CN104183730A - Organic light emitting device and manufacturing method thereof - Google Patents

Organic light emitting device and manufacturing method thereof Download PDF

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Publication number
CN104183730A
CN104183730A CN201310196290.7A CN201310196290A CN104183730A CN 104183730 A CN104183730 A CN 104183730A CN 201310196290 A CN201310196290 A CN 201310196290A CN 104183730 A CN104183730 A CN 104183730A
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China
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layer
evaporation
hafnium
electroluminescence device
organic electroluminescence
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周明杰
王平
黄辉
张振华
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Priority to CN201310196290.7A priority Critical patent/CN104183730A/en
Publication of CN104183730A publication Critical patent/CN104183730A/en
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H10K50/165—Electron transporting layers comprising dopants
    • 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
    • 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
    • H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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
    • H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition

Abstract

The invention discloses an organic light emitting device, which comprises an anode, a hole injection layer, a first hole transmission layer, a first light emitting layer, a first electron transmission layer, a charge generation layer, a second hole transmission layer, a second light emitting layer, a second electron transmission layer, an electron injection layer and a cathode stacked sequentially. Material of the charge generation layer comprises electron transmission material and lanthanide oxide and hafnium compounds doped in the electron transmission material, wherein the mass ratio of the lanthanide oxide to the electron transmission material is 1:100 to 1:5; and the mass ratio of the hafnium compounds to the electron transmission material is 1:100 to 1:20. The light emitting efficiency of the organic light emitting device is high. The invention also provides an organic light emitting device manufacturing method.

Description

Organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to a kind of organic electroluminescence device and preparation method thereof.
Background technology
The principle of luminosity of organic electroluminescence device is based under the effect of extra electric field, and electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Electronics and hole meet at luminescent layer, compound, form exciton, exciton moves under electric field action, and energy is passed to luminescent material, and excitation electron is from ground state transition to excitation state, excited energy, by Radiation-induced deactivation, produces photon, discharges luminous energy.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.
A kind of organic electroluminescence device, comprise the anode stacking gradually, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode, described charge generation layer material comprises electron transport material and is entrained in lanthanide oxide in electron transport material and the compound of hafnium, described electron transport material is selected from 4, 7-diphenyl-1, 10-phenanthroline, 1, 2, at least one in 4-triazole derivative and N-aryl benzimidazole, described lanthanide oxide is selected from titanium dioxide praseodymium, praseodymium sesquioxide, in three ytterbium oxides and samarium oxide at least one, the compound of described hafnium is selected from least one in hafnium oxide and hafnium boride, wherein, the mass ratio of described lanthanide oxide and described electron transport material is 1:100～1:5, the compound of described hafnium and the mass ratio of described electron transport material are 1:100～1:20.
The thickness of described charge generation layer is 1nm～20nm.
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.
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.
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.
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 charge generation layer, described charge generation layer material comprises electron transport material and is entrained in lanthanide oxide in electron transport material and the compound of hafnium, described electron transport material is selected from 4, 7-diphenyl-1, 10-phenanthroline, 1, 2, at least one in 4-triazole derivative and N-aryl benzimidazole, described lanthanide oxide is selected from titanium dioxide praseodymium, praseodymium sesquioxide, in three ytterbium oxides and samarium oxide at least one, the compound of described hafnium is selected from least one in hafnium oxide and hafnium boride, wherein, the mass ratio of described lanthanide oxide and described electron transport material is 1:100～1:5, the compound of described hafnium and the mass ratio of described electron transport material are 1:100～1:20, evaporation is 2 * 10 at vacuum pressure -3～5 * 10 -5under Pa, carry out, the evaporation speed of organic material is 0.1nm/s～1nm/s, and the evaporation speed of metal and metallic compound is 1nm/s～10nm/s, and
On described charge generation 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.
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.
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.
The thickness of described charge generation layer is 1nm～20nm.
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 electron transport material and be entrained in lanthanide oxide in electron transport material and the compound of hafnium forms, wherein, electron transport material is mainly to provide electronics, and improve the transmission rate of electronics, lanthanide series compound improves the regeneration injectability in hole, and the chemical combination object height transmitted wave section of hafnium wide (in the transmitance of 200nm～10 μ m light higher than more than 70%), high index of refraction (refractive index is greater than 2.0), the feature with broad-band gap and high-k, can make most light directly see through, simultaneously, hafnium compound atomic radius is larger, can make to pile up closely between membrane-coating granules, improve rete density, reduce the existence of defect, this charge generation layer can improve exciton recombination probability, this charge generation layer 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 current density 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 TCTA.The thickness of the first hole transmission layer 32 is 20nm～60nm, is preferably 30nm.
The first luminescent layer 34 is formed at the surface of the first hole transmission layer 32.The material of the first luminescent layer 34 is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 1'-biphenyl (BCzVBi) and 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably BCzVBi.The thickness of luminescent layer 40 is 5nm～40nm, is preferably 20nm.
The first electron transfer layer 36 is formed at the surface of the first luminescent layer 32.The material of the first electron transfer layer 36 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and at least one in 4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TAZ.The thickness of the first electron transfer layer 36 is 40nm～300nm, is preferably 60nm.
Charge generation layer 40 is formed at the surface of the first electron transfer layer 36.Charge generation layer 40, charge generation layer 40 comprises electron transport material and is entrained in lanthanide oxide in electron transport material and the compound of hafnium, electron transport material is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1, in 2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI) at least one, lanthanide oxide material comprises titanium dioxide praseodymium (PrO 2), praseodymium sesquioxide (Pr 2o 3), three ytterbium oxide (Yb 2o 3) and samarium oxide (Sm 2o 3) at least one, the compound of hafnium comprises hafnium oxide (HfO 2) and hafnium boride (HfB 2); The mass ratio of described lanthanide oxide and described electron transport material is 1:100～1:5, and the compound of described hafnium and the mass ratio of described electron transport material are 1:100～1:20.The thickness of charge generation layer 40 is 1nm～20nm.
The second hole transmission layer 52 is formed at the surface of charge generation layer 40.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 30nm.
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 20nm.
The second electron transfer layer 56 is formed at the surface of the second luminescent layer 52.The material of the second electron transfer layer 56 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and at least one in 4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TPBI.The thickness of the second electron transfer layer 56 is 40nm～300nm, is preferably 210nm.
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 CsF.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 Al.The thickness of negative electrode 70 is 60nm～300nm, is preferably 150nm.
Above-mentioned organic electroluminescence device 100, charge generation layer 40 forms by being entrained in lanthanide oxide in electron transport material and the compound of hafnium, wherein, electron transport material is mainly to provide electronics, and improve the transmission rate of electronics, lanthanide series compound improves the regeneration injectability in hole, and the chemical combination object height transmitted wave section of hafnium wide (in the transmitance of 200nm～10 μ m light higher than more than 70%), high index of refraction (refractive index is greater than 2.0), the feature with broad-band gap and high-k, can make most light directly see through, simultaneously, hafnium compound atomic radius is larger, can make to pile up closely between membrane-coating granules, improve rete density, reduce the existence of defect, this charge generation layer can improve exciton recombination probability, this charge generation layer can effectively improve the luminous efficiency of organic electroluminescence device 100, organic electroluminescence device 100 has two luminescence units simultaneously, thereby has brightness and luminous efficiency at double.
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 2 * 10 at vacuum pressure -3～5 * 10 -5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/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 TCTA.The thickness of the first hole transmission layer 32 is 20nm～60nm, is preferably 30nm.Evaporation is 2 * 10 at vacuum pressure -3～5 * 10 -5under 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 20nm.Evaporation is 2 * 10 at vacuum pressure -3～5 * 10 -5pa carries out, and evaporation speed is 0.1nm/s～1nm/s.
The first electron transfer layer 36 is formed at the surface of the first luminescent layer 32.The first electron transfer layer 36 is prepared by evaporation.The material of the first electron transfer layer 36 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and at least one in 4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TAZ.The thickness of the first electron transfer layer 36 is 40nm～300nm, is preferably 60nm.Evaporation is 2 * 10 at vacuum pressure -3～5 * 10 -5under 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 charge generation layer 40.
Charge generation layer 40 is formed at the surface of the first electron transfer layer 36, charge generation layer 40 comprises electron transport material and is entrained in lanthanide oxide in electron transport material and the compound of hafnium, electron transport material is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1, in 2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI) at least one, lanthanide oxide material comprises titanium dioxide praseodymium (PrO 2), praseodymium sesquioxide (Pr 2o 3), three ytterbium oxide (Yb 2o 3) and samarium oxide (Sm 2o 3) at least one, the compound of hafnium comprises hafnium oxide (HfO 2) and hafnium boride (HfB 2); The mass ratio of described lanthanide oxide and described electron transport material is 1:100～1:5, and the compound of described hafnium and the mass ratio of described electron transport material are 1:100～1:20.The thickness of charge generation layer 40 is 1nm～20nm.Evaporation is 2 * 10 at vacuum pressure -3～5 * 10 -5under Pa, carry out, the evaporation speed of organic material is 0.1～1nm/s, and the evaporation speed of metal and metallic compound is 1～10nm/s.
Step S130, on charge generation layer 40 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 doped layer 402.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 30nm.Evaporation is 2 * 10 at vacuum pressure -3～5 * 10 -5under 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 20nm.Evaporation is 2 * 10 at vacuum pressure -3～5 * 10 -5under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
The second electron transfer layer 56 is formed at the surface of the second luminescent layer 52.The material of the second electron transfer layer 56 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and at least one in 4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TPBI.The thickness of the second electron transfer layer 56 is 40nm～300nm, is preferably 210nm.Evaporation is 2 * 10 at vacuum pressure -3～5 * 10 -5under 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 CsF.The thickness of electron injecting layer 60 is 0.5nm～10nm, is preferably 1nm.Evaporation is 2 * 10 at vacuum pressure -3～5 * 10 -5under 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 Al.The thickness of negative electrode 70 is 60nm～300nm, is preferably 150nm.Evaporation is 2 * 10 at vacuum pressure -3～5 * 10 -5under 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/MoO 3/ TCTA/BCzVBi/TAZ/HfO 2: Pr 2o 3: the organic electroluminescence device of Bphen/NPB/BCzVBi/TPBI/CsF/Al.Wherein, "/" presentation layer stack structure, ": " represents doping or mixes, following examples are identical.
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 TCTA, thickness is 30nm; Evaporation the first luminescent layer, material is BCzVBi, thickness is 20nm; Evaporation the first electron transfer layer, material is TAZ, thickness is 60nm; Evaporation charge generation layer forms by being entrained in lanthanide oxide in electron transport material and the compound of hafnium, and electron transport material is Bphen, and lanthanide oxide material is Pr 2o 3, the compound-material of hafnium is HfO 2, charge generation layer thickness is 10nm, Pr 2o 3with the mass ratio of Bphen be 3:20, HfO 2with the mass ratio of Bphen be 1:40; Evaporation the second hole transmission layer, material is NPB, thickness is 30nm; Evaporation the second luminescent layer, material is BCzVBi, thickness is 20nm; Evaporation the second electron transfer layer, material is TPBI, thickness is 210nm; Evaporation electron injecting layer, material is CsF, thickness is 1nm; Evaporation negative electrode, material is Al, thickness is 150nm.Finally obtain needed electroluminescent device.Evaporation is 8 * 10 at vacuum pressure -5under Pa, carry out, the evaporation speed of organic material is 0.2nm/s, and the evaporation speed of metal and metallic compound is 3nm/s.
Refer to Fig. 3, the structure that is depicted as preparation in embodiment 1 is ITO/MoO 3/ TCTA/BCzVBi/TAZ/HfO 2: Pr 2o 3: the organic electroluminescence device of Bphen/NPB/BCzVBi/TPBI/CsF/Al (curve 1) is ito glass/MoO with structure prepared by comparative example 3/ TCTA/BCzVBi/TPBi/CsF/Al(curve 2) current density 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 current densities, 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 4.7lm/W, and the luminous efficiency of organic electroluminescence device prepared by comparative example is only 3.4lm/W, this explanation, charge generation layer forms by being entrained in lanthanide oxide in electron transport material and the compound of hafnium, wherein, electron transport material is mainly to provide electronics, and improve the transmission rate of electronics, lanthanide series compound improves the regeneration injectability in hole, and the chemical combination object height transmitted wave section of hafnium wide (in the transmitance of 200nm～10 μ m light higher than more than 70%), high index of refraction (refractive index is greater than 2.0), the feature with broad-band gap and high-k, can make most light directly see through, simultaneously, hafnium compound atomic radius is larger, can make to pile up closely between membrane-coating granules, improve rete density, reduce the existence of defect, this charge generation layer can improve exciton recombination probability, 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/HfB 2: PrO 2: TAZ/TAPC/ADN/TAZ/CsN 3the organic electroluminescence device of/Pt.
First AZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface; Evaporation is prepared hole injection layer, and material is V 2o 5, thickness is 80nm; Evaporation is prepared the first hole transmission layer, and material is TAPC, and thickness is 60nm; Evaporation is prepared the first luminescent layer, and material is ADN, and thickness is 5nm; Evaporation is prepared the first electron transfer layer, and material is TPBi, and thickness is 200nm; Evaporation charge generation layer forms by being entrained in lanthanide oxide in electron transport material and the compound of hafnium, and electron transport material is TAZ, and lanthanide oxide material is PrO 2, the compound-material of hafnium is HfB 2, electric transmission layer thickness is 25nm, PrO 2with the mass ratio of TAZ be 1:5, HfB 2with the mass ratio of TAZ be 1:100; Evaporation is prepared the second hole transmission layer, and material is TAPC, and thickness is 20nm, the second luminescent layer, and material is ADN, thickness is 7nm; Evaporation is prepared the second electron transfer layer, and material is TAZ, and thickness is 40nm; Evaporation is prepared electron injecting layer, and material is CsN 3, thickness is 10nm; Evaporation is prepared negative electrode, and material is Pt, and thickness is 60nm, finally obtains needed electroluminescent device.Evaporation is 2 * 10 at vacuum pressure -3under Pa, carry out, the evaporation speed of organic material is 0.1nm/s, and the evaporation speed of metal and metallic compound is 10nm/s.
Embodiment 3
Structure prepared by the present embodiment is IZO/MoO 3/ NPB/Alq 3/ TAZ/HfB 2: Yb 2o 3: TPBI/NPB/Alq 3the organic electroluminescence device of/Bphen/CsF/Ag.
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 NPB, 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 and is formed by being entrained in lanthanide oxide in electron transport material and the compound of hafnium, and electron transport material is TPBI, and lanthanide oxide material is Yb 2o 3, the compound-material of hafnium is HfB 2, thickness is 20nm, Yb 2o 3with the mass ratio of TPBI be 1:100, HfB 2with the mass ratio of TPBI be 1:20; 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 Bphen, and thickness is 40nm; Evaporation is prepared electron injecting layer, and material is LiF, and thickness is 0.5nm; Evaporation is prepared negative electrode, and material is Ag, and thickness is 300nm, finally obtains needed electroluminescent device.Evaporation is 5 * 10 at vacuum pressure -5the evaporation speed of carrying out organic material under Pa is 1nm/s, and the evaporation speed of metal and metallic compound is 1nm/s.
Embodiment 4
Structure prepared by the present embodiment is IZO/WO 3/ TAPC/DCJTB/TPBi/HfO 2: Sm 2o 3: TAZ/TCTA/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 WO 3, thickness is 30nm; Evaporation is prepared the first hole transmission layer, and material is TAPC, and thickness is 40nm; 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 TPBi, and thickness is 40nm; Evaporation is prepared charge generation layer and is formed by being entrained in lanthanide oxide in electron transport material and the compound of hafnium, and electron transport material is TAZ, and lanthanide oxide material is Sm 2o 3, the compound-material of hafnium is HfB 2, charge generation layer thickness is 15nm, Sm 2o 3with the mass ratio of TAZ be 1:15, HfO 2with the mass ratio of TAZ be 3:100; Evaporation is prepared the second hole transmission layer, and material is TCTA, and thickness is 50nm; Evaporation the second luminescent layer, material is DCJTB, thickness is 5nm, evaporation the second electron transfer layer, material is Bphen, and thickness is 80nm, and 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 100nm, finally obtains needed electroluminescent device.Evaporation is 5 * 10 at vacuum pressure -4under Pa, carry out, the evaporation speed of organic material is 0.2nm/s, and the evaporation speed of metal and metallic compound is 5nm/s.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.

Claims (10)

1. an organic electroluminescence device, it is characterized in that, comprise the anode stacking gradually, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode, described charge generation layer material comprises electron transport material and is entrained in lanthanide oxide in electron transport material and the compound of hafnium, described electron transport material is selected from 4, 7-diphenyl-1, 10-phenanthroline, 1, 2, at least one in 4-triazole derivative and N-aryl benzimidazole, described lanthanide oxide is selected from titanium dioxide praseodymium, praseodymium sesquioxide, in three ytterbium oxides and samarium oxide at least one, the compound of described hafnium is selected from least one in hafnium oxide and hafnium boride, wherein, the mass ratio of described lanthanide oxide and described electron transport material is 1:100～1:5, the compound of described hafnium and the mass ratio of described electron transport material are 1:100～1:20.
2. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described charge generation layer is 1nm～20nm.
3. organic electroluminescence device according to claim 1, it is characterized in that, the material of described the first luminescent layer and described the second luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl and oxine aluminium.
4. organic electroluminescence device according to claim 1, it is characterized in that, the material of described the first hole transmission layer and described the second hole transmission layer is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4 " tri-(carbazole-9-yl) triphenylamine and N; N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine.
5. organic electroluminescence device according to claim 1, is characterized in that, the material of described the first electron transfer layer and described the second electron transfer layer is selected from 4,7-diphenyl-1,10-phenanthroline, 1,2, at least one in 4-triazole derivative and N-aryl benzimidazole.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
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 charge generation layer, described charge generation layer material comprises electron transport material and is entrained in lanthanide oxide in electron transport material and the compound of hafnium, described electron transport material is selected from 4, 7-diphenyl-1, 10-phenanthroline, 1, 2, at least one in 4-triazole derivative and N-aryl benzimidazole, described lanthanide oxide is selected from titanium dioxide praseodymium, praseodymium sesquioxide, in three ytterbium oxides and samarium oxide at least one, the compound of described hafnium is selected from least one in hafnium oxide and hafnium boride, wherein, the mass ratio of described lanthanide oxide and described electron transport material is 1:100～1:5, the compound of described hafnium and the mass ratio of described electron transport material are 1:100～1:20, evaporation is 2 * 10 at vacuum pressure -3～5 * 10 -5under Pa, carry out, the evaporation speed of organic material is 0.1nm/s～1nm/s, and the evaporation speed of metal and metallic compound is 1nm/s～10nm/s, and
On described charge generation 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 material of described the first hole transmission layer and described the second hole transmission layer is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4 " tri-(carbazole-9-yl) triphenylamine and N; N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine.
9. the preparation method of organic electroluminescence device according to claim 6, is characterized in that, the thickness of described charge generation layer is 1nm～20nm.
10. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that, before described anode surface forms hole injection layer, first antianode carries out pre-treatment, pre-treatment comprises: anode is carried out to photoetching treatment, be cut into needed size, adopt liquid detergent, deionized water, acetone, ethanol, each Ultrasonic Cleaning of isopropyl acetone 15min, to remove the organic pollution of anode surface.
CN201310196290.7A 2013-05-24 2013-05-24 Organic light emitting device and manufacturing method thereof Pending CN104183730A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060040132A1 (en) * 2004-08-20 2006-02-23 Eastman Kodak Company White OLED having multiple white electroluminescence units
CN101444142A (en) * 2006-05-11 2009-05-27 出光兴产株式会社 organic electroluminescent element
CN102779947A (en) * 2007-09-27 2012-11-14 株式会社半导体能源研究所 Light-emitting element, light-emitting device and electronic appliance

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060040132A1 (en) * 2004-08-20 2006-02-23 Eastman Kodak Company White OLED having multiple white electroluminescence units
CN101444142A (en) * 2006-05-11 2009-05-27 出光兴产株式会社 organic electroluminescent element
CN102779947A (en) * 2007-09-27 2012-11-14 株式会社半导体能源研究所 Light-emitting element, light-emitting device and electronic appliance

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Application publication date: 20141203