CN103972407A - Organic light-emitting device and production method thereof - Google Patents

Organic light-emitting device and production method thereof Download PDF

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Publication number
CN103972407A
CN103972407A CN201310038894.9A CN201310038894A CN103972407A CN 103972407 A CN103972407 A CN 103972407A CN 201310038894 A CN201310038894 A CN 201310038894A CN 103972407 A CN103972407 A CN 103972407A
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layer
evaporation
electroluminescence device
organic electroluminescence
hole
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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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Priority to CN201310038894.9A priority Critical patent/CN103972407A/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
    • 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

Abstract

The invention provides an organic light-emitting device. The organic light-emitting device comprises an anode, a hole injection layer, a first hole transport layer, a first light-emitting layer, a first electron transport layer, a charge generation layer, a second hole transport layer, a second light-emitting layer, a second electron transport layer, an electron injection layer and a cathode which are laminated sequentially. The charge generation layer comprises a metal oxide layer laminated on the surface of the first electron transport layer and a ternary doped layer formed on the surface of the metal oxide layer, the metal oxide layer is made of materials selected from at least one of molybdenum trioxide, tungsten trioxide and vanadium pentoxide, the ternary doped layer is made of materials including phthalocyanine compounds, metal and hole transport materials, a mass ratio between the metal and the phthalocyanine compounds in the ternary doped layer is 1:50-1:5, and a mass ration between the hole transport materials and the phthalocyanine compounds in the ternary doped layer is 1:1000-1:10. The organic light-emitting device is high in light emitting efficiency. The invention further provides a production 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
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, comprises 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 ternary doping layer that is laminated in the metal oxide layer on described the first electron transfer layer surface and is formed at described metal oxide layer surface, the material of described metal oxide layer is selected from molybdenum trioxide, at least one in tungstic acid and vanadic oxide, the material of described ternary doping layer comprises phthalocyanine compound and is entrained in metal and the hole mobile material in described phthalocyanine compound, described phthalocyanine compound is selected from CuPc, at least one in Phthalocyanine Zinc and magnesium phthalocyanine, described metal is selected from silver, aluminium, at least one in platinum and gold, described hole mobile material is selected from 2,3,5,6-tetrafluoro-7, and 7,8,8 ,-four cyano-benzoquinone bismethane, 4,4,4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine and dinaphthyl-N, N '-diphenyl-4, at least one in 4 '-benzidine, described in described ternary doping layer, the mass ratio of metal and described phthalocyanine compound is 1:50 ~ 1:5, described in described ternary doping layer, the mass ratio of hole mobile material and described phthalocyanine compound is 1:1000 ~ 1:10.
In an embodiment, the thickness of described metal oxide layer is 5nm ~ 20nm therein, and the thickness of described ternary doping layer is 5nm ~ 40nm.
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 metal oxide layer at described the first electron transfer layer surface evaporation, the material of described metal oxide layer is selected from least one in molybdenum trioxide, tungstic acid and 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 metal oxide layer surface, evaporation is prepared ternary doping layer, the material of described ternary doping layer comprises phthalocyanine compound and is entrained in metal and the hole mobile material in described phthalocyanine compound, described phthalocyanine compound is selected from CuPc, at least one in Phthalocyanine Zinc and magnesium phthalocyanine, described metal is selected from silver, aluminium, at least one in platinum and gold, described hole mobile material is selected from 2, 3, 5, 6-tetrafluoro-7, 7, 8, 8,-four cyano-benzoquinone bismethane, 4, 4, 4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine and dinaphthyl-N, N '-diphenyl-4, at least one in 4 '-benzidine, described in described ternary doping layer, the mass ratio of metal and described phthalocyanine compound is 1:50 ~ 1:5, described in described ternary doping layer, the mass ratio of hole mobile material and described phthalocyanine compound is 1: 1000 ~ 1: 10, described metal, described hole mobile material and described phthalocyanine compound evaporate respectively in three evaporation boats, and evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, the evaporation speed of described metal is 1nm/s ~ 10nm/s, and the evaporation speed of described hole mobile material is 0.1nm/s ~ 1nm/s, and the evaporation speed of described phthalocyanine compound is 1nm/s ~ 10nm/s, and
Form the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode on ternary doping 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 metal oxide layer is 5nm ~ 20nm therein, and the thickness of described ternary doping layer is 5nm ~ 40nm.
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 metal oxide layer and ternary doping layer, metal oxide is bipolarity metal oxide, electronics and hole can be provided simultaneously, therefore, can be used as the electronic shell of charge generation layer, and the absorption of bipolarity metal oxide in visible-range lower (below 20%), can ensure the transmitance of light, and ternary doping layer can make HOMO energy level potential barrier reduce after adding metal, thereby reduce hole injection barrier, improve hole injection efficiency, add hole mobile material can form p doping, the less raising transmission rate that can be larger of hole mobile material doping, make hole transport speed improve two orders of magnitude, also saved material cost simultaneously, and the easy crystallization of phthalocyanine compound, after crystallization, light is carried out to scattering, the final luminous efficiency that improves organic electroluminescence device, organic electroluminescence device has two luminescence units simultaneously, thereby has current density and luminous efficiency at double.
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 current density and the current 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 30nm.
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 45nm.
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 Alq 3.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 Bphen.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 ternary doping layer 44 that is laminated in the metal oxide layer 42 on the first electron transfer layer 36 surfaces and is formed at metal oxide layer 42 surfaces.
The material of metal oxide layer 42 is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) at least one.The thickness of metal oxide layer 42 is 5nm ~ 20nm.
The material of ternary doping layer 44 comprises phthalocyanine compound and is entrained in metal and the hole mobile material in phthalocyanine compound.Phthalocyanine compound is selected from least one in CuPc (CuPc), Phthalocyanine Zinc (ZnPc) and magnesium phthalocyanine (MgPc).Metal is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au).Hole mobile material is selected from 2,3,5,6-tetrafluoro-7,7,8,8 ,-four cyano-benzoquinone bismethane (F4-TCNQ), 4,4,4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine (1T-NATA) and dinaphthyl-N, N '-diphenyl-4, at least one in 4 '-benzidine (2T-NATA).In ternary doping layer, the mass ratio of metal and phthalocyanine compound is 1:50 ~ 1:5; The mass ratio of hole mobile material and phthalocyanine compound is 1:1000 ~ 1: 10, and the thickness of ternary doping layer 44 is 5nm ~ 40nm.
The second hole transmission layer 52 is formed at the surface of ternary doping 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 TAPC.The thickness of the second hole transmission layer 52 is 20nm ~ 60nm, is preferably 35nm.
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 Alq 3.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 ~ 200nm, is preferably 50nm.
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 metal oxide layer 42 and ternary doping layer 44, metal oxide is bipolarity metal oxide, electronics and hole can be provided simultaneously, therefore, can be used as the electronic shell of charge generation layer 40, and the absorption of bipolarity metal oxide in visible-range lower (below 20%), can ensure the transmitance of light, and ternary doping layer 44 can make HOMO energy level potential barrier reduce after adding metal, thereby reduce hole injection barrier, improve hole injection efficiency, add hole transport guest materials can form p doping, the less raising transmission rate that can be larger of hole mobile material doping, make hole transport speed improve two orders of magnitude, also saved material cost simultaneously, and the easy crystallization of phthalocyanine compound, after crystallization, light is carried out to scattering, the final luminous efficiency that improves organic electroluminescence device, organic electroluminescence device 100 has two luminescence units simultaneously, thereby has current density and luminous efficiency at double.
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 execution mode, 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 30nm.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 45nm.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 Alq 3.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 20nm.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 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 Bphen.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 metal oxide layer 42 at the surperficial evaporation of the first electron transfer layer 36.
The material of metal oxide layer 42 is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) at least one.The thickness of metal oxide layer 42 is 5nm ~ 20nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, evaporation speed is 1nm/s ~ 10nm/s.
Step S130, prepare ternary doping layer 44 at the surperficial evaporation of metal oxide layer 42.
The material of ternary doping layer 44 comprises phthalocyanine compound and is entrained in metal and the hole mobile material in phthalocyanine compound.Phthalocyanine compound is selected from least one in CuPc (CuPc), Phthalocyanine Zinc (ZnPc) and magnesium phthalocyanine (MgPc).Metal is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au).Hole mobile material is selected from 2,3,5,6-tetrafluoro-7,7,8,8 ,-four cyano-benzoquinone bismethane (F4-TCNQ), 4,4,4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine (1T-NATA) and dinaphthyl-N, N '-diphenyl-4, at least one in 4 '-benzidine (2T-NATA).In ternary doping layer, the mass ratio of metal and phthalocyanine compound is 1:50 ~ 1:5; The mass ratio of hole mobile material and phthalocyanine compound is 1:1000 ~ 1: 10, and the thickness of ternary doping layer 44 is 5nm ~ 40nm.Metal, hole mobile material and phthalocyanine compound evaporate respectively in three evaporation boats, and evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, the evaporation speed of metal is 1nm/s～10nm/s, and the evaporation speed of hole mobile material is 0.1nm/s～1nm/s, and the evaporation speed of phthalocyanine compound 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 ternary doping layer 44 surface successively evaporation.
The second hole transmission layer 52 is formed at the surface of ternary doping 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 TAPC.The thickness of the second hole transmission layer 52 is 20nm ~ 60nm, is preferably 35nm.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'-, 1'-biphenyl (BCzVBi) 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 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 TAZ.The thickness of the second electron transfer layer 56 is 40nm ~ 200nm, is preferably 50nm.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/Alq 3/ Bphen/CuPc:Au:F4-TCNQ/TAPC/Alq 3the organic electroluminescence device of/TAZ/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 30nm; Evaporation the first hole transmission layer, material is TAPC, thickness is 45nm; Evaporation the first luminescent layer, material is Alq 3, thickness is 20nm; Evaporation the first electron transfer layer, material is Bphen, thickness is 150nm; Evaporation metal oxide skin(coating), material is MoO 3, thickness is 10nm; Evaporation ternary doping layer, material comprises CuPc and is entrained in Au and the F4-TCNQ in CuPc, and the mass ratio of Au and CuPc is 1:10, and the mass ratio of F4-TCNQ and CuPc is 1.5:100, and thickness is 20nm; Evaporation the second hole transmission layer, material is TAPC, thickness is 35nm; Evaporation the second luminescent layer, material is Alq 3, thickness is 20nm; Evaporation the second electron transfer layer, material is TAZ, thickness is 50nm; 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 0.2nm/s, and the evaporation speed of metallic compound is 5nm/s, and the evaporation speed of metal is 3nm/s.
Refer to Fig. 3, the structure that is depicted as preparation in embodiment 1 is ito glass/MoO 3/ TAPC/Alq 3/ Bphen/CuPc:Au:F4-TCNQ/TAPC/Alq 3the organic electroluminescence device (curve 1) of/TAZ/LiF/Ag is ito glass/MoO with structure prepared by comparative example 3/ TAPC/Alq 3the current density of the organic electroluminescence device (curve 2) of/TAZ/LiF/Ag and the relation of current efficiency.In the organic electroluminescence device that in organic electroluminescence device prepared by comparative example, each layer thickness is prepared with comparative example 1, each layer thickness is identical.
As seen from Figure 3, under different current efficiency, all large than comparative example of the current efficiency of embodiment 1, the maximum current efficiency of organic electroluminescence device prepared by embodiment 1 is 4.5cd/A, and the current efficiency of organic electroluminescence device prepared by comparative example is only 2.7cd/A, this explanation, charge generation layer is by being made up of metal oxide layer and ternary doping layer, metal oxide is bipolarity metal oxide, electronics and hole can be provided simultaneously, ternary doping layer can make HOMO energy level potential barrier reduce after adding metal, thereby reduce hole injection barrier, improve hole injection efficiency, add hole transport guest materials can form p doping, the less raising transmission rate that can be larger of hole mobile material doping, make hole transport speed improve two orders of magnitude, also saved material cost simultaneously, and the easy crystallization of phthalocyanine compound, after crystallization, light is carried out to scattering, this charge generation layer can effectively improve the luminous efficiency of organic electroluminescence device.
The current 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 current efficiency, repeats no more below.
Embodiment 2
Structure prepared by the present embodiment is AZO/V 2o 5/ NPB/ADN/TPBi/V 2o 5/ CuPc:Al:1T-NATA/TAPC/ADN/TPBi/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 NPB, 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 TPBi, and thickness is 200nm; The standby charge generation layer of evaporation preparation: be made up of metal oxide layer and ternary doping layer, the material of metal oxide layer is V 2o 5, thickness is 5nm, and the material of ternary doping layer comprises MgPc and is entrained in Ag and the 1T-NATA in MgPc, and the mass ratio of Ag and MgPc is 1:50, and the mass ratio of 1T-NATA and MgPc is 1:10, the thickness of ternary doping layer is 40nm; Evaporation is prepared the second hole transmission layer, and material is TCTA, and 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 TPBi, 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 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 10nm/s, and the evaporation speed of metal is 10nm/s.
Embodiment 3
Structure prepared by the present embodiment is IZO/WO 3/ TCTA/BCzVBi/Bphen/WO 3the organic electroluminescence device of/ZnPc:Pt:2T-NATA/TCTA/BCzVBi/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 WO 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 BCzVBi, and thickness is 40nm; 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 metal oxide layer and ternary doping layer, the material of metal oxide layer is WO 3, thickness is 20nm, and the material of ternary doping layer comprises ZnPc and is entrained in Pt and the 2T-NATA in ZnPc, and the mass ratio of Pt and ZnPc is 1:5, and the mass ratio of 2T-NATA and ZnPc is 1:1000, the thickness of ternary doping layer is 5nm; 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 BCzVBi, and 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 2 × 10 at vacuum pressure -4under Pa, carry out, organic material evaporation speed is 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/ CuPc:Al:1T-NATA/NPB/DCJTB/TPBi/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 metal oxide layer and ternary doping layer, the material of metal oxide layer is MoO 3, thickness is 8nm, and the material of ternary doping layer comprises CuPc and is entrained in Al and the 1T-NATA in CuPc, and the mass ratio of the quality of Al and CuPc is 7:100, and the mass ratio of 1T-NATA and CuPc is 1:40, the thickness of ternary doping layer is 30nm; 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 TPBi, 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 0.6nm/s, and the evaporation speed of metallic compound is 3nm/s, and the evaporation speed of metal is 2nm/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, is characterized in that, comprises 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 ternary doping layer that is laminated in the metal oxide layer on described the first electron transfer layer surface and is formed at described metal oxide layer surface, the material of described metal oxide layer is selected from molybdenum trioxide, at least one in tungstic acid and vanadic oxide, the material of described ternary doping layer comprises phthalocyanine compound and is entrained in metal and the hole mobile material in described phthalocyanine compound, described phthalocyanine compound is selected from CuPc, at least one in Phthalocyanine Zinc and magnesium phthalocyanine, described metal is selected from silver, aluminium, at least one in platinum and gold, described hole mobile material is selected from 2,3,5,6-tetrafluoro-7, and 7,8,8 ,-four cyano-benzoquinone bismethane, 4,4,4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine and dinaphthyl-N, N '-diphenyl-4, at least one in 4 '-benzidine, described in described ternary doping layer, the mass ratio of metal and described phthalocyanine compound is 1:50 ~ 1:5, described in described ternary doping layer, the mass ratio of hole mobile material and described phthalocyanine compound is 1: 1000 ~ 1:10.
2. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described metal oxide layer is 5nm ~ 20nm, and the thickness of described ternary doping layer is 5nm ~ 40nm.
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 metal oxide layer at described the first electron transfer layer surface evaporation, the material of described metal oxide layer is selected from least one in molybdenum trioxide, tungstic acid and 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 metal oxide layer surface, evaporation is prepared ternary doping layer, the material of described ternary doping layer comprises phthalocyanine compound and is entrained in metal and the hole mobile material in described phthalocyanine compound, described phthalocyanine compound is selected from CuPc, at least one in Phthalocyanine Zinc and magnesium phthalocyanine, described metal is selected from silver, aluminium, at least one in platinum and gold, described hole mobile material is selected from 2, 3, 5, 6-tetrafluoro-7, 7, 8, 8,-four cyano-benzoquinone bismethane, 4, 4, 4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine and dinaphthyl-N, N '-diphenyl-4, at least one in 4 '-benzidine, described in described ternary doping layer, the mass ratio of metal and described phthalocyanine compound is 1:50 ~ 1:5, described in described ternary doping layer, the mass ratio of hole mobile material and described phthalocyanine compound is 1: 1000 ~ 1: 10, described metal, described hole mobile material and described phthalocyanine compound evaporate respectively in three evaporation boats, and evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4under Pa, carry out, the evaporation speed of described metal is 1nm/s ~ 10nm/s, and the evaporation speed of described hole mobile material is 0.1nm/s ~ 1nm/s, and the evaporation speed of described phthalocyanine compound is 1nm/s ~ 10nm/s, and
Form the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode on ternary doping 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 metal oxide layer is 5nm ~ 20nm, and the thickness of described ternary doping layer is 5nm ~ 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, the each Ultrasonic Cleaning 15min of isopropyl acetone, to remove the organic pollution of anode surface.
CN201310038894.9A 2013-01-31 2013-01-31 Organic light-emitting device and production method thereof Pending CN103972407A (en)

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Application publication date: 20140806