described metal is 1:10 ~ 1:2, evaporation is 2 × 10 at vacuum pressure -3~ 5 × 10 -5carry out under Pa, the evaporation rate of organic material is 0.1 ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1 ~ 10nm/s, and the energy density of electron beam evaporation plating is 10-l00W/cm 2, and
The second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode is formed on described charge generation layer surface successively evaporation.
7. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that, the material of described first luminescent layer and described second luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, at least one in two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl of 4'-and oxine aluminium.
8. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that, the material of described first hole transmission layer and described second hole transmission layer is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-base) triphenylamine and N, at least one in N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine.
9. the preparation method of organic electroluminescence device according to claim 6, is characterized in that, the thickness of described n-layer is 10nm ~ 100nm, and described intermediate layer thickness is 5nm ~ 20nm, and the thickness of described p-type layer is 5nm ~ 30nm.
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 photoetching treatment, be cut into required size, adopt liquid detergent, deionized water, acetone, ethanol, each Ultrasonic Cleaning 15min of isopropyl acetone, to remove the organic pollution of anode surface.
CN201310259867.4A 2013-06-26 2013-06-26 An organic light-emitting device and a preparation method thereof Pending CN104253226A (en)

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Application publication date: 20141231