CN103972419A - Organic light-emitting device and production method thereof - Google Patents
Organic light-emitting device and production method thereof Download PDFInfo
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- CN103972419A CN103972419A CN201310039178.2A CN201310039178A CN103972419A CN 103972419 A CN103972419 A CN 103972419A CN 201310039178 A CN201310039178 A CN 201310039178A CN 103972419 A CN103972419 A CN 103972419A
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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]
- H10K50/17—Carrier injection layers
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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]
- H10K50/17—Carrier injection layers
- H10K50/171—Electron injection layers
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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
- H10K50/80—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 first metal sulfide doped layer laminated on the surface of the first electron transport layer, a metal layer formed on the surface of the first metal sulfide doped layer and a second metal sulfide doped layer formed on the surface of the metal layer, the first metal sulfide doped layer is made of materials including metal sulfides and bipolar metal oxides doped in the metal sulfide, the bipolar metal oxides are selected from at least one of molybdenum trioxide, tungsten trioxide and vanadium pentoxide, and the metal sulfides are selected from at least one of zinc sulfide, cadmium sulfide, calcium sulfide and magnesium sulfide. 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
Technical field
The present invention relates to a kind of organic electroluminescence device and preparation method thereof.
Background technology
The principle of luminosity of organic electroluminescence device is based under the effect of extra electric field, and electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Electronics and hole meet at luminescent layer, compound, form exciton, exciton moves under electric field action, and energy is passed to luminescent material, and excitation electron is from ground state transition to excitation state, excited energy, by Radiation-induced deactivation, produces photon, discharges luminous energy.Yet the luminous efficiency of organic electroluminescence device is lower at present.
Summary of the invention
Based on this, be necessary to provide organic electroluminescence device that a kind of luminous efficiency is higher and preparation method thereof.
An 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 first metal sulfide doped layer that is laminated in described the first electron transfer layer surface, be formed at the metal level on described the first metal sulfide doped layer surface and be formed at the second metal sulfide doped layer of described layer on surface of metal, the material of described the first metal sulfide doped layer comprises metal sulfide and is entrained in the bipolarity metal oxide in described metal sulfide, and described bipolarity metal oxide is selected from molybdenum trioxide, at least one in tungstic acid or vanadic oxide, described metal sulfide is selected from zinc sulphide, cadmium sulfide, at least one in calcium sulfide or magnesium sulfide, wherein, the mass ratio of described bipolarity metal oxide and described metal sulfide is 1:20～3:10, the material of described metal level is selected from silver, aluminium, in platinum or gold at least one, the material of described the second metal sulfide doped layer comprises metal sulfide and is entrained in the metal oxide in described metal sulfide, the material of described metal oxide is selected from tantalum pentoxide, in vanadium dioxide or niobium pentaoxide at least one, the mass ratio of described metal oxide and described metal sulfide is 1:100～1:10.
In an embodiment, the thickness of described the first metal sulfide doped layer is 5nm ~ 20nm therein, and the thickness of described metal level is 1nm ~ 10nm, and the thickness of described the second metal sulfide doped layer is 1nm ~ 10nm.
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:
At anode surface successively evaporation, prepare hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer;
At described the first electron transfer layer surface evaporation, prepare the first metal sulfide doped layer, the material of described the first metal sulfide doped layer comprises metal sulfide and is entrained in the bipolarity metal oxide in described metal sulfide, described bipolarity metal oxide is selected from molybdenum trioxide, at least one in tungstic acid or vanadic oxide, described metal sulfide is selected from zinc sulphide, cadmium sulfide, at least one in calcium sulfide or magnesium sulfide, wherein, the mass ratio of described bipolarity metal oxide and described metal sulfide is 1:20～3:10, evaporation is 5 * 10 at vacuum pressure
-3~ 2 * 10
-4under Pa, carry out, described metal sulfide and described bipolarity metal oxide evaporate respectively in two evaporation boats, and the evaporation speed of described metal sulfide is 1nm/s ~ 10nm/s, and the evaporation speed of described bipolarity metal oxide is 1nm/s ~ 10nm/s,
At described the first metal sulfide layer surface evaporation, prepare metal level, the material of described metal level is selected from least one in silver, aluminium, platinum or gold, 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;
At described layer on surface of metal evaporation, prepare the second metal sulfide layer, the material of described the second metal sulfide doped layer comprises metal sulfide and is entrained in the metal oxide in described metal sulfide, the material of described metal oxide is selected from least one in tantalum pentoxide, vanadium dioxide or niobium pentaoxide, the mass ratio of described metal oxide and described metal sulfide is 1:100～1:10, and evaporation is 5 * 10 at vacuum pressure
-3~ 2 * 10
-4under Pa, carry out, described metal sulfide and described metal oxide evaporate respectively in two evaporation boats, metal sulfide evaporation speed 1nm/s ~ 10nm/s, and the evaporation speed of described metal oxide is 1nm/s ~ 10nm/s; And
On the second metal sulfide layer surface successively evaporation, form the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode.
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.
In an embodiment, the thickness of described the first metal sulfide doped layer is 5nm ~ 20nm therein, and the thickness of described metal level is 1nm ~ 10nm, and the thickness of described the second metal sulfide doped layer is 1nm ~ 10nm.
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, each Ultrasonic Cleaning of isopropyl acetone 15min, to remove the organic pollution of anode surface.。
Above-mentioned organic electroluminescence device and preparation method thereof, charge generation layer is by low the first metal sulfide doped layer, metal level and the first metal sulfide doped layer form, the first metal sulfide doped layer doping bipolarity metal oxide can improve the power of regeneration of electronics, thereby improve the recombination probability of exciton, there is larger energy gap, guarantee to absorb within the scope of visible light wave range less, the second metal sulfide doped layer doping high index of refraction metal can improve scattering of light effect, improve light extraction efficiency, metallic intermediate layer has higher permeability and conductivity, the charge generation layer of this structure can effectively improve the luminous efficiency of organic electroluminescence device.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is preparation method's the flow chart of the organic electroluminescence device of an execution mode;
Fig. 3 is brightness and the luminous efficiency graph of a relation of the organic electroluminescence device of embodiment 1 preparation.
Embodiment
Below in conjunction with the drawings and specific embodiments, organic electroluminescence device and preparation method thereof is further illustrated.
Refer to Fig. 1, the organic electroluminescence device 100 of an execution mode comprises anode 10, hole injection layer 20, the first hole transmission layer 32, the first luminescent layer 34, the first electron transfer layer 36, charge generation layer 40, the second hole transmission layer 52, the second luminescent layer 54, the second electron transfer layer 56, electron injecting layer 60 and the negative electrode 70 stacking gradually.
Anode 10 is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), is preferably ITO.
Hole injection layer 20 is formed at anode 10 surfaces.The material of hole injection layer 20 is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) at least one, be preferably MoO
3.The thickness of hole injection layer 20 is 20nm ~ 80nm, is preferably 40nm.
The first hole transmission layer 32 is formed at the surface of hole injection layer 20.The material of the first hole transmission layer 32 is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4; at least one in 4 '-benzidine (NPB), is preferably NPB.The thickness of the first hole transmission layer 32 is 20nm ~ 60nm, is preferably 25nm.
The first luminescent layer 34 is formed at the surface of the first hole transmission layer 32.The material of the first luminescent layer 34 is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 1'-biphenyl (BCzVBi) and 8-hydroxyquinoline aluminum (Alq
3) at least one, be preferably BCzVBi.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 30nm.
The first electron transfer layer 36 is formed at the surface of the first luminescent layer 34.The material of the first electron transfer layer 36 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and at least one in 4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TAZ.The thickness of the first electron transfer layer 36 is 40nm ~ 200nm, is preferably 60nm.
Charge generation layer 40 is formed at the surface of the first electron transfer layer 36.Described charge generation layer 40 comprise be laminated in the first electron transfer layer 36 surfaces the first metal sulfide doped layer 42, be formed at the metal level 44 on the first metal sulfide doped layer 42 surfaces and be formed at the second metal sulfide doped layer 46 on metal level 44 surfaces.
The material of the first metal sulfide doped layer 42 comprises metal sulfide and is entrained in the bipolarity metal oxide in described metal sulfide, described bipolarity metal oxide is selected from least one in molybdenum trioxide, tungstic acid or vanadic oxide, described metal sulfide is selected from least one in zinc sulphide, cadmium sulfide, calcium sulfide or magnesium sulfide, wherein, the mass ratio of described bipolarity metal oxide and described metal sulfide is 1:20～3:10.The thickness of the first metal-doped layer 42 is 5nm ~ 20nm.
Metal level 44 is formed at the first metal sulfide doped layer 42 surfaces.The material of metal level 44 is selected from least one in silver, aluminium, platinum or gold.The thickness of metal level 44 is 1nm ~ 10nm.
The second metal sulfide doped layer 46 is formed at the surface of metal level 44.The material of the second metal sulfide doped layer 46 comprises metal sulfide and is entrained in the metal oxide in described metal sulfide, the material of described metal oxide is selected from least one in tantalum pentoxide, vanadium dioxide or niobium pentaoxide, described metal sulfide is selected from least one in zinc sulphide, cadmium sulfide, calcium sulfide or magnesium sulfide, and the mass ratio of described metal oxide and described metal sulfide is 1:100～1: 10.The thickness of the second metal sulfide doped layer 46 is 1nm ~ 10nm.
The second hole transmission layer 52 is formed at the surface of the second metal sulfide doped layer 46.The material of the second hole transmission layer 52 is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4; at least one in 4 '-benzidine (NPB), is preferably NPB.The thickness of the second hole transmission layer 52 is 20nm ~ 60nm, is preferably 25nm.
The second luminescent layer 54 is formed at the surface of the second hole transmission layer 52.The material of the second luminescent layer 54 is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 1'-biphenyl (BCzVBi) and 8-hydroxyquinoline aluminum (Alq
3) at least one, be preferably BCzVBi.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 30nm.
The second electron transfer layer 56 is formed at the surface of the second luminescent layer 52.The material of the second electron transfer layer 56 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and at least one in 4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TAZ.The thickness of the second electron transfer layer 56 is 40nm ~ 200nm, is preferably 60nm.
Electron injecting layer 60 is formed at the second electron transfer layer 56 surfaces.The material of electron injecting layer 60 is selected from cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) and lithium fluoride (LiF) at least one, be preferably LiF.The thickness of electron injecting layer 60 is 0.5nm ~ 10nm, is preferably 1nm.
Negative electrode 70 is formed at electron injecting layer 60 surfaces.The material of negative electrode 70 is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au), is preferably Ag.The thickness of negative electrode 70 is 60nm ~ 300nm, is preferably 150nm.
Above-mentioned organic electroluminescence device 100, charge generation layer 40 is by the first metal sulfide doped layer 42, metal level 44 and the second metal sulfide doped layer 46 form, the first metal sulfide doped layer 42 doping bipolarity metal oxides can improve the power of regeneration of electronics, thereby improve the recombination probability of exciton, there is larger energy gap, guarantee to absorb within the scope of visible light wave range less, the second metal sulfide doped layer 46 doping high index of refraction metals can improve scattering of light effect, improve light extraction efficiency, metallic intermediate layer 44 has higher permeability and conductivity, the charge generation layer 40 of this structure can effectively improve the luminous efficiency of organic electroluminescence device.
Be appreciated that in this organic electroluminescence device 100 and also other functional layers can be set as required.
Please refer to Fig. 2, the preparation method of the organic electroluminescence device 100 of an embodiment, it comprises the following steps:
Step S110, at anode surface successively evaporation, prepare hole injection layer 20, the first hole transmission layer 32, the first luminescent layer 34 and the first electron transfer layer 36.
Anode 10 is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), is preferably ITO.
In present embodiment, before anode 10 surfaces form hole injection layer 20, first antianode 10 carries out pre-treatment, pre-treatment comprises: anode 10 is carried out to photoetching treatment, be cut into needed size, adopt liquid detergent, deionized water, acetone, ethanol, each Ultrasonic Cleaning of isopropyl acetone 15min, to remove the organic pollution on anode 10 surfaces.
Hole injection layer 20 is formed at the surface of anode 10.Hole injection layer 20 is prepared by evaporation.The material of hole injection layer 20 is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) at least one, be preferably MoO
3.The thickness of hole injection layer 20 is 20nm ~ 80nm, is preferably 40nm.Evaporation is 5 * 10 at vacuum pressure
-3~ 2 * 10
-4under Pa, carry out, evaporation speed is 1nm/s ~ 10nm/s.
The first hole transmission layer 32 is formed at the surface of hole injection layer 20.The first hole transmission layer 32 is prepared by evaporation.The material of the first hole transmission layer 32 is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4; at least one in 4 '-benzidine (NPB), is preferably NPB.The thickness of the first hole transmission layer 32 is 20nm ~ 60nm, is preferably 25nm.Evaporation is 5 * 10 at vacuum pressure
-3~ 2 * 10
-4under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
The first luminescent layer 34 is formed at the surface of the first hole transmission layer 32.The first luminescent layer 34 is prepared by evaporation.The material of the first luminescent layer 34 is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 1'-biphenyl (BCzVBi) and 8-hydroxyquinoline aluminum (Alq
3) at least one, be preferably BCzVBi.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 30nm.Evaporation is 5 * 10 at vacuum pressure
-3~ 2 * 10
-4under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
The first electron transfer layer 36 is formed at the surface of the first luminescent layer 34.The first electron transfer layer 36 is prepared by evaporation.The material of the first electron transfer layer 36 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and at least one in 4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TAZ.The thickness of the first electron transfer layer 36 is 40nm ~ 200nm, is preferably 60nm.Evaporation is 5 * 10 at vacuum pressure
-3~ 2 * 10
-4under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
Step S120, at the surperficial evaporation of the first electron transfer layer 36, prepare the first metal sulfide doped layer 42.
The material metal sulfide of the first metal sulfide doped layer 42 and be entrained in the bipolarity metal oxide in described metal sulfide, described bipolarity metal oxide is selected from least one in molybdenum trioxide, tungstic acid or vanadic oxide, described metal sulfide is selected from least one in zinc sulphide, cadmium sulfide, calcium sulfide or magnesium sulfide, wherein, the mass ratio of described bipolarity metal oxide and described metal sulfide is 1:20～3:10.The thickness of the first metal sulfide doped layer 42 is 5nm ~ 20nm.
Evaporation is 5 * 10 at vacuum pressure
-3~ 2 * 10
-4under Pa, carry out, described metal sulfide and described bipolarity metal oxide are put into respectively two different boats and are carried out evaporation, and the evaporation speed of metal sulfide is 1nm/s ~ 10nm/s, and the evaporation speed of described bipolarity metal oxide is 1nm/s ~ 10nm/s.
Step S130, at the surperficial evaporation of the first metal sulfide doped layer 42, prepare metal level 44.
Metal level 44 is formed at the first metal sulfide doped layer 42 surfaces.The material of metal level 44 is selected from least one in silver, aluminium, platinum or gold.The thickness of the second metal-doped layer 44 is 1nm ~ 10nm.
Evaporation is 5 * 10 at vacuum pressure
-3~ 2 * 10
-4under Pa, carry out, the evaporation speed of metal is 1nm/s ~ 10nm/s.
Step S140, at the surperficial evaporation of metal level 44, prepare the second metal sulfide doped layer 46.
The second metal sulfide doped layer 46 is formed at the surface of metal level 44.The material of the second metal sulfide doped layer 46 comprises metal sulfide and is entrained in the metal oxide in described metal sulfide, the material of described metal oxide is selected from least one in tantalum pentoxide, vanadium dioxide or niobium pentaoxide, described metal sulfide is selected from least one in zinc sulphide, cadmium sulfide, calcium sulfide or magnesium sulfide, and the mass ratio of described metal oxide and described metal sulfide is 1:100～1:10.The thickness of the second metal sulfide doped layer 46 is 1nm ~ 10nm.
Evaporation is 5 * 10 at vacuum pressure
-3~ 2 * 10
-4under Pa, carry out, described metal sulfide and described metal oxide are put into respectively two different boats and are carried out evaporation, and the evaporation speed of metal sulfide is 1nm/s ~ 10nm/s, and the evaporation speed of described metal oxide is 1nm/s ~ 10nm/s.
Step S150, on the second metal sulfide doped layer 46 surfaces successively evaporation, prepare the second hole transmission layer 52, the second luminescent layer 54, the second electron transfer layer 56, electron injecting layer 60 and negative electrode 70.
The second hole transmission layer 52 is formed at the surface of high-work-function metal layer 46.The material of the second hole transmission layer 52 is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4; at least one in 4 '-benzidine (NPB), is preferably NPB.The thickness of the second hole transmission layer 52 is 20nm ~ 60nm, is preferably 25nm.Evaporation is 5 * 10 at vacuum pressure
-3~ 2 * 10
-4under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
The second luminescent layer 54 is formed at the surface of the second hole transmission layer 52.The material of the second luminescent layer 54 is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 1'-biphenyl (BCzVBi) and 8-hydroxyquinoline aluminum (Alq
3) at least one, be preferably BCzVBi.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 30nm.Evaporation is 5 * 10 at vacuum pressure
-3~ 2 * 10
-4under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
The 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 60nm.Evaporation is 5 * 10 at vacuum pressure
-3~ 2 * 10
-4under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
Electron injecting layer 60 is formed at the second electron transfer layer 56 surfaces.The material of electron injecting layer 60 is selected from cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) and lithium fluoride (LiF) at least one, be preferably LiF.The thickness of electron injecting layer 60 is 0.5nm～10nm, is preferably 2.5nm.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 U.S. Keithley company, CS-100A colorimeter test brightness and the colourity of Japanese Konica Minolta company.
Embodiment 1
Structure prepared by the present embodiment is: ito glass/MoO
3/ NPB/BCzVBi/TAZ/ZnS:MoO
3/ Au/CdS:Ta
2o
5the organic electroluminescence device of/NPB/BCzVBi/TAZ/LiF/Ag.
First ITO is carried out to photoetching treatment, be cut into needed size, use successively liquid detergent, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface; Evaporation hole injection layer, material is MoO
3, thickness is 40nm; Evaporation the first hole transmission layer, material is NPB, thickness is 25nm; Evaporation the first luminescent layer, material is BCzVBi, thickness is 30nm; Evaporation the first electron transfer layer, material is TAZ, thickness is 60nm; Prepare charge generation layer: by the first metal sulfide doped layer, metal level and the second metal sulfide doped layer, formed.The material of evaporation the first metal sulfide doped layer comprises ZnS and MoO
3, wherein, MoO
3with the mass ratio of ZnS be 1:10, evaporation is 8 * 10 at vacuum pressure
-4under Pa, carry out ZnS and MoO
3put into respectively two boat evaporations, the evaporation evaporation speed of ZnS is 2nm/s, MoO
3evaporation speed be 4nm/s, the thickness of the first metal sulfide doped layer is 10nm; Evaporated metal layer, materials A u, metal layer thickness is 2nm, the material of evaporation the second metal sulfide doped layer comprises CdS and Ta
2o
5, wherein, Ta
2o
5with the mass ratio of CdS be 1:50, evaporation is 8 * 10 at vacuum pressure
-4under Pa, carry out CdS and Ta
2o
5put into respectively two boat evaporations, the evaporation evaporation speed of CdS is 3nm/s, Ta
2o
5evaporation speed be 5nm/s, the thickness of the second metal sulfide doped layer is 5nm; Evaporation the second hole transmission layer, material is NPB, thickness is 25nm; Evaporation the second luminescent layer, material is BCzVBi, thickness is 30nm; Evaporation the second electron transfer layer, material is TAZ, thickness is 30nm; Evaporation electron injecting layer, material is LiF, thickness is 2.5nm; Evaporation negative electrode, material is Ag, thickness is 150nm.Finally obtain needed electroluminescent device.
Refer to Fig. 3, the structure that is depicted as preparation in embodiment 1 is ito glass/MoO
3/ NPB/BCzVBi/TAZ/ZnS:MoO
3/ Au/CdS:Ta
2o
5the organic electroluminescence device of/NPB/BCzVBi/TAZ/LiF/Ag (curve 1) is ito glass/MoO with structure prepared by comparative example
3the brightness of the organic electroluminescence device of/NPB/BCzVBi/Bphen/LiF/Ag (curve 2) and the relation of luminous efficiency.In the organic electroluminescence device that in organic electroluminescence device prepared by comparative example, each layer thickness is prepared with embodiment 1, each layer thickness is identical.
As seen from Figure 3, under different brightness, the luminous efficiency of embodiment 1 is large than comparative example all, the maximum lumen efficiency of the organic electroluminescence device of embodiment 1 preparation is 4.8lm/W, and the luminous efficiency of organic electroluminescence device prepared by comparative example is only 3.5lm/W, and the luminous efficiency of comparative example along with the increase of brightness fast-descending, this explanation, charge generation layer is by the first metal sulfide doped layer, metal level and the second metal sulfide doped layer form, the first metal sulfide doped layer doping bipolarity metal oxide can improve the power of regeneration of electronics, thereby improve the recombination probability of exciton, there is larger energy gap, guarantee to absorb within the scope of visible light wave range less, the second metal sulfide doped layer doping high index of refraction metal can improve scattering of light effect, improve light extraction efficiency, metallic intermediate layer has higher permeability and conductivity, , this charge generation layer can effectively improve the luminous efficiency of organic electroluminescence device.
The luminous efficiency of the organic electroluminescence device that below prepared by each embodiment is all similar with embodiment 1, and each organic electroluminescence device also has similar luminous efficiency, repeats no more below.
Embodiment 2
Structure prepared by the present embodiment is AZO/V
2o
5/ TAPC/ADN/TPBi/CaS:WO
3/ Pt/ZnS:Nb
2o
5/ TCTA/ADN/Bphen/CsN
3the organic electroluminescence device of/Pt.
First AZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface; Evaporation is prepared hole injection layer, and material is V
2o
5, thickness is 80nm; Evaporation is prepared the first hole transmission layer, and material is TAPC, and thickness is 60nm; Evaporation is prepared the first luminescent layer, and material is ADN, and thickness is 5nm; Evaporation is prepared the first electron transfer layer, and material is TPBi, and thickness is 200nm; Evaporation is prepared charge generation layer: the first metal sulfide doped layer, metal level and the second metal sulfide doped layer, consist of.The material of evaporation the first metal sulfide doped layer comprises CaS and WO
3, wherein, WO
3with the mass ratio of CaS be 1:20, evaporation is 5 * 10 at vacuum pressure
-3under Pa, carry out CaS and WO
3put into respectively two boat evaporations, WO
3evaporation evaporation speed be 1nm/s, the evaporation speed of CaS is 1nm/s, the thickness of the first metal sulfide doped layer is 20nm; Evaporated metal layer, material is Pt, and metal layer thickness is 1nm, and evaporation is 5 * 10 at vacuum pressure
-3under Pa, carry out, the evaporation speed of Pt is 10nm/s, and the material of evaporation the second metal sulfide doped layer comprises ZnS and Nb
2o
5, wherein, Nb
2o
5with the mass ratio of ZnS be 1:10, evaporation is 5 * 10 at vacuum pressure
-3under Pa, carry out ZnS and Nb
2o
5put into respectively two boat evaporations, Nb
2o
5evaporation evaporation speed be 10nm/s, the evaporation speed of ZnS is 10nm/s; Then evaporation the second hole transmission layer, material is TCTA, 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 Bphen, 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.
Embodiment 3
Structure prepared by the present embodiment is IZO/MoO
3/ TCTA/Alq
3/ TAZ/CdS:V
2o
5/ Ag/CaS:VO
2/ NPB/Alq
3the organic electroluminescence device of/TPBi/CsF/Al.
First IZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface; Evaporation is prepared hole injection layer, and material is MoO
3, thickness is 20nm; Evaporation is prepared the first hole transmission layer, and material is TCTA, and thickness is 30nm; Evaporation is prepared the first luminescent layer, and material is Alq
3, thickness is 40nm; Evaporation is prepared the first electron transfer layer, and material is TAZ, and thickness is 200nm; Evaporation is prepared charge generation layer: the first metal sulfide doped layer, metal level and the second metal sulfide doped layer, consist of.The material of evaporation the first metal sulfide doped layer comprises CdS and V
2o
5, wherein, V
2o
5with the mass ratio of CdS be 3:10, evaporation is 2 * 10 at vacuum pressure
-4under Pa, carry out CdS and V
2o
5put into respectively two boat evaporations, the evaporation evaporation speed of CdS is 10nm/s, V
2o
5evaporation speed be 10nm/s, the thickness of the first metal sulfide doped layer is 5nm; Evaporated metal layer, material is Ag, and metal layer thickness is 10nm, and the material of evaporation the second metal sulfide doped layer comprises CaS and VO
2, wherein, VO
2with the mass ratio of CaS be 1:100, evaporation is 2 * 10 at vacuum pressure
-4under Pa, carry out VO
2put into respectively two boat evaporations with CaS, the evaporation evaporation speed of CaS is 1nm/s, VO
2evaporation speed be 1nm/s, the thickness of the second metal sulfide doped layer is 1nm; Evaporation is prepared the second hole transmission layer, and material is NPB, and thickness is 60nm; Evaporation is prepared the second luminescent layer, and material is Alq
3, thickness is 30nm; Evaporation is prepared the second electron transfer layer, and material is TPBi, 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.
Embodiment 4
Structure prepared by the present embodiment is IZO/MoO
3/ TCTA/DCJTB/Bphen/MgS:MoO
3/ Al/MgS:Ta
2o
5/ TAPC/DCJTB/Bphen/Cs
2cO
3the organic electroluminescence device of/Au.
First IZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface; Evaporation is prepared hole injection layer, and material is MoO
3, thickness is 30nm; Evaporation is prepared the first hole transmission layer, and material is TCTA, and thickness is 50nm; Evaporation is prepared the first luminescent layer, and material is DCJTB, and thickness is 5nm; Evaporation is prepared the first electron transfer layer, and material is Bphen, and thickness is 40nm; Evaporation is prepared charge generation layer: the first metal sulfide doped layer, metal level and the second metal sulfide doped layer, consist of.The material of evaporation the first metal sulfide doped layer comprises MgS and MoO
3, wherein, MoO
3with the mass ratio of MgS be 1:5, evaporation is 5 * 10 at vacuum pressure
-4under Pa, carry out MgS and MoO
3put into respectively two boat evaporations, MoO
3evaporation evaporation speed be 3nm/s, the evaporation speed of MgS is 4nm/s, the thickness of the first metal sulfide doped layer is 15nm; Evaporated metal layer, material is Al, and metal layer thickness is 8nm, and the material of evaporation the second metal sulfide doped layer comprises MgS and Ta
2o
5, wherein, Ta
2o
5with the mass ratio of MgS be 9:200, evaporation is 5 * 10 at vacuum pressure
-4under Pa, carry out MgS and Ta
2o
5put into respectively two boat evaporations, Ta
2o
5evaporation evaporation speed be 6nm/s, the evaporation speed of MgS is 8nm/s, the thickness of the second metal sulfide doped layer is 3nm; Evaporation is prepared the second hole transmission layer, and material is TAPC, and thickness is 50nm; Evaporation is prepared the second luminescent layer, and material is DCJTB, and thickness is 5nm; Evaporation is prepared the second electron transfer layer, and material is Bphen, and thickness is 100nm; Evaporation is prepared electron injecting layer, and material is Cs
2cO
3, thickness is 2nm; Evaporation is prepared negative electrode, and material is Au, and thickness is 180nm, finally obtains needed electroluminescent device.
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 (9)
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 first metal sulfide doped layer that is laminated in described the first electron transfer layer surface, be formed at the metal level on described the first metal sulfide doped layer surface and be formed at the second metal sulfide doped layer of described layer on surface of metal, the material of described the first metal sulfide doped layer comprises metal sulfide and is entrained in the bipolarity metal oxide in described metal sulfide, and described bipolarity metal oxide is selected from molybdenum trioxide, at least one in tungstic acid or vanadic oxide, described metal sulfide is selected from zinc sulphide, cadmium sulfide, at least one in calcium sulfide or magnesium sulfide, wherein, the mass ratio of described bipolarity metal oxide and described metal sulfide is 1:20～3:10, the material of described metal level is selected from silver, aluminium, in platinum or gold at least one, the material of described the second sulfide doped layer comprises metal sulfide and is entrained in the metal oxide in described metal sulfide, the material of described metal oxide is selected from tantalum pentoxide, in vanadium dioxide or niobium pentaoxide at least one, the mass ratio of described metal oxide and described metal sulfide is 1:100～1:10.
2. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described the first sulfide doped layer is 5nm ~ 20nm, and the thickness of described metal level is 1nm ~ 10nm, and the thickness of described the second sulfide doped layer is 1nm ~ 10nm.
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:
At anode surface successively evaporation, prepare hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer;
At described the first electron transfer layer surface evaporation, prepare the first metal sulfide doped layer, the material of described the first metal sulfide doped layer comprises metal sulfide and is entrained in the bipolarity metal oxide in described metal sulfide, described bipolarity metal oxide is selected from molybdenum trioxide, at least one in tungstic acid or vanadic oxide, described metal sulfide is selected from zinc sulphide, cadmium sulfide, at least one in calcium sulfide or magnesium sulfide, wherein, the mass ratio of described bipolarity metal oxide and described metal sulfide is 1:20～3:10, evaporation is 5 * 10 at vacuum pressure
-3~ 2 * 10
-4under Pa, carry out, described metal sulfide and described bipolarity metal oxide evaporate respectively in two evaporation boats, and the evaporation speed of described metal sulfide is 1nm/s ~ 10nm/s, and the evaporation speed of described bipolarity metal oxide is 1nm/s ~ 10nm/s,
At described the first metal sulfide layer surface evaporation, prepare metal level, the material of described metal level is selected from least one in silver, aluminium, platinum or gold, 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;
At described layer on surface of metal evaporation, prepare the second metal sulfide layer, the material of described the second metal sulfide doped layer comprises metal sulfide and is entrained in the metal oxide in described metal sulfide, the material of described metal oxide is selected from least one in tantalum pentoxide, vanadium dioxide or niobium pentaoxide, the mass ratio of described metal oxide and described metal sulfide is 1:100～1:10, and evaporation is 5 * 10 at vacuum pressure
-3~ 2 * 10
-4under Pa, carry out, described metal sulfide and described metal oxide evaporate respectively in two evaporation boats, metal sulfide evaporation speed 1nm/s ~ 10nm/s, and the evaporation speed of described metal oxide is 1nm/s ~ 10nm/s; And
On the second metal sulfide layer surface successively evaporation, form the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode.
7. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that: the material of described the first luminescent layer and described the second luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, 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 thickness of described the first metal sulfide doped layer is 5nm ~ 20nm, the thickness of described metal level is 1nm ~ 10nm, and the thickness of described the second metal sulfide doped layer is 1nm ~ 10nm.
9. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that: before described anode surface forms hole injection layer, first antianode carries out pre-treatment, pre-treatment comprises: anode is carried out to photoetching treatment, be cut into needed size, adopt liquid detergent, deionized water, acetone, ethanol, each Ultrasonic Cleaning of isopropyl acetone 15min, to remove the organic pollution of anode surface.
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| CN101006594A (en) * | 2004-08-20 | 2007-07-25 | 伊斯曼柯达公司 | White OLED having multiple white electroluminescent units |
| US20120187859A1 (en) * | 2007-10-15 | 2012-07-26 | Novaled Ag | Organic Electroluminescent Component |
| CN102723442A (en) * | 2011-03-30 | 2012-10-10 | 海洋王照明科技股份有限公司 | Organic electroluminescent device and preparation method thereof |
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| CN1474633A (en) * | 2002-08-09 | 2004-02-11 | ��ʽ����뵼����Դ�о��� | Organic electroluminescence element |
| CN101006594A (en) * | 2004-08-20 | 2007-07-25 | 伊斯曼柯达公司 | White OLED having multiple white electroluminescent units |
| US20120187859A1 (en) * | 2007-10-15 | 2012-07-26 | Novaled Ag | Organic Electroluminescent Component |
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Application publication date: 20140806 |