CN104638164A - Organic light-emitting device and preparation method thereof - Google Patents

Organic light-emitting device and preparation method thereof Download PDF

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Publication number
CN104638164A
CN104638164A CN201310561267.3A CN201310561267A CN104638164A CN 104638164 A CN104638164 A CN 104638164A CN 201310561267 A CN201310561267 A CN 201310561267A CN 104638164 A CN104638164 A CN 104638164A
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layer
doped layer
doped
bis
phenyl
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周明杰
钟铁涛
王平
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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    • 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
    • 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
    • H10K85/00—Organic materials used in the body or electrodes of 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
    • H10K2102/301—Details of OLEDs
    • H10K2102/302—Details of OLEDs of OLED structures

Abstract

The invention discloses an organic light-emitting device. The organic light-emitting device comprises a conductive anode, a hole injection layer, a hole transmission layer, a green light emitting layer, an electron transmission layer, an electron injection layer and a cathode layer in sequentially laminated arrangement. The green light emitting layer comprises a first doped layer, a second doped layer, a third doped layer, a fourth doped layer and a fifth doped layer, and the first doped layer, the second doped layer, the third doped layer, the fourth doped layer and the fifth doped layer are overlapped sequentially and all made of mixed materials formed by doping guest materials into host materials, and mass fractions of the guest materials in the first doped layer, the second doped layer, the third doped layer, the fourth doped layer and the fifth doped layer are 3a%, 2a%, a%, 2a% and 3a% respectively, wherein a is larger than or equal to 0.5 and smaller than or equal to 4. The invention further provides a preparation method of the organic light-emitting device.

Description

A kind of organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to field of organic electroluminescence, particularly a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (Organic light-emitting Devices, be called for short OLEDs) be a kind of multilayer luminescent device using luminous organic material, comprise the anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the cathode layer that stack gradually.
Under the principle of luminosity of OLED 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.
Material and the formation of luminescent layer are the important factors affecting luminous efficiency, therefore.The luminous efficiency how improving luminescent layer becomes research emphasis in the future.
Summary of the invention
For solving the problems of the technologies described above, the invention provides a kind of organic electroluminescence device, the green light emitting layer of this organic electroluminescence device comprises the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer that stack gradually, the material of described first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer is the composite material that guest materials doped body material is formed, and present invention also offers the preparation method of this organic electroluminescence device.
First aspect, the invention provides a kind of organic electroluminescence device, comprise the conductive anode stacked gradually, hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer, electron injecting layer and cathode layer, described green light emitting layer comprises the first doped layer stacked gradually, second doped layer, 3rd doped layer, 4th doped layer and the 5th doped layer, described first doped layer, second doped layer, 3rd doped layer, the material of the 4th doped layer and the 5th doped layer is guest materials and is doped to the composite material formed in material of main part, described guest materials accounts for described first doped layer, second doped layer, 3rd doped layer, the mass fraction of the 4th doped layer and the 5th doped layer is respectively 3a%, 2a%, a%, 2a% and 3a%, wherein, 0.5≤a≤4, described guest materials is that three (2-phenylpyridines) close iridium) (Ir (ppy) 3), acetopyruvic acid two (2-phenylpyridine) iridium) (Ir (ppy) 2(acac)) or three [2-(p-methylphenyl) pyridines] close iridium (Ir (mppy) 3), described material of main part is 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), 9,9'-(1,3-phenyl) two-9H-carbazole (mCP), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD), 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC) or two (1-naphthyl) anthracene (ADN) of 9,10-.
Preferably, described first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer are all identical with the thickness of the 5th doped layer, and the thickness of described green light emitting layer is 10 ~ 30nm.
Preferably, the material of described hole injection layer is the composite material that the material doped hole-injecting material of p-type is formed, and described p-type material is molybdenum trioxide (MoO 3), tungstic acid (WO 3), vanadic oxide (V 2o 5) or rhenium trioxide (ReO 3), described hole-injecting material is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) or 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), the quality of described p-type material accounts for 25% ~ 35% of described hole injection layer quality.The thickness of described hole injection layer is 10 ~ 15nm.
Preferably, the material of described hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) or 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), the thickness of described hole transmission layer is 30 ~ 50nm.
Preferably, the material of described electron transfer layer is 4,7-diphenyl-1,10-ferrosin (Bphen), 2,9-dimethyl-4,7-diphenyl-1,10-ferrosin (BCP), 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq 3), 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ) or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI), the thickness of described electron transfer layer is 10 ~ 60nm.
Preferably, the material of described electron injecting layer is the composite material that the material doped electron injection material of N-shaped is formed, and described N-shaped material is cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), cesium azide (CsN 3), lithium carbonate (Li 2cO 3), lithium fluoride (LiF) or lithia (Li 2o), described electron injection material is 4,7-diphenyl-1,10-phenanthroline (Bphen), 2,9-dimethyl-4,7-diphenyl-1,10-ferrosin (BCP), 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq 3), 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ) or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI), the quality of described N-shaped material accounts for 25% ~ 35% of the quality of described electron injecting layer.The thickness of described electron injecting layer is 20 ~ 40nm.
Preferably, described conductive anode is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), and more preferably, described conductive anode is ITO.The thickness of described ITO is 100nm.
Preferably, described cathode layer material is silver (Ag), aluminium (Al) or gold (Au), and thickness is 50 ~ 200nm.
On the other hand, the invention provides a kind of preparation method of organic electroluminescence device, comprise following operating procedure:
The conductive anode of required size is provided, dry after cleaning; Then on conductive anode, adopt the method for vacuum evaporation to prepare hole injection layer and hole transmission layer successively;
The method of vacuum evaporation is adopted to prepare the first doped layer successively on the hole transport layer, second doped layer, 3rd doped layer, 4th doped layer and the 5th doping, obtain described green light emitting layer, described first doped layer, second doped layer, 3rd doped layer, the material of the 4th doped layer and the 5th doped layer is guest materials and is doped to the composite material formed in material of main part, and described guest materials accounts for described first doped layer, second doped layer, 3rd doped layer, the mass fraction of the 4th doped layer and the 5th doped layer is respectively 3a%, 2a%, a%, 2a% and 3a%, wherein, 0.5≤a≤4, described guest materials is that three (2-phenylpyridines) close iridium), acetopyruvic acid two (2-phenylpyridine) iridium) or three [2-(p-methylphenyl) pyridines] close iridium, described material of main part is 4,4', 4''-tri-(carbazole-9-base) triphenylamine, 9,9'-(1,3-phenyl) two-9H-carbazole, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine, 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane or two (1-naphthyl) anthracene of 9,10-, evaporation vacuum degree is 1 × 10 -5pa ~ 1 × 10 -3pa, evaporation rate is
Prepare electron transfer layer, electron injecting layer and cathode layer successively at described green light emitting layer, obtain described organic electroluminescence device.
When preparing described green light emitting layer, described guest materials is doped to the composite material that formed in the material of main part raw material as evaporation green light emitting layer, when evaporation, direct evaporation raw material, obtains described green light emitting layer on the hole transport layer.
Preferably, described first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer are all identical with the thickness of the 5th doped layer, and the thickness of described green light emitting layer is 10 ~ 30nm.
Preferably, vacuum degree when preparing described hole injection layer is 1 × 10 -5pa ~ 1 × 10 -3pa, evaporation rate is
Preferably, vacuum degree when preparing described hole transmission layer is 1 × 10 -5pa ~ 1 × 10 -3pa, evaporation rate is
Preferably, vacuum degree when preparing described electron transfer layer is 1 × 10 -5pa ~ 1 × 10 -3pa, evaporation rate is
Preferably, vacuum degree when preparing described electron injecting layer is 8 × 10 -5pa ~ 3 × 10 -4pa, evaporation rate is
Preferably, vacuum degree when preparing described cathode layer is 1 × 10 -5pa ~ 1 × 10 -3pa, evaporation rate is
Preferably, the material of described hole injection layer is the composite material that the material doped hole-injecting material of p-type is formed, and described p-type material is molybdenum trioxide (MoO 3), tungstic acid (WO 3), vanadic oxide (V 2o 5) or rhenium trioxide (ReO 3), described hole-injecting material is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines (NPB), 4, 4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), 4, 4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4, 4'-benzidine (TPD) or 1, 1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), the quality of described p-type material accounts for 25% ~ 35% of described hole injection layer quality, the thickness of described hole injection layer is 10 ~ 15nm.
Preferably, the material of described hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) or 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), the thickness of described hole transmission layer is 30 ~ 50nm.
Preferably, the material of described electron transfer layer is 4,7-diphenyl-1,10-ferrosin (Bphen), 2,9-dimethyl-4,7-diphenyl-1,10-ferrosin (BCP), 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq 3), 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ) or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI), the thickness of described electron transfer layer is 10 ~ 60nm.
Preferably, the material of described electron injecting layer is the composite material that the material doped electron injection material of N-shaped is formed, and described N-shaped material is cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), cesium azide (CsN 3), lithium carbonate (Li 2cO 3), lithium fluoride (LiF) or lithia (Li 2o), described electron injection material is 4,7-diphenyl-1,10-phenanthroline (Bphen), 2,9-dimethyl-4,7-diphenyl-1,10-ferrosin (BCP), 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq 3), 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ) or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI), the quality of described N-shaped material accounts for 25% ~ 35% of described electron injecting layer quality.The thickness of described electron injecting layer is 20 ~ 40nm.
Preferably, described conductive anode is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), and more preferably, described conductive anode is ITO.The thickness of described ITO is 100nm.
Preferably, described cathode layer material is silver (Ag), aluminium (Al) or gold (Au), and thickness is 50 ~ 200nm.
Green light emitting layer of the present invention comprises the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer that stack gradually, adopt the luminescent material that " Host-guest " adulterates, energy can be transferred to the guest materials of high fluorescence efficiency from material of main part by guest materials, be divided into by green light emitting layer five layers can increase light-emitting area, increase light-emitting zone, the multiple interfaces realizing luminescent layer are luminous, improve luminous efficiency.The mass fraction that described guest materials accounts for described first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer is respectively 3a%, 2a%, a%, 2a% and 3a%, wherein, 0.5≤a≤4, the concentration gradient change of guest materials can be formed like this, this graded can produce uneven internal field at green light emitting layer, make energy trasfer easier, improve the luminous efficiency of device.
Accompanying drawing explanation
In order to be illustrated more clearly in technical scheme of the present invention, be briefly described to the accompanying drawing used required in execution mode below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the structural representation of organic electroluminescence device of the present invention.
Embodiment
Below in conjunction with the accompanying drawing in embodiment of the present invention, the technical scheme in embodiment of the present invention is clearly and completely described.
Embodiment 1
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) conductive anode 1 selects indium tin oxide glass (ITO), uses liquid detergent successively, deionized water, acetone and each ultrasonic 5 minutes of ethanol, removes the organic pollution of glass surface, cleans up rear air-dry; Also need to carry out surface activation process to the ito glass after cleaning, to increase the oxygen content on ITO surface, improve the work function on ITO surface; The thickness of conductive anode 1 is 100nm; Then on conductive anode 1, hole injection layer 2 and hole transmission layer 3 are prepared in vacuum evaporation successively, and the material of hole injection layer 2 is MoO 3be doped to N, the composite material formed in N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), MoO 3quality account for 30% of hole injection layer 2 quality, the thickness of hole injection layer 2 is 12.5nm, and during evaporation, vacuum degree is 1 × 10 -5pa, evaporation rate is the material of hole transmission layer 3 is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), and thickness is 40nm, and during evaporation, vacuum degree is 1 × 10 -5pa, evaporation rate is
(2) on hole transmission layer 3, prepare the first doped layer 41, second doped layer 42, the 3rd doped layer 43, the 4th doped layer 44 and the 5th doped layer 45 successively, the material obtaining green light emitting layer 4, first doped layer 41, second doped layer 42, the 3rd doped layer 43, the 4th doped layer 44 and the 5th doped layer 45 that thickness is 20nm is guest materials Ir (ppy) 3be doped to the composite material formed in material of main part TCTA, first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer are all identical with the 5th doped layer thickness, Ir (ppy) in the first doped layer 41, second doped layer 42, the 3rd doped layer 43, the 4th doped layer 44 and the 5th doped layer 45 3mass fraction be respectively 12%, 8%, 4%, 8% and 12%, vacuum degree is 1 × 10 -5pa, evaporation rate is
(3) on green light emitting layer 4, adopt the method for vacuum evaporation to prepare electron transfer layer 5, electron injecting layer 6 and cathode layer 7 successively, obtain organic electroluminescence device;
The material of electron transfer layer 5 is Bphen, and thickness is 35nm, and during evaporation, vacuum degree is 1 × 10 -5pa, evaporation rate is
The material of electron injecting layer 6 is the material doped composite material formed in electron injection material of N-shaped, and N-shaped material is Cs 2cO 3, electron injection material is Bphen, and the quality of N-shaped material accounts for 30% of Bphen quality, and during evaporation, vacuum degree is 5 × 10 -5pa, evaporation rate is the thickness of electron injecting layer is 30nm;
The material of cathode layer 7 is Ag, and thickness is 125nm, and vacuum degree during evaporation is 1 × 10 -5pa, evaporation rate is
Fig. 1 is the structural representation of organic electroluminescence device prepared by the present embodiment, organic electroluminescence device prepared by the present embodiment, comprises the conductive anode 1, hole injection layer 2, hole transmission layer 3, green light emitting layer 4, electron transfer layer 5, electron injecting layer 6 and the cathode layer 7 that stack gradually.Green light emitting layer 4 comprises the first doped layer 41, second doped layer 42, the 3rd doped layer 43, the 4th doped layer 44 and the 5th doped layer 45 that stack gradually.
Embodiment 2
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) conductive anode selects indium tin oxide glass (ITO), uses liquid detergent successively, deionized water, acetone and each ultrasonic 5 minutes of ethanol, removes the organic pollution of glass surface, cleans up rear air-dry; Also need to carry out surface activation process to the ito glass after cleaning, to increase the oxygen content on ITO surface, improve the work function on ITO surface; The thickness of conductive anode is 100nm; Then on conductive anode, hole injection layer and hole transmission layer are prepared in vacuum evaporation successively, and the material of hole injection layer is WO 3be doped to 4,4', the composite material formed in 4''-tri-(carbazole-9-base) triphenylamine (TCTA), WO 3quality account for 25% of hole injection layer quality, the thickness of hole injection layer is 10nm, and during evaporation, vacuum degree is 5 × 10 -5pa, evaporation rate is the material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), and thickness is 30nm, and during evaporation, vacuum degree is 5 × 10 -5pa; Evaporation rate is
(2) on hole transmission layer, the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer is then prepared successively, obtain the green light emitting layer that thickness is 10nm, the material of the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer is guest materials Ir (ppy) 2(acac) composite material formed in material of main part mCP is doped to, Ir (ppy) in the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer 2(acac) mass fraction is respectively 9%, 6%, 3%, 6% and 9%, and the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer are all identical with the 5th doped layer thickness, and during evaporation, vacuum degree is 5 × 10 -5pa, evaporation rate is
(3) on green light emitting layer, adopt the method for vacuum evaporation to prepare electron transfer layer, electron injecting layer and cathode layer successively, obtain organic electroluminescence device;
The material of electron transfer layer is BCP, and thickness is 10nm, and during evaporation, vacuum degree is 5 × 10 -5pa, evaporation rate is
The material of electron injecting layer is the material doped composite material formed in electron injection material of N-shaped, and N-shaped material is CsF, and electron injection material is BCP, and the quality of N-shaped material accounts for 25% of BCP quality, and during evaporation, vacuum degree is 5 × 10 -5pa, evaporation rate is the thickness of electron injecting layer is 20nm;
The material of cathode layer is Al, and thickness is 50nm, and vacuum degree during evaporation is 5 × 10 -5pa, evaporation rate is
Organic electroluminescence device prepared by the present embodiment, comprises the conductive anode, hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer, electron injecting layer and the cathode layer that stack gradually.Green light emitting layer comprises the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer that stack gradually.
Embodiment 3
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) conductive anode selects indium tin oxide glass (ITO), uses liquid detergent successively, deionized water, acetone and each ultrasonic 5 minutes of ethanol, removes the organic pollution of glass surface, cleans up rear air-dry; Also need to carry out surface activation process to the ito glass after cleaning, to increase the oxygen content on ITO surface, improve the work function on ITO surface; The thickness of conductive anode is 100nm; Then on conductive anode, hole injection layer and hole transmission layer are prepared in vacuum evaporation successively, and the material of hole injection layer is V 2o 5be doped to the composite material formed in 4,4'-bis-(9-carbazole) biphenyl (CBP), V 2o 5quality account for 35% of hole injection layer quality, the thickness of hole injection layer is 15nm, and during evaporation, vacuum degree is 5 × 10 -5pa, evaporation rate is the material of hole transmission layer is 4,4'-bis-(9-carbazole) biphenyl (CBP), and thickness is 50nm, and during evaporation, vacuum degree is 5 × 10 -5pa; Evaporation rate is
(2) then on hole transmission layer successively vacuum evaporation prepare the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer, obtain the green light emitting layer that thickness is 30nm, the material of the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer is guest materials Ir (mppy) 3be doped to the composite material that material of main part CBP is formed, first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer are all identical with the 5th doped layer thickness, Ir (mppy) in the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer 3mass fraction be respectively 6%, 4%, 2%, 4% and 6%, vacuum degree is 5 × 10 -5pa, evaporation rate is
(3) on green light emitting layer, adopt the method for vacuum evaporation to prepare electron transfer layer, electron injecting layer and cathode layer successively, obtain organic electroluminescence device;
The material of electron transfer layer is BAlq, and thickness is 60nm, and during evaporation, vacuum degree is 5 × 10 -5pa, evaporation rate is
The material of electron injecting layer is the material doped composite material formed in electron injection material of N-shaped, and N-shaped material is CsN 3, electron injection material is BAlq, and the quality of N-shaped material accounts for 35% of BAlq quality, and during evaporation, vacuum degree is 5 × 10 -5pa, evaporation rate is the thickness of electron injecting layer is 40nm;
The material of cathode layer is Au, and thickness is 200nm, and vacuum degree during evaporation is 5 × 10 -5pa, evaporation rate is
Organic electroluminescence device prepared by the present embodiment, comprises the conductive anode, hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer, electron injecting layer and the cathode layer that stack gradually.Green light emitting layer comprises the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer that stack gradually.
Embodiment 4
A preparation method for organic electroluminescence device, comprises following operating procedure:
(1) conductive anode selects indium tin oxide glass (ITO), uses liquid detergent successively, deionized water, acetone and each ultrasonic 5 minutes of ethanol, removes the organic pollution of glass surface, cleans up rear air-dry; Also need to carry out surface activation process to the ito glass after cleaning, to increase the oxygen content on ITO surface, improve the work function on ITO surface; The thickness of conductive anode is 100nm; Then on conductive anode, hole injection layer and hole transmission layer are prepared in vacuum evaporation successively, and the material of hole injection layer is ReO 3be doped to N, the composite material formed in N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD), ReO 3quality account for 30% of hole injection layer quality, the thickness of hole injection layer is 13nm, and during evaporation, vacuum degree is 5 × 10 -5pa, evaporation rate is the material of hole transmission layer is N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD), and thickness is 40nm, and during evaporation, vacuum degree is 5 × 10 -5pa; Evaporation rate is
(2) then on hole transmission layer successively vacuum evaporation prepare the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer, obtain the hole injection layer that thickness is 20nm, the material of the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer is guest materials Ir (ppy) 3be doped to the composite material that material of main part TPD is formed, first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer are all identical with the 5th doped layer thickness, Ir (ppy) in the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer 3mass fraction be respectively 3%, 2%, 1%, 2% and 3%, vacuum degree is 5 × 10 -5pa, evaporation rate is
(3) on green light emitting layer, adopt the method for vacuum evaporation to prepare electron transfer layer, electron injecting layer and cathode layer successively, obtain organic electroluminescence device;
The material of electron transfer layer is Alq 3, thickness is 30nm, and during evaporation, vacuum degree is 5 × 10 -5pa, evaporation rate is
The material of electron injecting layer is the material doped composite material formed in electron injection material of N-shaped, and N-shaped material is Li 2cO 3, electron injection material is Alq 3, the quality of N-shaped material accounts for Alq 330% of quality, during evaporation, vacuum degree is 5 × 10 -5pa, evaporation rate is the thickness of electron injecting layer is 30nm;
The material of cathode layer is Ag, and thickness is 100nm, and vacuum degree during evaporation is 5 × 10 -5pa, evaporation rate is
Organic electroluminescence device prepared by the present embodiment, comprises the conductive anode, hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer, electron injecting layer and the cathode layer that stack gradually.Green light emitting layer comprises the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer that stack gradually.
Embodiment 5
(1) conductive anode selects indium tin oxide glass (ITO), uses liquid detergent successively, deionized water, acetone and each ultrasonic 5 minutes of ethanol, removes the organic pollution of glass surface, cleans up rear air-dry; Also need to carry out surface activation process to the ito glass after cleaning, to increase the oxygen content on ITO surface, improve the work function on ITO surface; The thickness of conductive anode is 100nm; Then on conductive anode, hole injection layer and hole transmission layer are prepared in vacuum evaporation successively, and the material of hole injection layer is MoO 3be doped to the composite material formed in 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane (TAPC), MoO 3quality account for 25% of hole injection layer quality, the thickness of hole injection layer is 10nm, and during evaporation, vacuum degree is 5 × 10 -5pa, evaporation rate is the material of hole transmission layer is 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane (TAPC), and thickness is 40nm, and during evaporation, vacuum degree is 5 × 10 -5pa; Evaporation rate is
(2) then on hole transmission layer successively vacuum evaporation prepare the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer, obtain the green light emitting layer that thickness is 20nm, the material of the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer is guest materials Ir (ppy) 2(acac) composite material formed in material of main part TAPC is doped to, first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer are all identical with the 5th doped layer thickness, Ir (ppy) in the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer 2(acac) mass fraction is respectively 1.5%, 1%, 0.5%, 1% and 1.5%, and vacuum degree is 5 × 10 -5pa, evaporation rate is
(3) on green light emitting layer, adopt the method for vacuum evaporation to prepare electron transfer layer, electron injecting layer and cathode layer successively, obtain organic electroluminescence device;
The material of electron transfer layer is TAZ, and thickness is 50nm, and during evaporation, vacuum degree is 5 × 10 -5pa, evaporation rate is
The material of electron injecting layer is the material doped composite material formed in electron injection material of N-shaped, and N-shaped material is LiF, and electron injection material is TAZ, and the quality of N-shaped material accounts for 30% of TAZ quality, and during evaporation, vacuum degree is 5 × 10 -5pa, evaporation rate is the thickness of electron injecting layer is 30nm;
The material of cathode layer is Al, and thickness is 100nm, and vacuum degree during evaporation is 5 × 10 -5pa, evaporation rate is
Organic electroluminescence device prepared by the present embodiment, comprises the conductive anode, hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer, electron injecting layer and the cathode layer that stack gradually.Green light emitting layer comprises the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer that stack gradually.
Embodiment 6
(1) conductive anode selects indium tin oxide glass (ITO), uses liquid detergent successively, deionized water, acetone and each ultrasonic 5 minutes of ethanol, removes the organic pollution of glass surface, cleans up rear air-dry; Also need to carry out surface activation process to the ito glass after cleaning, to increase the oxygen content on ITO surface, improve the work function on ITO surface; The thickness of conductive anode is 100nm; Then on conductive anode, hole injection layer and hole transmission layer are prepared in vacuum evaporation successively, and the material of hole injection layer is WO 3be doped to N, the composite material formed in N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), WO 3quality account for 30% of hole injection layer quality, the thickness of hole injection layer is 12nm, and during evaporation, vacuum degree is 1 × 10 -3pa, evaporation rate is the material of hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), and thickness is 40nm, and during evaporation, vacuum degree is 1 × 10 -3pa; Evaporation rate is
(2) then on hole transmission layer successively vacuum evaporation prepare the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer, obtain the green light emitting layer that thickness is 20nm, the material of the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer is Ir (mppy) 3be doped to the composite material that ADN is formed, first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer are all identical with the 5th doped layer thickness, Ir (mppy) in the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer 3mass fraction be respectively 4.5%, 3%, 1.5%, 3%, 4.5%, vacuum degree is 1 × 10 -3pa, evaporation rate is
(3) on green light emitting layer, adopt the method for vacuum evaporation to prepare electron transfer layer, electron injecting layer and cathode layer successively, obtain organic electroluminescence device;
The material of electron transfer layer is TPBI, and thickness is 30nm, and during evaporation, vacuum degree is 1 × 10 -3pa, evaporation rate is
The material of electron injecting layer is the material doped composite material formed in electron injection material of N-shaped, and N-shaped material is Li 2o, electron injection material is TPBI, and the quality of N-shaped material accounts for 30% of TPBI quality, and during evaporation, vacuum degree is 5 × 10 -5pa, evaporation rate is the thickness of electron injecting layer is 30nm;
The material of cathode layer is Al, and thickness is 100nm, and vacuum degree during evaporation is 1 × 10 -3pa, evaporation rate is
Organic electroluminescence device prepared by the present embodiment, comprises the conductive anode, hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer, electron injecting layer and the cathode layer that stack gradually.Green light emitting layer comprises the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer that stack gradually.
Comparative example
(1) conductive anode selects indium tin oxide glass (ITO), uses liquid detergent successively, deionized water, acetone and each ultrasonic 5 minutes of ethanol, removes the organic pollution of glass surface, cleans up rear air-dry; Also need to carry out surface activation process to the ito glass after cleaning, to increase the oxygen content on ITO surface, improve the work function on ITO surface; The thickness of conductive anode is 100nm; Then on conductive anode, the hole injection layer that thickness is 12nm is prepared in vacuum evaporation, then the hole transmission layer that thickness is 40nm is prepared in vacuum evaporation on hole injection layer, and hole injection layer material is V 2o 5be doped to the composite material that CBP is formed, vacuum degree is 5 × 10 -5pa, evaporation rate is v 2o 5quality account for 30% of hole injection layer quality; The material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), and during evaporation, vacuum degree is 5 × 10 -5pa, evaporation rate is
(2) on hole transmission layer, green light emitting layer is prepared in vacuum evaporation, and the material of green light emitting layer is guest materials Ir (ppy) 3with the composite material that material of main part TCTA is formed, guest materials Ir (ppy) 3quality accounts for 8% of green light emitting layer quality, and the thickness of green light emitting layer is 20nm, and vacuum degree is 5 × 10 -5pa, evaporation rate is
(3) on green light emitting layer, adopt the method for vacuum evaporation to prepare electron transfer layer, electron injecting layer and cathode layer successively, obtain organic electroluminescence device;
The material of electron transfer layer is Bphen, and thickness is 40nm, and during evaporation, vacuum degree is 5 × 10 -5pa, evaporation rate is
The material of electron injecting layer is the material doped composite material formed in electron injection material of N-shaped, and N-shaped material is Li 2o, electron injection material is TPBI, and the quality of N-shaped material accounts for 30% of TPBI quality, and during evaporation, vacuum degree is 5 × 10 -5pa, evaporation rate is the thickness of electron injecting layer is 30nm;
The material of cathode layer is Al, and thickness is 138nm, and vacuum degree during evaporation is 5 × 10 -5pa, evaporation rate is
Organic electroluminescence device prepared by the present embodiment, comprises the conductive anode, hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer, electron injecting layer and the cathode layer that stack gradually, and green light emitting layer is single layer structure.
Effect example
Adopt digital sourcemeter 2400 to provide current source, luminance meter CS-100A test brightness, then test organic electroluminescence device at brightness 1000cd/m 2under electric current and voltage, then calculate the luminous efficiency of device.
Table 1 is the organic electroluminescence device of embodiment 1 ~ 6 and comparative example is 1000cd/m at luminosity 2time device luminous efficiency.
As can be seen from Table 1, the organic electroluminescence device prepared of the present invention is at 1000cd/m 2under light efficiency compare raising more than 0.6 times with comparative example.Illustrate that green light emitting layer is divided into the first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer and the 5th doped layer stacked gradually by organic electroluminescence device of the present invention, improve the luminous efficiency of device.
The luminous efficiency of organic electroluminescence device prepared by table 1 embodiment 1 ~ 6 and comparative example
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.

Claims (10)

1. an organic electroluminescence device, is characterized in that, comprises the conductive anode stacked gradually, hole injection layer, hole transmission layer, green light emitting layer, electron transfer layer, electron injecting layer and cathode layer, described green light emitting layer comprises the first doped layer stacked gradually, second doped layer, 3rd doped layer, 4th doped layer and the 5th doped layer, described first doped layer, second doped layer, 3rd doped layer, the material of the 4th doped layer and the 5th doped layer is guest materials and is doped to the composite material formed in material of main part, and described guest materials accounts for described first doped layer, second doped layer, 3rd doped layer, the mass fraction of the 4th doped layer and the 5th doped layer is respectively 3a%, 2a%, a%, 2a% and 3a%, wherein, 0.5≤a≤4, described guest materials is that three (2-phenylpyridines) close iridium), acetopyruvic acid two (2-phenylpyridine) iridium) or three [2-(p-methylphenyl) pyridines] close iridium, described material of main part is 4,4', 4''-tri-(carbazole-9-base) triphenylamine, 9,9'-(1,3-phenyl) two-9H-carbazole, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine, 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane or two (1-naphthyl) anthracene of 9,10-.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, described first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer are all identical with the thickness of the 5th doped layer, and the thickness of described green light emitting layer is 10 ~ 30nm.
3. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described hole injection layer is the material doped composite material formed to hole-injecting material of p-type, described p-type material is molybdenum trioxide, tungstic acid, vanadic oxide or rhenium trioxide, described hole-injecting material is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines, 4, 4', 4''-tri-(carbazole-9-base) triphenylamine, 4, 4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4, 4'-benzidine or 1, 1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, the quality of described p-type material accounts for 25% ~ 35% of described hole injection layer quality.
4. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-base) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane.
5. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described electron transfer layer is 4,7-diphenyl-1,10-ferrosin, 2,9-dimethyl-4,7-diphenyl-1,10-ferrosin, 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene.
6. organic electroluminescence device as claimed in claim 1, it is characterized in that, the material of described electron injecting layer is the material doped composite material formed to electron injection material of N-shaped, described N-shaped material is cesium carbonate, cesium fluoride, cesium azide, lithium carbonate, lithium fluoride or lithia, described electron injection material is 4, 7-diphenyl-1, 10-ferrosin, 2, 9-dimethyl-4, 7-diphenyl-1, 10-ferrosin, 4-biphenyl phenolic group-two (2-methyl-oxine) closes aluminium, oxine aluminium, 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, 2, 4-triazole or 1, 3, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene, the quality of described N-shaped material accounts for 25% ~ 35% of described electron injecting layer quality.
7. a preparation method for organic electroluminescence device, is characterized in that, comprises following operating procedure:
The conductive anode of required size is provided, dry after cleaning; Then on conductive anode, adopt the method for vacuum evaporation to prepare hole injection layer and hole transmission layer successively;
The method of vacuum evaporation is adopted to prepare the first doped layer successively on the hole transport layer, second doped layer, 3rd doped layer, 4th doped layer and the 5th doping, obtain described green light emitting layer, described first doped layer, second doped layer, 3rd doped layer, the material of the 4th doped layer and the 5th doped layer is guest materials and is doped to the composite material formed in material of main part, and described guest materials accounts for described first doped layer, second doped layer, 3rd doped layer, the mass fraction of the 4th doped layer and the 5th doped layer is respectively 3a%, 2a%, a%, 2a% and 3a%, wherein, 0.5≤a≤4, described guest materials is that three (2-phenylpyridines) close iridium), acetopyruvic acid two (2-phenylpyridine) iridium) or three [2-(p-methylphenyl) pyridines] close iridium, described material of main part is 4,4', 4''-tri-(carbazole-9-base) triphenylamine, 9,9'-(1,3-phenyl) two-9H-carbazole, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine, 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane or two (1-naphthyl) anthracene of 9,10-, evaporation vacuum degree is 1 × 10 -5pa ~ 1 × 10 -3pa, evaporation rate is
Prepare electron transfer layer, electron injecting layer and cathode layer successively at described green light emitting layer, obtain described organic electroluminescence device.
8. the preparation method of organic electroluminescence device as claimed in claim 7, it is characterized in that, described first doped layer, the second doped layer, the 3rd doped layer, the 4th doped layer are all identical with the thickness of the 5th doped layer, and the thickness of described green light emitting layer is 10 ~ 30nm.
9. the preparation method of organic electroluminescence device as claimed in claim 7, it is characterized in that, the evaporation rate preparing described hole transmission layer, electron transfer layer and electron injecting layer is the evaporation rate of described cathode layer is
10. the preparation method of organic electroluminescence device as claimed in claim 7, it is characterized in that, the evaporation rate of described hole injection layer is
CN201310561267.3A 2013-11-12 2013-11-12 Organic light-emitting device and preparation method thereof Pending CN104638164A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111384252A (en) * 2018-12-27 2020-07-07 广东阿格蕾雅光电材料有限公司 OLED device structure
WO2021077486A1 (en) * 2019-10-22 2021-04-29 Tcl华星光电技术有限公司 Oled display panel and display device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111384252A (en) * 2018-12-27 2020-07-07 广东阿格蕾雅光电材料有限公司 OLED device structure
WO2021077486A1 (en) * 2019-10-22 2021-04-29 Tcl华星光电技术有限公司 Oled display panel and display device

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