CN104037349A - Stacked organic light emitting device and preparation method thereof - Google Patents
Stacked organic light emitting device and preparation method thereof Download PDFInfo
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- CN104037349A CN104037349A CN201310071827.7A CN201310071827A CN104037349A CN 104037349 A CN104037349 A CN 104037349A CN 201310071827 A CN201310071827 A CN 201310071827A CN 104037349 A CN104037349 A CN 104037349A
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- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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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
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- 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
- H10K71/10—Deposition of organic active material
- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
- H10K71/166—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using selective deposition, e.g. using a mask
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- 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
- H10K85/6565—Oxadiazole compounds
Abstract
Provided are a stacked organic light emitting device and a preparation method thereof. The device comprises an anode, a first light emitting unit, a charge generating layer, a second light emitting unit and a cathode which are sequentially stacked. The charge generating layer comprises an n-type layer, a middle layer and a p-type layer which are sequentially stacked, wherein the n-type layer is formed by doping cesium salt in a first metal oxide, the middle layer is formed by an electron transport material, and the p-type layer is formed by a second metal oxide. The cesium salt is cesium phosphate, cesium carbonate, cesium fluoride or cesium chloride. The first metal oxide and the second metal oxide are molybdenum trioxide, tungsten trioxide or vanadium pentoxide. The electron transport material is 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-biphenyl-1,10-orthophenanthroline, 2,2'-(1,3-phenyl)di[5-(4-tert-butytphenyl)-1,3,4-oxadiazole or 2-(4'-tert-butytphenyl)-5-(4'-biphenylyl)-1,3,4-oxadiazole. The light emitting efficiency of the device is high.
Description
Technical field
The present invention relates to electroluminescent technology field, particularly relate to a kind of laminated organic electroluminescent device and preparation method thereof.
Background technology
1987, the C.W.Tang of Eastman Kodak company of the U.S. and VanSlyke reported the breakthrough in organic electroluminescent research.Utilize ultrathin film technology to prepare high brightness, high efficiency double-deck organic electroluminescence device (OLED).In this double-deck device, under 10V, brightness reaches 1000cd/m
2, its luminous efficiency is 1.51lm/W, life-span to be greater than 100 hours.
The principle of luminosity of OLED 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.In order to improve luminosity and luminous efficiency, increasing research is taking laminated device as main, this structure is normally together in series several luminescence units as articulamentum with charge generation layer, and compared with unit component, multilayer devices often has current efficiency and luminosity at double.
At present research many be utilize two or more to have that hole is injected or material of electronic injection as charge generating layers (as Cs:BCP/V
2o
5), or N-shaped and p-type doped layer as charge generation layer (as N-shaped (Alq
3: Li) and p-type (NPB:FeCl
3)), or Al-WO
3-Au etc. are linked in sequence multiple luminescence units and form, but general transmitance is lower, and luminous efficiency is all lower.
Summary of the invention
Based on this, be necessary the laminated organic electroluminescent device that provides a kind of luminous efficiency higher.
A kind of preparation method of laminated organic electroluminescent device further, is provided.
A kind of laminated organic electroluminescent device, comprise the anode, the first luminescence unit, charge generating layers, the second luminescence unit and the negative electrode that stack gradually, described the first luminescence unit comprises the hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer that stack gradually on described anode; Described the second luminescence unit comprises the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the electron injecting layer that stack gradually on described charge generation layer; Described charge generating layers comprises the N-shaped layer, intermediate layer and the p-type layer that stack gradually on described the first luminescence unit, and described N-shaped layer is doped in the first metal oxide and is formed by cesium salt; Described intermediate layer is formed by electron transport material; Described p-type layer is formed by the second metal oxide; Wherein, described cesium salt is phosphoric acid caesium, cesium carbonate, cesium fluoride or cesium chloride, described the first metal oxide is molybdenum trioxide, tungstic acid or vanadic oxide, described electron transport material is 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles] or 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1,3,4-oxadiazoles; Described the second metal oxide is molybdenum trioxide, tungstic acid or vanadic oxide.
In an embodiment, the mass ratio of described cesium salt and described the first metal oxide is 2～5:10 therein.
In an embodiment, the thickness of described N-shaped layer is 5 nanometer～20 nanometers therein.
In an embodiment, the thickness in described intermediate layer is 1 nanometer～10 nanometer therein.
In an embodiment, the thickness of described p-type layer is 5 nanometer～30 nanometers therein.
Therein in an embodiment,
Described hole injection layer is formed by molybdenum trioxide, tungstic acid or vanadic oxide;
Described the first hole transmission layer is by 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine forms;
Described the first luminescent layer is by 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'-, 1'-biphenyl or oxine aluminium form;
Described the first electron transfer layer is by 4,7-diphenyl-1,10-phenanthroline, 1,2, and 4-triazole derivative or N-aryl benzimidazole form.
In an embodiment, the thickness of described hole injection layer is 20 nanometer～80 nanometers therein; The thickness of described the first hole transmission layer is 20 nanometer～60 nanometers; The thickness of described the first luminescent layer is 5 nanometer～40 nanometers; The thickness of described the first electron transfer layer is 40 nanometer～200 nanometers.
Therein in an embodiment,
Described the second hole transmission layer is by 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine forms;
Described the second luminescent layer is by 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'-, 1'-biphenyl or oxine aluminium form;
Described the second electron transfer layer is by 4,7-diphenyl-1,10-phenanthroline, 1,2, and 4-triazole derivative or N-aryl benzimidazole form;
Described electron injecting layer is formed by cesium carbonate, cesium fluoride, cesium azide or lithium fluoride.
In an embodiment, the thickness of described the second hole transmission layer is 20 nanometer～60 nanometers therein; The thickness of described the second luminescent layer is 5 nanometer～40 nanometers; The thickness of described the second electron transfer layer is 40 nanometer～200 nanometers; The thickness of described electron injecting layer is 0.5 nanometer～10 nanometer.
A preparation method for laminated organic electroluminescent device, comprises the steps:
Thereby adopt vacuum evaporation on anode, to form successively hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer and on described anode, form the first luminescence unit;
Adopt vacuum evaporation to form N-shaped layer on described the first luminescence unit, described N-shaped layer is doped in the first metal oxide and is formed by cesium salt;
Adopt vacuum evaporation to form intermediate layer on described N-shaped layer, described intermediate layer is formed by electron transport material;
Adopt vacuum evaporation on described intermediate layer, to form p-type layer, described p-type layer is formed by the second metal oxide, and described N-shaped layer, intermediate layer and p-type layer stack gradually formation charge generation layer; Wherein, described cesium salt is phosphoric acid caesium, cesium carbonate, cesium fluoride or cesium chloride, described the first metal oxide is molybdenum trioxide, tungstic acid or vanadic oxide, described electron transport material is 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles] or 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1,3,4-oxadiazoles, described the second metal oxide is molybdenum trioxide, tungstic acid or vanadic oxide;
Thereby adopt vacuum evaporation on described p-type layer, to form successively the second hole transmission layer, the second luminescent layer, the second electron transfer layer and electron injecting layer and form the second luminescence unit on described p-type layer; And
Adopt vacuum evaporation to form negative electrode on described the second luminescence unit, obtain laminated organic electroluminescent device.
The charge generation layer of above-mentioned laminated organic electroluminescent device comprises the N-shaped layer, intermediate layer and the p-type layer that stack gradually, N-shaped layer is doped in ambipolar the first metal oxide and is formed by cesium salt, can reduce electronic injection potential barrier, improve electron injection efficiency and electric transmission efficiency, thereby improve exciton recombination probability; Intermediate layer is formed by crystallinity electron transport material, can further improve the power of regeneration of electronics, hole is mated with electron amount, p-type layer is formed by the second metal oxide, can improve injection and the transmission in hole, thereby make the luminous efficiency of laminated organic electroluminescent device higher.
Brief description of the drawings
Fig. 1 is the structural representation of the laminated organic electroluminescent device of an execution mode;
Fig. 2 is preparation method's flow chart of the laminated organic electroluminescent device of an execution mode;
Fig. 3 is that embodiment 1 is related to schematic diagram with voltage and the current efficiency of the laminated organic electroluminescent device of comparative example 1.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details are set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, and therefore the present invention is not subject to the restriction of following public concrete enforcement.
Refer to Fig. 1, the laminated organic electroluminescent device 100 of an execution mode, comprises the anode 10, the first luminescence unit 20, charge generating layers 30, the second luminescence unit 40 and the negative electrode 50 that stack gradually.
Anode 10 is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO).
The first luminescence unit 20 comprises the hole injection layer 21, the first hole transmission layer 22, the first luminescent layer 23 and the first electron transfer layer 24 that stack gradually on anode 10.
Hole injection layer 21 is by molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5) form, preferably by molybdenum trioxide (MoO
3) form.
The thickness of hole injection layer 21 is 20 nanometer～80 nanometers, is preferably 40 nanometers.
The first hole transmission layer 22 is by 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB) forms.Preferably by 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC) formation.
The thickness of the first hole transmission layer 22 is 20 nanometer～60 nanometers, is preferably 25 nanometers.
The first luminescent layer 23 is by 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) or oxine aluminium (Alq
3) form, preferably, by two (the 9-ethyl-3-carbazole vinyl)-1 of 4,4'-, 1'-biphenyl (BCzVBi) forms.
The thickness of the first luminescent layer 23 is 5 nanometer～40 nanometers, is preferably 10 nanometers.
The first electron transfer layer 24 is by 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and 4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBi) form, and are preferably formed by N-aryl benzimidazole (TPBi).
The thickness of the first electron transfer layer 24 is 40 nanometer～200 nanometers, is preferably 100 nanometers.
Charge generation layer 30 comprises the N-shaped layer 31, intermediate layer 32 and the p-type layer 33 that stack gradually on the first luminescence unit 20.
N-shaped layer 31 is doped in the first metal oxide and is formed by cesium salt.
Cesium salt is phosphoric acid caesium (Cs
3pO
4), cesium carbonate (Cs
2cO
3), cesium fluoride (CsF) or cesium chloride (CsCl).
The first metal oxide is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5).
These several metal oxides are bipolarity metal oxide, cesium salt is doped in the N-shaped layer 31 forming in bipolarity metal oxide can reduce electronic injection potential barrier, thereby raising injection efficiency, also can improve the transmission rate of electronics, and exciton recombination probability is got a promotion.
Preferably, the mass ratio of cesium salt and the first metal oxide is 2～5:10.
Preferably, the thickness of N-shaped layer 31 is 5 nanometer～20 nanometers.
Intermediate layer 32 is formed by electron transport material.Electron transport material is 4,7-diphenyl-1,10-phenanthroline (Bphen), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles] (OXD-7) or 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1,3,4-oxadiazoles (PBD).
These several electron transport materials are crystallinity electron transport material, and its glass transition temperature is lower than 100 DEG C, and this different materials can carry out scattering to light after forming crystallization, improves light extraction efficiency.
Preferably, the thickness in intermediate layer 32 is 1 nanometer～10 nanometer.
P-type layer 33 is formed by the second metal oxide.The second metal oxide is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5).
In same laminated organic electroluminescent device, the first metal oxide and the second metal oxide can be the same or different.
Preferably, the thickness of p-type layer 33 is 5 nanometer～30 nanometers.
The second luminescence unit 40 comprises the second hole transmission layer 41, the second luminescent layer 42, the second electron transfer layer 43 and the electron injecting layer 44 that stack gradually on p-type layer 33.
The second hole transmission layer 41 is by 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB) forms.Preferably by 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC) formation.
The thickness of the second hole transmission layer 41 is 20 nanometer～60 nanometers, is preferably 25 nanometers.
The second luminescent layer 42 is by 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) or oxine aluminium (Alq
3) form, preferably, by two (the 9-ethyl-3-carbazole vinyl)-1 of 4,4'-, 1'-biphenyl (BCzVBi) forms.
The thickness of the second luminescent layer 42 is 5 nanometer～40 nanometers, is preferably 10 nanometers.
The second electron transfer layer 43 is by 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and 4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBi) form, and are preferably formed by N-aryl benzimidazole (TPBi).
The thickness of the second electron transfer layer 43 is 40 nanometer～200 nanometers, is preferably 100 nanometers.
Electron injecting layer 44 is by cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), cesium azide (CsN
3) or lithium fluoride (LiF) formation, preferably by cesium carbonate (Cs
2cO
3) form.
The thickness of electron injecting layer 44 is 0.5 nanometer～10 nanometer, is preferably 3 nanometers.
Negative electrode 50 is formed by silver (Ag), aluminium (Al), platinum (Pt) or gold (Au), is preferably formed by silver (Ag).
The thickness of negative electrode 50 is 60 nanometer～300 nanometers, is preferably 150 nanometers.
Above-mentioned laminated organic electroluminescent device 100 connects the first luminescence unit 20 and the second luminescence unit 40 by charge generation layer 30, charge generation layer 30 comprises the N-shaped layer 31, intermediate layer 32 and the p-type layer 33 that stack gradually, N-shaped layer 31 can reduce electronic injection potential barrier, improve electron injection efficiency and electric transmission efficiency, thereby improve exciton recombination probability; The power of regeneration of electronics can be further improved in intermediate layer 32, and hole is mated with electron amount, and p-type layer 33 is formed by the second metal oxide, can improve injection and the transmission in hole, thereby makes the luminous efficiency of laminated organic electroluminescent device 100 higher.
Refer to Fig. 2, the preparation method of the laminated organic electroluminescent device of an execution mode, comprises the steps:
Step S110: form the first luminescence unit thereby adopt vacuum evaporation to form successively hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer on anode on anode.
Anode is provided.Anode is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO).
Anode is used to liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15 minutes of isopropyl alcohol, the organic pollution of removal anode surface, then dry, for subsequent use.
Adopt vacuum evaporation to form successively hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer on clean, dry anode and on anode, form the first luminescence unit.
Wherein, hole injection layer is by molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5) form, preferably by molybdenum trioxide (MoO
3) form.
The thickness of hole injection layer is 20 nanometer～80 nanometers, is preferably 40 nanometers.
The first hole transmission layer is by 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB) forms.Preferably by 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC) formation.
The thickness of the first hole transmission layer is 20 nanometer～60 nanometers, is preferably 25 nanometers.
The first luminescent layer is by 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) or oxine aluminium (Alq
3) form, preferably, by two (the 9-ethyl-3-carbazole vinyl)-1 of 4,4'-, 1'-biphenyl (BCzVBi) forms.
The thickness of the first luminescent layer is 5 nanometer～40 nanometers, is preferably 10 nanometers.
The first electron transfer layer is by 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and 4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBi) form, and are preferably formed by N-aryl benzimidazole (TPBi).
The thickness of the first electron transfer layer is 40 nanometer～200 nanometers, is preferably 100 nanometers.
The pressure of vacuum evaporation is preferably 5 × 10
-3pa～2 × 10
-4pa.
Step S120: adopt vacuum evaporation to form N-shaped layer on the first luminescence unit.
N-shaped layer is doped in the first metal oxide and is formed by cesium salt.
Cesium salt is phosphoric acid caesium (Cs
3pO
4), cesium carbonate (Cs
2cO
3), cesium fluoride (CsF) or cesium chloride (CsCl).
The first metal oxide is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5).
Preferably, the mass ratio of cesium salt and the first metal oxide is 2～5:10.
Preferably, the thickness of N-shaped layer is 5 nanometer～20 nanometers.
The pressure of vacuum evaporation is preferably 5 × 10
-3pa～2 × 10
-4pa.
Step S130: adopt vacuum evaporation to form intermediate layer on N-shaped layer.
Intermediate layer is formed by electron transport material.Electron transport material is 4,7-diphenyl-1,10-phenanthroline (Bphen), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles] (OXD-7) or 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1,3,4-oxadiazoles (PBD).
Preferably, the thickness in intermediate layer is 1 nanometer～10 nanometer.
The pressure of vacuum evaporation is preferably 5 × 10
-3pa～2 × 10
-4pa.
Step S140: adopt vacuum evaporation to form p-type layer on intermediate layer, p-type layer is formed by the second metal oxide, and N-shaped layer, intermediate layer and p-type layer stack gradually formation charge generation layer.
P-type layer is formed by the second metal oxide.The second metal oxide is molybdenum trioxide (MoO
3), tungstic acid (WO
3) or vanadic oxide (V
2o
5).
In same laminated organic electroluminescent device, the first metal oxide and the second metal oxide can be the same or different.
Preferably, the thickness of p-type layer is 5 nanometer～30 nanometers.
The pressure of vacuum evaporation is preferably 5 × 10
-3pa～2 × 10
-4pa.
Step S150: form the second luminescence unit thereby adopt vacuum evaporation to form successively the second hole transmission layer, the second luminescent layer, the second electron transfer layer and electron injecting layer on p-type layer on p-type layer.
The second luminescence unit comprises the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the electron injecting layer that stack gradually on p-type layer.
The second hole transmission layer is by 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine (NPB) forms.Preferably by 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC) formation.
The thickness of the second hole transmission layer is 20 nanometer～60 nanometers, is preferably 25 nanometers.
The second luminescent layer is by 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) or oxine aluminium (Alq
3) form, preferably, by two (the 9-ethyl-3-carbazole vinyl)-1 of 4,4'-, 1'-biphenyl (BCzVBi) forms.
The thickness of the second luminescent layer is 5 nanometer～40 nanometers, is preferably 10 nanometers.
The second electron transfer layer is by 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and 4-triazole derivative (as TAZ) or N-aryl benzimidazole (TPBi) form, and are preferably formed by N-aryl benzimidazole (TPBi).
The thickness of the second electron transfer layer is 40 nanometer～200 nanometers, is preferably 100 nanometers.
Electron injecting layer is by cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), cesium azide (CsN
3) or lithium fluoride (LiF) formation, preferably by cesium carbonate (Cs
2cO
3) form.
The thickness of electron injecting layer is 0.5 nanometer～10 nanometer, is preferably 3 nanometers.
The pressure of vacuum evaporation is preferably 5 × 10
-3pa～2 × 10
-4pa.
Step S160: adopt vacuum evaporation to form negative electrode on the second luminescence unit, obtain laminated organic electroluminescent device.
Negative electrode is formed by silver (Ag), aluminium (Al), platinum (Pt) or gold (Au), is preferably formed by silver (Ag).
The thickness of negative electrode is 60 nanometer～300 nanometers, is preferably 150 nanometers.
The pressure of vacuum evaporation is preferably 5 × 10
-3pa～2 × 10
-4pa.
Preparation method's technique of above-mentioned laminated organic electroluminescent device is simple, is easy to extensive preparation.
It is below specific embodiment.
Embodiment 1
Structure is ITO/MoO
3/ TAPC/BCzVBi/TPBi/Cs
3pO
4: MoO
3/ PBD/WO
3/ TAPC/BCzVBi/TPBi/Cs
2cO
3the preparation of the laminated organic electroluminescent device of/Ag
(1) provide anode, anode is indium tin oxide glass, is expressed as ITO.Anode is used to liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15 minutes of isopropyl alcohol, the organic pollution of removal anode surface, then dry, for subsequent use;
(2) hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer that adopt vacuum evaporation to form successively on the surface of anode, the pressure of vacuum evaporation is 5 × 10
-3pa; Hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer stack gradually and form the first luminescence unit being laminated on anode; Wherein, hole injection layer is formed by molybdenum trioxide, and thickness is 40 nanometers; The first hole transmission layer is by 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, thickness is 25 nanometers; The first luminescent layer is by two (the 9-ethyl-3-carbazole vinyl)-1 of 4,4'-, and 1'-biphenyl forms, and thickness is 10 nanometers; The first electron transfer layer is formed by N-aryl benzimidazole, and thickness is 100 nanometers; The first luminescence unit is expressed as MoO
3/ TAPC/BCzVBi/TPBi;
(3) adopt vacuum evaporation on the surface of the first electron transfer layer, to form successively N-shaped layer, intermediate layer and p-type layer, N-shaped layer, intermediate layer and p-type layer stack gradually formation charge generation layer, and the pressure of vacuum evaporation is 5 × 10
-3pa.Wherein, N-shaped layer is doped in molybdenum trioxide and is formed by phosphoric acid caesium, is expressed as Cs
3pO
4: MoO
3, Cs
3pO
4with MoO
3mass ratio be 3:10, the thickness of N-shaped layer is 7 nanometers; Intermediate layer is by 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1,3, and 4-oxadiazoles forms, and the thickness in intermediate layer is 2 nanometers; P-type layer is formed by tungstic acid, and the thickness of p-type layer is 20 nanometers, and charge generation layer is expressed as Cs
3pO
4: MoO
3/ PBD/WO
3;
(4) adopt vacuum evaporation to stack gradually on the surface of p-type layer and form the second hole transmission layer, the second luminescent layer, the second electron transfer layer and electron injecting layer, the pressure of vacuum evaporation is 5 × 10
-3pa; The second hole transmission layer, the second luminescent layer, the second electron transfer layer and electron injecting layer stack gradually and form the second luminescence unit being laminated on charge generation layer; Wherein, the second hole transmission layer is by 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane formation, thickness is 25 nanometers; The second luminescent layer is by two (the 9-ethyl-3-carbazole vinyl)-1 of 4,4'-, and 1'-biphenyl forms, and thickness is 10 nanometers; The second electron transfer layer is formed by N-aryl benzimidazole, and thickness is 100 nanometers; Electron injecting layer is formed by cesium carbonate, and the thickness of electron injecting layer is 3 nanometers; The second luminescence unit is expressed as TAPC/BCzVBi/TPBi/Cs
2cO
3;
(5) adopt vacuum evaporation to form negative electrode on the surface of electron injecting layer, the pressure of vacuum evaporation is 5 × 10
-3pa; Negative electrode is formed by silver, and the thickness of negative electrode is 150 nanometers.
The structure that stacked anode, the first luminescence unit, charge generating layer, the second luminescence unit and negative electrode successively forms is:
ITO/MoO
3/ TAPC/BCzVBi/TPBi/Cs
3pO
4: MoO
3/ PBD/WO
3/ TAPC/BCzVBi/TPBi/Cs
2cO
3the laminated organic electroluminescent device of/Ag; Wherein, brace "/" represents layer structure, Cs
3pO
4: MoO
3in colon ": " represent doping mix, lower with.
Embodiment 2
Structure is AZO/V
2o
5/ TCTA/Alq
3/ TAZ/CsF:V
2o
5/ Bphen/MoO
3/ NPB/Alq
3/ Bphen/CsN
3the preparation of the laminated organic electroluminescent device of/Pt
(1) provide anode, anode is aluminium zinc oxide glass, is expressed as ITO.Anode is used to liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15 minutes of isopropyl alcohol, the organic pollution of removal anode surface, then dry, for subsequent use;
(2) hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer that adopt vacuum evaporation to form successively on the surface of anode, the pressure of vacuum evaporation is 2 × 10
-4pa; Hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer stack gradually and form the first luminescence unit being laminated on anode; Wherein, hole injection layer is formed by vanadic oxide, and thickness is 40 nanometers; The first hole transmission layer is by 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, thickness is 80 nanometers; The first luminescent layer is formed by oxine aluminium, and thickness is 5 nanometers; The first electron transfer layer is formed by 1,2,4-triazole derivative, and thickness is 40 nanometers; The first luminescence unit is expressed as V
2o
5/ TCTA/Alq
3/ TAZ;
(3) adopt vacuum evaporation on the surface of the first electron transfer layer, to form successively N-shaped layer, intermediate layer and p-type layer, N-shaped layer, intermediate layer and p-type layer stack gradually formation charge generation layer, and the pressure of vacuum evaporation is 2 × 10
-4pa.Wherein, N-shaped layer is doped in vanadic oxide and is formed by cesium fluoride, is expressed as CsF:V
2o
5, CsF and V
2o
5mass ratio be 2:10, the thickness of N-shaped layer is 5 nanometers; Intermediate layer is by 4,7-diphenyl-1, and 10-phenanthroline forms, and the thickness in intermediate layer is 1 nanometer; P-type layer is formed by molybdenum trioxide, and the thickness of p-type layer is 30 nanometers, and charge generation layer is expressed as CsF:V
2o
5/ Bphen/MoO
3;
(4) adopt vacuum evaporation to stack gradually on the surface of p-type layer and form the second hole transmission layer, the second luminescent layer, the second electron transfer layer and electron injecting layer, the pressure of vacuum evaporation is 2 × 10
-4pa; The second hole transmission layer, the second luminescent layer, the second electron transfer layer and electron injecting layer stack gradually and form the second luminescence unit being laminated on charge generation layer; Wherein, the second hole transmission layer is by N, N '-(1-naphthyl)-N, and N '-diphenyl-4,4 '-benzidine forms, and thickness is 20 nanometers; The second luminescent layer is formed by oxine aluminium, and thickness is 40 nanometers; The second electron transfer layer is by 4,7-diphenyl-1, and 10-phenanthroline forms, and thickness is 200 nanometers; Electron injecting layer is formed by cesium azide, and the thickness of electron injecting layer is 0.5 nanometer; The second luminescence unit is expressed as NPB/Alq
3/ Bphen/CsN
3;
(5) adopt vacuum evaporation to form negative electrode on the surface of electron injecting layer, the pressure of vacuum evaporation is 2 × 10
-4pa; Negative electrode is formed by platinum, and the thickness of negative electrode is 60 nanometers.
The structure that stacked anode, the first luminescence unit, charge generating layer, the second luminescence unit and negative electrode successively forms is AZO/V
2o
5/ TCTA/Alq
3/ TAZ/CsF:V
2o
5/ Bphen/MoO
3/ NPB/Alq
3/ Bphen//CsN
3the laminated organic electroluminescent device of/Pt.
Embodiment 3
Structure is ITO/WO
3/ TAPC/DCJTB/TAZ/Cs
3pO
4: WO
3/ BCP/MoO
3the preparation of the laminated organic electroluminescent device of/NBP/DCJTB/TAZ/CsF/Al
(1) provide anode, anode is indium tin oxide glass, is expressed as ITO.Anode is used to liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15 minutes of isopropyl alcohol, the organic pollution of removal anode surface, then dry, for subsequent use;
(2) hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer that adopt vacuum evaporation to form successively on the surface of anode, the pressure of vacuum evaporation is 3 × 10
-4pa; Hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer stack gradually and form the first luminescence unit being laminated on anode; Wherein, hole injection layer is formed by tungstic acid, and thickness is 20 nanometers; The first hole transmission layer is by 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, thickness is 30 nanometers; The first luminescent layer is by 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl) formation of-4H-pyrans, thickness is 10 nanometers; The first electron transfer layer is formed by 1,2,4-triazole derivative, and thickness is 200 nanometers; The first luminescence unit is expressed as WO
3/ TAPC/DCJTB/TAZ;
(3) adopt vacuum evaporation on the surface of the first electron transfer layer, to form successively N-shaped layer, intermediate layer and p-type layer, N-shaped layer, intermediate layer and p-type layer stack gradually formation charge generation layer, and the pressure of vacuum evaporation is 3 × 10
-4pa.Wherein, N-shaped layer is doped in tungstic acid and is formed by phosphoric acid caesium, is expressed as Cs
3pO
4: WO
3, Cs
3pO
4with WO
3mass ratio be 5:10, the thickness of N-shaped layer is 20 nanometers; Intermediate layer is by 2,9-dimethyl-4,7-biphenyl-1, and 10-phenanthrolene forms, and the thickness in intermediate layer is 5 nanometers; P-type layer is formed by molybdenum trioxide, and the thickness of p-type layer is 5 nanometers, and charge generation layer is expressed as Cs
3pO
4: WO
3/ BCP/MoO
3;
(4) adopt vacuum evaporation to stack gradually on the surface of p-type layer and form the second hole transmission layer, the second luminescent layer, the second electron transfer layer and electron injecting layer, the pressure of vacuum evaporation is 3 × 10
-4pa; The second hole transmission layer, the second luminescent layer, the second electron transfer layer and electron injecting layer stack gradually and form the second luminescence unit being laminated on charge generation layer; Wherein, the second hole transmission layer is by N, N '-(1-naphthyl)-N, and N '-diphenyl-4,4 '-benzidine forms, and thickness is 60 nanometers; The second luminescent layer is by 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl) formation of-4H-pyrans, thickness is 5 nanometers; The second electron transfer layer is formed by 1,2,4-triazole derivative, and thickness is 40 nanometers; Electron injecting layer is formed by cesium fluoride, and the thickness of electron injecting layer is 10 nanometers; The second luminescence unit is expressed as NBP/DCJTB/TAZ/CsF;
(5) adopt vacuum evaporation to form negative electrode on the surface of electron injecting layer, the pressure of vacuum evaporation is 3 × 10
-4pa; Negative electrode is formed by aluminium, and the thickness of negative electrode is 300 nanometers.
The structure that stacked anode, the first luminescence unit, charge generating layer, the second luminescence unit and negative electrode successively forms is ITO/WO
3/ TAPC/DCJTB/TAZ/Cs
3pO
4: WO
3/ BCP/MoO
3the laminated organic electroluminescent device of/NBP/DCJTB/TAZ/CsF/Al.
Embodiment 4
Structure is ITO/MoO
3/ NPB/ADN/Bphen/CsCl:MoO
3/ OXD-7/WO
3the preparation of the laminated organic electroluminescent device of/NBP/ADN/TAZ/LiF/Au
(1) provide anode, anode is indium tin oxide glass, is expressed as ITO.Anode is used to liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15 minutes of isopropyl alcohol, the organic pollution of removal anode surface, then dry, for subsequent use;
(2) hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer that adopt vacuum evaporation to form successively on the surface of anode, the pressure of vacuum evaporation is 4 × 10
-4pa; Hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer stack gradually and form the first luminescence unit being laminated on anode; Wherein, hole injection layer is formed by molybdenum trioxide, and thickness is 30 nanometers; The first hole transmission layer is by N, N '-(1-naphthyl)-N, and N '-diphenyl-4,4 '-benzidine, thickness is 50 nanometers; The first luminescent layer is formed by 9,10-, bis--β-naphthylene anthracene, and thickness is 8 nanometers; The first electron transfer layer is by 4,7-diphenyl-1, and 10-phenanthroline forms, and thickness is 40 nanometers; The first luminescence unit is expressed as MoO
3/ NPB/ADN/Bphen;
(3) adopt vacuum evaporation on the surface of the first electron transfer layer, to form successively N-shaped layer, intermediate layer and p-type layer, N-shaped layer, intermediate layer and p-type layer stack gradually formation charge generation layer, and the pressure of vacuum evaporation is 4 × 10
-4pa.Wherein, N-shaped layer is doped in molybdenum trioxide and is formed by cesium chloride, is expressed as CsCl:MoO
3, CsCl accounts for MoO
3mass percent be 3.5:10, the thickness of N-shaped layer is 15 nanometers; Intermediate layer is formed by 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles], and the thickness in intermediate layer is 8 nanometers; P-type layer is formed by tungstic acid, and the thickness of p-type layer is 12 nanometers, and charge generation layer is expressed as CsCl:MoO
3/ OXD-7/WO
3;
(4) adopt vacuum evaporation to stack gradually on the surface of p-type layer and form the second hole transmission layer, the second luminescent layer, the second electron transfer layer and electron injecting layer, the pressure of vacuum evaporation is 4 × 10
-4pa; The second hole transmission layer, the second luminescent layer, the second electron transfer layer and electron injecting layer stack gradually and form the second luminescence unit being laminated on charge generation layer; Wherein, the second hole transmission layer is by N, N '-(1-naphthyl)-N, and N '-diphenyl-4,4 '-benzidine forms, and thickness is 50 nanometers; The second luminescent layer is formed by 9,10-, bis--β-naphthylene anthracene, and thickness is 7 nanometers; The second electron transfer layer is formed by 1,2,4-triazole derivative, and thickness is 40 nanometers; Electron injecting layer is formed by lithium fluoride, and the thickness of electron injecting layer is 0.7 nanometer; The second luminescence unit is expressed as NBP/ADN/TAZ/LiF;
(5) adopt vacuum evaporation to form negative electrode on the surface of electron injecting layer, the pressure of vacuum evaporation is 4 × 10
-4pa; Negative electrode is formed by gold, and the thickness of negative electrode is 180 nanometers.
The structure that stacked anode, the first luminescence unit, charge generating layer, the second luminescence unit and negative electrode successively forms is ITO/MoO
3/ NPB/ADN/Bphen/CsCl:MoO
3/ OXD-7/WO
3the laminated organic electroluminescent device of/NBP/ADN/TAZ/LiF/Au.
Comparative example 1
Structure is ITO/MoO
3/ TAPC/BCzVBi/TPBi/Al/WO
3/ Au/TAPC/BCzVBi/TPBi/Cs
2cO
3the preparation of the laminated organic electroluminescent device of/Ag
(1) provide anode, anode is indium tin oxide glass, is expressed as ITO.Anode is used to liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15 minutes of isopropyl alcohol, the organic pollution of removal anode surface, then dry, for subsequent use;
(2) hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer that adopt vacuum evaporation to form successively on the surface of anode, the pressure of vacuum evaporation is 5 × 10
-3pa; Hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer stack gradually and form the first luminescence unit being laminated on anode; Wherein, hole injection layer is formed by molybdenum trioxide, and thickness is 40 nanometers; The first hole transmission layer is by 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, thickness is 25 nanometers; The first luminescent layer is by two (the 9-ethyl-3-carbazole vinyl)-1 of 4,4'-, and 1'-biphenyl forms, and thickness is 10 nanometers; The first electron transfer layer is formed by N-aryl benzimidazole, and thickness is 100 nanometers; The first luminescence unit is expressed as MoO
3/ TAPC/BCzVBi/TPBi;
(3) adopt vacuum evaporation on the surface of the first electron transfer layer, to form successively aluminium lamination, tungstic acid layer and gold layer, the pressure of vacuum evaporation is 5 × 10
-3pa; Aluminium lamination, tungstic acid layer and gold be the folded charge generation layer that forms layer by layer, is expressed as Al/WO
3/ Au, the thickness of charge generation layer is 29 nanometers;
(4) adopt vacuum evaporation to stack gradually on the surface of charge generation layer and form the second hole transmission layer, the second luminescent layer, the second electron transfer layer and electron injecting layer, the pressure of vacuum evaporation is 5 × 10
-3pa; The second hole transmission layer, the second luminescent layer, the second electron transfer layer and electron injecting layer stack gradually and form the second luminescence unit being laminated on charge generation layer; Wherein, the second hole transmission layer is by 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane formation, thickness is 25 nanometers; The second luminescent layer is by two (the 9-ethyl-3-carbazole vinyl)-1 of 4,4'-, and 1'-biphenyl forms, and thickness is 10 nanometers; The second electron transfer layer is formed by N-aryl benzimidazole, and thickness is 100 nanometers; Electron injecting layer is formed by cesium carbonate, and the thickness of electron injecting layer is 3 nanometers; The second luminescence unit is expressed as TAPC/BCzVBi/TPBi/Cs
2cO
3;
(5) adopt vacuum evaporation to form negative electrode on the surface of electron injecting layer, the pressure of vacuum evaporation is 5 × 10
-3pa; Negative electrode is formed by silver, and the thickness of negative electrode is 150 nanometers.
The structure that stacked anode, the first luminescence unit, charge generating layer, the second luminescence unit and negative electrode successively forms is ITO/MoO
3/ TAPC/BCzVBi/TPBi/Al/WO
3/ Au/TAPC/BCzVBi/TPBi/Cs
2cO
3the laminated organic electroluminescent device of/Ag.
The laminated organic electroluminescent device of above-described embodiment 1～4 and comparative example 1 adopts high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd) to be prepared.
Adopt the electric property of the Keithley2400 test implementation example 1 of Keithley company of the U.S. and the laminated organic electroluminescent device of comparative example 1, test structure as shown in Figure 3, wherein, curve 1 is the schematic diagram that is related to of the voltage of laminated organic electroluminescent device of embodiment 1 and current efficiency; Curve 2 is the schematic diagram that is related to of the voltage of laminated organic electroluminescent device of comparative example 1 and current efficiency.
As can be seen from Figure 3, under different brightness, all large than comparative example 1 of the luminous efficiency of the laminated organic electroluminescent device of embodiment 1, the luminous efficiency of embodiment 1 maximum is 7.5lm/W, and that comparative example 1 is only 4.2lm/W, and the luminous efficiency of comparative example 1 along with the increase of brightness fast-descending, this explanation, the charge generation layer of the laminated organic electroluminescent device of embodiment 1 can further improve the power of regeneration of electronics, hole is mated with electron amount, the injection and the transmission that improve hole, improve luminous efficiency greatly.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a laminated organic electroluminescent device, it is characterized in that, comprise the anode, the first luminescence unit, charge generating layers, the second luminescence unit and the negative electrode that stack gradually, described the first luminescence unit comprises the hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer that stack gradually on described anode; Described the second luminescence unit comprises the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the electron injecting layer that stack gradually on described charge generation layer; Described charge generating layers comprises the N-shaped layer, intermediate layer and the p-type layer that stack gradually on described the first luminescence unit, and described N-shaped layer is doped in the first metal oxide and is formed by cesium salt; Described intermediate layer is formed by electron transport material; Described p-type layer is formed by the second metal oxide; Wherein, described cesium salt is phosphoric acid caesium, cesium carbonate, cesium fluoride or cesium chloride, described the first metal oxide is molybdenum trioxide, tungstic acid or vanadic oxide, described electron transport material is 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles] or 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1,3,4-oxadiazoles; Described the second metal oxide is molybdenum trioxide, tungstic acid or vanadic oxide.
2. laminated organic electroluminescent device according to claim 1, is characterized in that, the mass ratio of described cesium salt and described the first metal oxide is 2～5:10.
3. laminated organic electroluminescent device according to claim 1, is characterized in that, the thickness of described N-shaped layer is 5 nanometer～20 nanometers.
4. laminated organic electroluminescent device according to claim 1, is characterized in that, the thickness in described intermediate layer is 1 nanometer～10 nanometer.
5. laminated organic electroluminescent device according to claim 1, is characterized in that, the thickness of described p-type layer is 5 nanometer～30 nanometers.
6. laminated organic electroluminescent device according to claim 1, is characterized in that,
Described hole injection layer is formed by molybdenum trioxide, tungstic acid or vanadic oxide;
Described the first hole transmission layer is by 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine forms;
Described the first luminescent layer is by 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'-, 1'-biphenyl or oxine aluminium form;
Described the first electron transfer layer is by 4,7-diphenyl-1,10-phenanthroline, 1,2, and 4-triazole derivative or N-aryl benzimidazole form.
7. laminated organic electroluminescent device according to claim 6, is characterized in that, the thickness of described hole injection layer is 20 nanometer～80 nanometers; The thickness of described the first hole transmission layer is 20 nanometer～60 nanometers; The thickness of described the first luminescent layer is 5 nanometer～40 nanometers; The thickness of described the first electron transfer layer is 40 nanometer～200 nanometers.
8. laminated organic electroluminescent device according to claim 1, is characterized in that,
Described the second hole transmission layer is by 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine or N, N '-(1-naphthyl)-N, N '-diphenyl-4,4 '-benzidine forms;
Described the second luminescent layer is by 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'-, 1'-biphenyl or oxine aluminium form;
Described the second electron transfer layer is by 4,7-diphenyl-1,10-phenanthroline, 1,2, and 4-triazole derivative or N-aryl benzimidazole form;
Described electron injecting layer is formed by cesium carbonate, cesium fluoride, cesium azide or lithium fluoride.
9. laminated organic electroluminescent device according to claim 8, is characterized in that, the thickness of described the second hole transmission layer is 20 nanometer～60 nanometers; The thickness of described the second luminescent layer is 5 nanometer～40 nanometers; The thickness of described the second electron transfer layer is 40 nanometer～200 nanometers; The thickness of described electron injecting layer is 0.5 nanometer～10 nanometer.
10. a preparation method for laminated organic electroluminescent device claimed in claim 1, is characterized in that, comprises the steps:
Thereby adopt vacuum evaporation on anode, to form successively hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer and on described anode, form the first luminescence unit;
Adopt vacuum evaporation to form N-shaped layer on described the first luminescence unit, described N-shaped layer is doped in the first metal oxide and is formed by cesium salt;
Adopt vacuum evaporation to form intermediate layer on described N-shaped layer, described intermediate layer is formed by electron transport material;
Adopt vacuum evaporation on described intermediate layer, to form p-type layer, described p-type layer is formed by the second metal oxide, and described N-shaped layer, intermediate layer and p-type layer stack gradually formation charge generation layer; Wherein, described cesium salt is phosphoric acid caesium, cesium carbonate, cesium fluoride or cesium chloride, described the first metal oxide is molybdenum trioxide, tungstic acid or vanadic oxide, described electron transport material is 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, 2,2'-(1,3-phenyl) two [5-(4-tert-butyl-phenyl)-1,3,4-oxadiazoles] or 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1,3,4-oxadiazoles, described the second metal oxide is molybdenum trioxide, tungstic acid or vanadic oxide;
Thereby adopt vacuum evaporation on described p-type layer, to form successively the second hole transmission layer, the second luminescent layer, the second electron transfer layer and electron injecting layer and form the second luminescence unit on described p-type layer; And
Adopt vacuum evaporation to form negative electrode on described the second luminescence unit, obtain laminated organic electroluminescent device.
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| WO2023020538A1 (en) * | 2021-08-18 | 2023-02-23 | 清华大学 | Serial organic electroluminescent device |
| CN116583133A (en) * | 2023-06-19 | 2023-08-11 | 季华恒烨(佛山)电子材料有限公司 | Laminated organic electroluminescent device and application thereof |
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