CN103972405A - Organic light-emitting device and method for manufacturing same - Google Patents

Organic light-emitting device and method for manufacturing same Download PDF

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Publication number
CN103972405A
CN103972405A CN201310038882.6A CN201310038882A CN103972405A CN 103972405 A CN103972405 A CN 103972405A CN 201310038882 A CN201310038882 A CN 201310038882A CN 103972405 A CN103972405 A CN 103972405A
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layer
metal oxide
evaporation
electroluminescence device
organic electroluminescence
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周明杰
王平
黄辉
张振华
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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 CN201310038882.6A priority Critical patent/CN103972405A/en
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting 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
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting 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]
    • H10K50/17—Carrier injection 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]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (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 transport layer, a first light-emitting layer, a first electron transport layer, a charge generating layer, a second hole transport layer, a second light-emitting layer, a second electron transport layer, an electron injection layer and a cathode. The anode, the hole injection layer, the first hole transport layer, the first light-emitting layer, the first electron transport layer, the charge generating layer, the second hole transport layer, the second light-emitting layer, the second electron transport layer, the electron injection layer and the cathode are sequentially stacked on one another, the charge generating layer comprises a bipolar metal oxide layer and a metal oxide layer, the bipolar metal oxide layer is stacked on the surface of the first electron transport layer, the metal oxide layer is formed on the surface of the bipolar metal oxide layer, the bipolar metal oxide layer is at least selectively made of one type of molybdenum trioxide, tungsten trioxide and vanadium pentoxide, and the metal oxides are at least one type of copper oxide, silver oxide and cuprous oxide selectively. The organic light-emitting device has the advantage of high light-emitting efficiency. The invention further provides a method for manufacturing 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
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.But 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 the bipolarity metal oxide layer that is laminated in described the first electron transfer layer surface, be formed at the metal oxide layer on bipolarity metal oxide layer surface, the material of described bipolarity metal oxide layer is selected from molybdenum trioxide, at least one in tungstic acid or vanadic oxide, described metal oxide materials is selected from cupric oxide, at least one in silver oxide or cuprous oxide.
In an embodiment, the thickness of described bipolarity metal oxide layer is 1nm ~ 10nm therein, and the thickness of described metal oxide layer is 1nm ~ 20nm.
Therein in an embodiment, 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, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl and oxine aluminium.
Therein in an embodiment, 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.
In an embodiment, the material of described the first electron transfer layer and described the second electron transfer layer is selected from 4,7-diphenyl-1 therein, 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:
Prepare hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer at anode surface successively evaporation;
Prepare bipolarity metal oxide layer at described the first electron transfer layer surface evaporation, described bipolarity metal oxide layer material is selected from least one in molybdenum trioxide, tungstic acid or vanadic oxide, and evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, evaporation speed is 1nm/s ~ 10nm/s;
On described bipolarity metal oxide layer surface, evaporation is prepared metal oxide layer, and the material of described metal oxide layer is selected from least one in cupric oxide, silver oxide or cuprous oxide, and evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, the evaporation speed of described metal oxide is 1nm/s ~ 10nm/s;
Form the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode on described metal oxide layer surface successively evaporation.
Therein in an embodiment, 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, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl and oxine aluminium.
Therein in an embodiment, 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.
In an embodiment, the thickness of described bipolarity metal oxide layer is 1nm ~ 10nm therein, and the thickness of described metal oxide layer is 1nm ~ 20nm.
Therein in an embodiment, 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, the 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 made up of bipolarity metal oxide layer and metal oxide layer, bipolarity metal oxide can produce electronics as the N-shaped structure sheaf of charge generation layer, be conducive to the injection of electronics and the transmission of electronics, in visible-range, absorb lower, and metal oxide is the oxide of copper family row, this oxide has stronger hole injectability, improved the injection efficiency in hole, charge generation layer can effectively improve the luminous efficiency of organic electroluminescence device.
Brief description of the drawings
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is the preparation method's of the organic electroluminescence device of an execution mode flow chart;
Fig. 3 is brightness and the luminous efficiency graph of a relation of the organic electroluminescence device prepared of embodiment 1.
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 an execution mode comprises the 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 that stack gradually.
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 MoO 3.The thickness of hole injection layer 20 is 20nm ~ 80nm, is preferably 40nm.
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 TAPC.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, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 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 30nm.
The first electron transfer layer 36 is formed at the surface of the first luminescent layer 34.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 ~ 200nm, is preferably 150nm.
Charge generation layer 40 is formed at the surface of the first electron transfer layer 36.Described charge generation layer 40 comprises the metal oxide layer 44 that is laminated in the bipolarity metal oxide layer 42 on the first electron transfer layer 36 surfaces and is formed at bipolarity metal oxide layer 42 surfaces.
The material of bipolarity metal oxide layer 42 is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3) or vanadic oxide (V 2o 5) at least one.The thickness of bipolarity metal oxide layer 42 is 1nm ~ 10nm.
Metal oxide layer 44 is formed at bipolarity metal oxide layer 42 surfaces.The material of metal oxide layer 44 is selected from least one in cupric oxide (CuO), silver oxide or cuprous oxide.The thickness of doped metallic oxide layer 44 is 1nm ~ 20nm.
The second hole transmission layer 52 is formed at the surface of metal oxide layer 44.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 NPB.The thickness of the second hole transmission layer 52 is 20nm ~ 60nm, is preferably 25nm.
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, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 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 30nm.
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 TPBI.The thickness of the second electron transfer layer 56 is 40nm ~ 200nm, is preferably 60nm.
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 LiF.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 Ag.The thickness of negative electrode 70 is 60nm ~ 300nm, is preferably 150nm.
Above-mentioned organic electroluminescence device 100, charge generation layer 40 is made up of bipolarity metal oxide layer 42 and metal oxide layer 44, bipolarity metal oxide layer 42 can produce electronics as the N-shaped structure sheaf of charge generation layer, be conducive to the injection of electronics and the transmission of electronics, in visible-range, absorb lower, and metal oxide layer 44 is oxides of copper family row, this oxide has stronger hole injectability, and charge generation layer 40 can effectively improve the luminous efficiency of organic electroluminescence device.
Be appreciated that other functional layers also can be set in this organic electroluminescence device 100 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, the first hole transmission layer 32, the 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 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, the each Ultrasonic Cleaning 15min of isopropyl acetone, 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 MoO 3.The thickness of hole injection layer 20 is 20nm ~ 80nm, is preferably 40nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, evaporation speed is 1nm/s ~ 10nm/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 TAPC.The thickness of the first hole transmission layer 32 is 20nm ~ 60nm, is preferably 30nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under 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, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 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 30nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under 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 34.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 ~ 200nm, is preferably 150nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
Step S120, prepare bipolarity metal oxide layer 42 at the surperficial evaporation of the first electron transfer layer 36.
At least one in material molybdenum trioxide, tungstic acid or the vanadic oxide of bipolarity metal oxide layer 42.The thickness of bipolarity metal oxide layer 42 is 1nm ~ 10nm.
Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, evaporation speed is 1nm/s ~ 10nm/s.
Step S130, prepare metal oxide layer 44 at the surperficial evaporation of bipolarity metal oxide layer 42.
Metal oxide layer 44 is formed at bipolarity metal oxide layer 42 surfaces.The material of metal oxide layer 44 is selected from least one in cupric oxide, silver oxide or cuprous oxide.The thickness of metal oxide layer 44 is 1nm ~ 20nm.
Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, the evaporation speed of metal oxide is 1nm/s ~ 10nm/s.
Step S140, 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 on metal oxide layer 44 surfaces successively evaporation.
The second hole transmission layer 52 is formed at the surface of high-work-function metal layer 46.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 NPB.The thickness of the second hole transmission layer 52 is 20nm ~ 60nm, is preferably 25nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under 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, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl (BCzVBi) and 8-hydroxyquinoline aluminum (Alq3), is preferably BCzVBi.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 30nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under 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 TPBI.The thickness of the second electron transfer layer 56 is 40nm ~ 200nm, is preferably 60nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under 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 LiF.The thickness of electron injecting layer 60 is 0.5nm～10nm, is preferably 1nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under 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 Ag.The thickness of negative electrode 70 is 60nm ~ 300nm, is preferably 150nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under 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 Keithley company of the U.S., CS-100A colorimeter test brightness and the colourity of Japanese Konica Minolta company.
Embodiment 1
Structure prepared by the present embodiment is: ito glass/MoO 3/ TAPC/BCzVBi/TPBI/MoO 3the organic electroluminescence device of/CuO/NPB/BCzVBi/TPBI/LiF/Ag.
First ITO is carried out to photoetching treatment, be cut into needed size, use successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface; Evaporation hole injection layer, material is MoO 3, thickness is 40nm; Evaporation the first hole transmission layer, material is TAPC, 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; Prepare charge generation layer: formed by bipolarity metal oxide layer and metal oxide layer.Evaporation bipolarity metal oxide layer, material is MoO 3, thickness is 8nm; Evaporation metal oxide skin(coating), material is CuO, thickness is 5nm; Evaporation the second hole transmission layer, material is NPB, thickness is 25nm; Evaporation the second luminescent layer, material is BCzVBi, thickness is 30nm; Evaporation the second electron transfer layer, material is TPBI, thickness is 60nm; Evaporation electron injecting layer, material is LiF, thickness is 1nm; Evaporation negative electrode, material is Ag, thickness is 150nm.Finally obtain needed electroluminescent device.Evaporation is 8 × 10 at vacuum pressure -4under Pa, carry out, organic material evaporation speed is 0.3nm/s, and the evaporation speed of metallic compound is 4nm/s, and the evaporation speed of metal is 5nm/s.
Refer to Fig. 3, the structure that is depicted as preparation in embodiment 1 is ito glass/MoO 3/ TAPC/BCzVBi/TPBI/MoO 3the organic electroluminescence device (curve 1) of/CuO/NPB/BCzVBi/TPBI/LiF/Ag is ito glass/MoO with structure prepared by comparative example 3the brightness of the organic electroluminescence device (curve 2) of/TAPC/BCzVBi/TPBi/LiF/Ag 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 brightness, all large than comparative example of the luminous efficiency of embodiment 1, the maximum lumen efficiency of organic electroluminescence device prepared by embodiment 1 is 6.5lm/W, and the luminous efficiency of organic electroluminescence device prepared by comparative example is only 5.0lm/W, and the luminous efficiency of comparative example along with the increase of brightness fast-descending, this explanation, charge generation layer is made up of bipolarity metal oxide layer and metal oxide layer, bipolarity metal oxide can improve injectability and the electric transmission efficiency of electronics, and three bronze medal family oxides have effectively been avoided the generation of electron trap, 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/V 2o 5/ TAPC/ADN/Bphen/WO 3/ Cu 2o/NPB/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 V 2o 5, 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 is prepared charge generation layer: be made up of bipolarity metal oxide layer and metal oxide layer; The material of bipolarity metal oxide layer is WO 3, thickness is 10nm; The material of metal oxide layer is Cu 2o, thickness is 20nm; ; Then evaporation the second hole transmission layer, material is NPB, thickness is 20nm; Evaporation is prepared the second luminescent layer, and material is ADN, and 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 -4under Pa, carry out, organic material evaporation speed is 1nm/s, and the evaporation speed of metallic compound is 10nm/s, and the evaporation speed of metal is 10nm/s.
Embodiment 3
Structure prepared by the present embodiment is IZO/MoO 3/ TCTA/Alq 3/ TAZ/V 2o 5/ Ag 2o/TCTA/Alq 3the organic electroluminescence device of/Bphen/CsF/Al.
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 MoO 3, thickness is 20nm; Evaporation is prepared the first hole transmission layer, and material is TCTA, 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: be made up of layer by layer bipolarity metal oxide layer and metal oxide; The material of bipolarity metal oxide layer is V 2o 5, thickness is 1nm; The material of metal oxide layer is Ag 2o, thickness is 1nm; Evaporation is prepared the second hole transmission layer, and material is TCTA, 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 CsF, and thickness is 10nm; Evaporation is prepared negative electrode, and material is Al, and thickness is 300nm, finally obtains needed electroluminescent device.Evaporation is 5 × 10 at vacuum pressure -3under Pa, carry out, organic material evaporation speed is 0.1nm/s, and the evaporation speed of metallic compound is 1nm/s, and the evaporation speed of metal is 1nm/s.
Embodiment 4
Structure prepared by the present embodiment is IZO/MoO 3/ TCTA/DCJTB/TAZ/MoO 3/ Cu 2o/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 MoO 3, thickness is 30nm; Evaporation is prepared the first hole transmission layer, and material is TCTA, 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 TAZ, and thickness is 40nm; Evaporation is prepared charge generation layer: be made up of bipolarity metal oxide layer and metal oxide layer; The material of bipolarity metal oxide layer is MoO 3, thickness is 5nm; The material of metal oxide layer is Cu 2o, thickness is 5nm; Evaporation is prepared the second hole transmission layer, and material is NPB, and thickness is 50nm; Evaporation is prepared the second luminescent layer, and material is DCJTB, and thickness is 5nm; Evaporation is prepared the second electron transfer layer, and material is Bphen, and thickness is 100nm; 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 180nm, finally obtains needed electroluminescent device.Evaporation is 5 × 10 at vacuum pressure -4under Pa, carry out, organic material evaporation speed is 0.5nm/s, and the evaporation speed of metal compound layer is 2nm/s, and the evaporation speed of metal is 3nm/s.
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 the bipolarity metal oxide layer that is laminated in described the first electron transfer layer surface, be formed at the metal oxide layer on bipolarity metal oxide layer surface, the material of described bipolarity metal oxide layer is selected from molybdenum trioxide, at least one in tungstic acid or vanadic oxide, described metal oxide materials is selected from cupric oxide, at least one in silver oxide or cuprous oxide.
2. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described bipolarity metal oxide layer is 1nm ~ 10nm, and the thickness of described metal oxide layer is 1nm ~ 20nm.
3. organic electroluminescence device according to claim 1, 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, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl and oxine aluminium.
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:
Prepare hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer at anode surface successively evaporation;
Prepare bipolarity metal oxide layer at described the first electron transfer layer surface evaporation, described bipolarity metal oxide layer material is selected from least one in molybdenum trioxide, tungstic acid or vanadic oxide, and evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, evaporation speed is 1nm/s ~ 10nm/s;
On described bipolarity metal oxide layer surface, evaporation is prepared metal oxide layer, and the material of described metal oxide layer is selected from least one in cupric oxide, silver oxide or cuprous oxide, and evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, the evaporation speed of described metal oxide is 1nm/s ~ 10nm/s;
Form the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode on described metal oxide 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 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, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 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 bipolarity metal oxide layer is 1nm ~ 10nm, and the thickness of described metal oxide layer is 1nm ~ 20nm.
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, the each Ultrasonic Cleaning 15min of isopropyl acetone, to remove the organic pollution of anode surface.
CN201310038882.6A 2013-01-31 2013-01-31 Organic light-emitting device and method for manufacturing same Pending CN103972405A (en)

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CN101447555A (en) * 2008-12-29 2009-06-03 中国科学院长春应用化学研究所 Laminated organic electro-luminescent device of an organic semiconductor-based hetero-junction electric-charge generating layer taken as a connecting layer and preparation method thereof
JP2010040444A (en) * 2008-08-07 2010-02-18 Panasonic Electric Works Co Ltd Organic electroluminescent element
CN102544385A (en) * 2012-01-19 2012-07-04 友达光电股份有限公司 Serial connection type organic light-emitting component

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1957486A (en) * 2004-05-28 2007-05-02 伊斯曼柯达公司 Tandem OLED having stable intermediate connectors
JP2008294356A (en) * 2007-05-28 2008-12-04 Panasonic Electric Works Co Ltd Organic electrominescence element
JP2010040444A (en) * 2008-08-07 2010-02-18 Panasonic Electric Works Co Ltd Organic electroluminescent element
CN101447555A (en) * 2008-12-29 2009-06-03 中国科学院长春应用化学研究所 Laminated organic electro-luminescent device of an organic semiconductor-based hetero-junction electric-charge generating layer taken as a connecting layer and preparation method thereof
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Application publication date: 20140806