CN104518145A - Organic electroluminescent device and method for preparing same - Google Patents

Organic electroluminescent device and method for preparing same Download PDF

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Publication number
CN104518145A
CN104518145A CN201310452076.3A CN201310452076A CN104518145A CN 104518145 A CN104518145 A CN 104518145A CN 201310452076 A CN201310452076 A CN 201310452076A CN 104518145 A CN104518145 A CN 104518145A
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layer
sulfide
metal
organic
electron transport
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周明杰
黄辉
张娟娟
王平
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/82—Cathodes
    • H10K50/826—Multilayers, e.g. opaque multilayers
    • 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

Abstract

Provided is an organic electroluminescent device, comprising an anode, a hole injection layer, a hole transport layer, a luminous layer, an electron transfer layer, an electron injection layer, and a cathode stacked in sequence. The cathode layer is formed by a metallic oxide doping layer, an organic electron transport material doping layer, and a metal sulfide doping layer. The metallic oxide doping layer contains metallic oxides and metal sulfides doped in the metallic oxides. The metal sulfides are selected from at least one of zinc sulfide, cadmium sulfide, magnesium sulfide, and copper sulphide. The organic electron transport material doping layer contains an organic electron transport material and metal doped in the organic electron transport material. The metal sulfide doping layer contains metal sulfides and titanium dioxide doped in the metal sulfides. The metal sulfides are selected from at least one of zinc sulfide, cadmium sulfide, magnesium sulfide, and copper sulphide. The luminescence efficiency of the organic electroluminescent device is high. The invention also provides a method for preparing the organic electroluminescent device.

Description

Organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Under the principle of luminosity of organic electroluminescence device is based on the effect of extra electric field, electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Meet at luminescent layer in electronics and hole, compound, formation exciton, and exciton moves under electric field action, and by energy transferring to luminescent material, and excitation electron is from ground state transition to excitation state, and excited energy, by Radiation-induced deactivation, produces photon, release luminous energy.
The negative electrode of traditional organic electroluminescence device is generally the metal such as silver (Ag), gold (Au), and after preparation, negative electrode very easily penetrates into organic layer, damage, electronics easy cancellation near negative electrode, thus luminous efficiency is lower to organic layer.
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 stacked gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described cathode layer is by doped metallic oxide layer, Organic Electron Transport Material doped layer and metal sulfide doped layer composition, described doped metallic oxide layer comprises metal oxide and is entrained in the metal sulfide in described metal oxide, described metal oxide is selected from molybdenum trioxide, at least one in tungstic acid and vanadic oxide, described metal sulfide is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide, described Organic Electron Transport Material doped layer comprises Organic Electron Transport Material and is entrained in the metal in described Organic Electron Transport Material, described Organic Electron Transport Material is selected from 1, 2, 4-triazole derivative, 2, 2'-(1, 3-phenyl) two [5-(4-tert-butyl-phenyl)-1, 3, 4-oxadiazoles], 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene and 2, 8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] at least one in thiophene, described metal is selected from silver, aluminium, at least one in platinum and gold, described metal sulfide doped layer comprises metal sulfide and is entrained in the titanium dioxide in described metal sulfide, described metal sulfide is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide.
Described in described doped metallic oxide layer, the mass ratio of metal oxide and described metal sulfide is 1:1 ~ 5:1, described in described Organic Electron Transport Material doped layer, the mass ratio of Organic Electron Transport Material and metal is 2:1 ~ 5:1, and described in described metal sulfide doped layer, the doping mass ratio of metal sulfide and described titanium dioxide is 1:2 ~ 5:1.
Described doped metallic oxide layer thickness is 20nm ~ 50nm, and described Organic Electron Transport Material doped layer thickness is 50nm ~ 250nm, and described metal sulfide doped layer thickness is 100nm ~ 200nm.
The material of described luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, at least one in two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl of 4'-and oxine aluminium, the material of described hole injection layer is selected from least one in molybdenum trioxide, tungstic acid and vanadic oxide.
The material of described hole transmission layer is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, 4,4', 4''-tri-(carbazole-9-base) triphenylamine and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine, the material of described electron transfer layer is selected from 4,7-diphenyl-1,10-phenanthroline, 1, at least one in 2,4-triazole derivative and N-aryl benzimidazole, the material of described electron injecting layer is selected from least one in cesium carbonate, cesium fluoride, nitrine caesium and lithium fluoride.
A preparation method for organic electroluminescence device, comprises the following steps:
Hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer is formed successively at anode surface; And
Doped metallic oxide layer is prepared by the method for thermal resistance evaporation on electron injecting layer surface, described doped metallic oxide layer comprises metal oxide and is entrained in the metal sulfide in described metal oxide, described metal oxide is selected from molybdenum trioxide, at least one in tungstic acid and vanadic oxide, described metal sulfide is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide, then Organic Electron Transport Material doped layer is prepared on described doped metallic oxide layer surface by thermal resistance evaporation mode, described Organic Electron Transport Material doped layer comprises Organic Electron Transport Material and is entrained in the metal in described Organic Electron Transport Material, described Organic Electron Transport Material is selected from 1, 2, 4-triazole derivative, 2, 2'-(1, 3-phenyl) two [5-(4-tert-butyl-phenyl)-1, 3, 4-oxadiazoles], 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene and 2, 8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] at least one in thiophene, described metal is selected from silver, aluminium, at least one in platinum and gold, described metal sulfide doped layer is prepared at described Organic Electron Transport Material doped layer surface evaporation by the mode of electron beam evaporation plating, described metal sulfide doped layer comprises metal sulfide and is entrained in the titanium dioxide in described metal sulfide, described metal sulfide is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide.
Described in described doped metallic oxide layer, the mass ratio of metal oxide and described metal sulfide is 1:1 ~ 5:1, described in described Organic Electron Transport Material doped layer, the mass ratio of Organic Electron Transport Material and metal is 2:1 ~ 5:1, and described in described metal sulfide doped layer, the doping mass ratio of metal sulfide and described titanium dioxide is 1:2 ~ 5:1.
Described first metal sulfide layer thickness is 10nm ~ 30nm, and described metal sulfide doped layer thickness is 5nm ~ 50nm, and described second metal sulfide layer thickness is 100nm ~ 300nm.
The concrete technology condition of described thermal resistance evaporation mode is: operating pressure is 2 × 10 -3pa ~ 5 × 10 -5pa, operating current is 1A ~ 3A, and the evaporation rate of organic material is 0.1nm/s ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s.
The concrete technology condition of described electron beam evaporation plating mode is: operating pressure is 2 × 10 -3~ 5 × 10 -5pa, the energy density of electron beam evaporation plating is 10W/cm 2~ l00W/cm 2, the evaporation rate of organic material is 0.1nm/s ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s.
Above-mentioned organic electroluminescence device and preparation method thereof, by preparing the cathode construction of sandwich construction, this cathode construction layer is by doped metallic oxide layer, Organic Electron Transport Material doped layer and metal sulfide doped layer composition, metal oxide is the effect that bipolarity metal oxide can play electric transmission, electronic transmission performance can be strengthened, add the transmitance that metal sulfide can improve light, Organic Electron Transport Material in Organic Electron Transport Material doped layer has crystallinity, crystalline material and metal adulterate, film surface can be made to form ripple struction, make the light scattering of Vertical Launch, no longer vertical, thus not with the free electron generation coupling of metal level, improve photon utilance, metal can improve the conductivity of organic electroluminescence device, finally prepare layer of metal sulfide doped layer, metal sulfide and titanium dioxide form, metal sulfide can realize the reflection of light, the light to top-emission is made to be reflected back bottom, titanium dioxide can increase the scattering of light, thus strengthen reflection efficiency thus improve luminous efficiency.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is the cathode construction schematic diagram of the organic electroluminescence device of an execution mode;
Fig. 3 is current density and the luminous efficiency graph of a relation of organic electroluminescence device prepared by embodiment 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, organic electroluminescence device and preparation method thereof is illustrated further.
Refer to Fig. 1, the organic electroluminescence device 100 of an execution mode comprises the anode 10, hole injection layer 20, hole transmission layer 30, luminescent layer 40, electron transfer layer 50, electron injecting layer 60 and the negative electrode 70 that stack gradually.
Anode 10 is indium tin oxide glass (ITO), mixes the tin oxide glass (FTO) of fluorine, mixes the zinc oxide glass (AZO) of aluminium or mixes the zinc oxide glass (IZO) of indium, is preferably ITO.
Hole injection layer 20 is formed at anode 10 surface.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.
Hole transmission layer 30 is formed at the surface of hole injection layer 20.The material of hole transmission layer 30 is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine (NPB), is preferably NPB.The thickness of hole transmission layer 30 is 20nm ~ 60nm, is preferably 35nm.
Luminescent layer 40 is formed at the surface of hole transmission layer 30.The material of luminescent layer 40 is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-and 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably BCzVBi.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 35nm.
Electron transfer layer 50 is formed at the surface of luminescent layer 40.The material of electron transfer layer 50 is selected from least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably Bphen.The thickness of electron transfer layer 50 is 40nm ~ 300nm, is preferably 140nm.
Electron injecting layer 60 is formed at electron transfer layer 50 surface.The material of electron injecting layer 60 is selected from cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), nitrine caesium (CsN 3) and lithium fluoride (LiF) at least one, be preferably LiF.The thickness of electron injecting layer 60 is 0.5nm ~ 10nm, is preferably 1nm.
Be the cathode construction schematic diagram of the organic electroluminescence device of an execution mode please refer to Fig. 2, negative electrode 70 is formed at electron injecting layer 60 surface.Cathode layer 70 is made up of doped metallic oxide layer 701, Organic Electron Transport Material doped layer 702 and metal sulfide doped layer 703, described doped metallic oxide layer comprises metal oxide and is entrained in the metal sulfide in described metal oxide, and described metal oxide is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) middle at least one, described metal sulfide material is selected from zinc sulphide (ZnS), cadmium sulfide (CdS), magnesium sulfide (MgS) and the middle at least one of copper sulfide (CuS), described Organic Electron Transport Material doped layer 702 comprises Organic Electron Transport Material and is entrained in the metal in described Organic Electron Transport Material, the HOMO energy level of described Organic Electron Transport Material is at-6.5eV ~-7.5eV, glass transition temperature is at 50 DEG C ~ 100 DEG C, specifically be selected from 1, 2, 4-triazole derivative (TAZ), 2, 2'-(1, 3-phenyl) two [5-(4-tert-butyl-phenyl)-1, 3, 4-oxadiazoles] (OXD-7), 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene (BCP) and 2, 8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] the middle at least one of thiophene (PO15), described metal material is selected from silver (Ag), aluminium (Al), platinum (Pt) and the middle at least one of gold (Au), described metal sulfide doped layer 703 comprises metal sulfide and is entrained in the titanium dioxide in described metal sulfide, described metal sulfide material is selected from zinc sulphide (ZnS), cadmium sulfide (CdS), magnesium sulfide (MgS) and the middle at least one of copper sulfide (CuS), described titanium dioxide particle diameter is 20nm ~ 200nm.
Described in described doped metallic oxide layer 701, the mass ratio of metal oxide and described metal sulfide is 1:1 ~ 5:1, described in described Organic Electron Transport Material doped layer 702, the mass ratio of Organic Electron Transport Material and metal is 2:1 ~ 5:1, and described in described metal sulfide doped layer 703, the doping mass ratio of metal sulfide and described titanium dioxide is 1:2 ~ 5:1.
Described doped metallic oxide layer 701 thickness is 20nm ~ 50nm, and described Organic Electron Transport Material doped layer 702 thickness is 50nm ~ 250nm, and described metal sulfide doped layer 703 thickness is 100nm ~ 200nm.
Above-mentioned organic electroluminescence device 100 is by preparing the cathode construction of sandwich construction, this cathode construction layer is by doped metallic oxide layer, Organic Electron Transport Material doped layer and metal sulfide doped layer composition, metal oxide is the effect that bipolarity metal oxide can play electric transmission, electronic transmission performance can be strengthened, add the transmitance that metal sulfide can improve light, Organic Electron Transport Material in Organic Electron Transport Material doped layer has crystallinity, crystalline material and metal adulterate, film surface can be made to form ripple struction, make the light scattering of Vertical Launch, no longer vertical, thus not with the free electron generation coupling of metal level, improve photon utilance, metal can improve the conductivity of organic electroluminescence device, finally prepare layer of metal sulfide doped layer, metal sulfide and titanium dioxide form, metal sulfide can realize the reflection of light, the light to top-emission is made to be reflected back bottom, titanium dioxide can increase the scattering of light, thus strengthen reflection efficiency thus improve luminous efficiency.
Be appreciated that in this organic electroluminescence device 100 and also can other functional layers be set as required.
The preparation method of the organic electroluminescence device 100 of one embodiment, it comprises the following steps:
Step S110, form hole injection layer 20, hole transmission layer 30, luminescent layer 40, electron transfer layer 50 and electron injecting layer 60 successively on anode 10 surface.
Anode 10 is indium tin oxide glass (ITO), mixes the tin oxide glass (FTO) of fluorine, mixes the zinc oxide glass (AZO) of aluminium or mixes the zinc oxide glass (IZO) of indium, is preferably ITO.
In present embodiment, before anode 10 surface forms hole injection layer 20, first antianode 10 carries out pre-treatment, pre-treatment comprises: anode 10 is carried out photoetching treatment, be cut into required size, adopt liquid detergent, deionized water, acetone, ethanol, each Ultrasonic Cleaning 15min of isopropyl acetone, to remove the organic pollution on anode 10 surface.
Hole injection layer 20 is formed at the surface of anode 10.Hole injection layer 20 is prepared by evaporation.The material of hole injection layer 20 is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) at least one, be preferably MoO 3.The thickness of hole injection layer 20 is 20nm ~ 80nm, is preferably 40nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Hole transmission layer 30 is formed at the surface of hole injection layer 20.Hole-injecting Buffer Layer for Improvement 30 is prepared by evaporation.The material of hole transmission layer 30 is selected from 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA) and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine (NPB), is preferably NPB.The thickness of hole transmission layer 30 is 20nm ~ 60nm, is preferably 35nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Luminescent layer 40 is formed at the surface of hole transmission layer 30.Luminescent layer 40 is prepared by evaporation.The material of luminescent layer 40 is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis--β-naphthylene anthracene (ADN), 4, two (9-ethyl-3-carbazole vinyl)-1, the 1'-biphenyl (BCzVBi) of 4'-and 8-hydroxyquinoline aluminum (Alq 3) at least one, be preferably BCzVBi.The thickness of luminescent layer 40 is 0.5nm ~ 40nm, is preferably 35nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Electron transfer layer 50 is formed at the surface of luminescent layer 40.The material of electron transfer layer 50 is selected from least one in 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2,4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably Bphen.The thickness of electron transfer layer 50 is 40nm ~ 300nm, is preferably 140nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Electron injecting layer 60 is formed at electron transfer layer 50 surface.Electron injecting layer 60 is prepared by evaporation.The material of electron injecting layer 60 is selected from cesium carbonate (Cs 2cO 3), cesium fluoride (CsF), nitrine caesium (CsN 3) and lithium fluoride (LiF) at least one, be preferably LiF.The thickness of electron injecting layer 60 is 0.5nm ~ 10nm, is preferably 1nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Step S120, electron injecting layer surface prepare doped metallic oxide layer by the method for thermal resistance evaporation, described doped metallic oxide layer comprises metal oxide and is entrained in the metal sulfide in described metal oxide, and described metal oxide is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) middle at least one, described metal sulfide is selected from zinc sulphide (ZnS), cadmium sulfide (CdS), magnesium sulfide (MgS) and the middle at least one of copper sulfide (CuS), then Organic Electron Transport Material doped layer is prepared on described doped metallic oxide layer surface by thermal resistance evaporation mode, described Organic Electron Transport Material doped layer comprises Organic Electron Transport Material and is entrained in the metal in described Organic Electron Transport Material, the HOMO energy level of described Organic Electron Transport Material is at-6.5eV ~-7.5eV, glass transition temperature is at 50 DEG C ~ 100 DEG C, specifically be selected from 1, 2, 4-triazole derivative (TAZ), 2, 2'-(1, 3-phenyl) two [5-(4-tert-butyl-phenyl)-1, 3, 4-oxadiazoles] (OXD-7), 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene (BCP) and 2, 8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] the middle at least one of thiophene (PO15), described metal material is selected from silver (Ag), aluminium (Al), platinum (Pt) and the middle at least one of gold (Au), described metal sulfide doped layer is prepared at described Organic Electron Transport Material doped layer surface evaporation by the mode of electron beam evaporation plating, described metal sulfide doped layer comprises metal sulfide and is entrained in the titanium dioxide in described metal sulfide, described metal sulfide material is selected from zinc sulphide (ZnS), cadmium sulfide (CdS), magnesium sulfide (MgS) and the middle at least one of copper sulfide (CuS), described titanium dioxide particle diameter is 20nm ~ 200nm.
Described in described doped metallic oxide layer 701, the mass ratio of metal oxide and described metal sulfide is 1:1 ~ 5:1, described in described Organic Electron Transport Material doped layer 702, the mass ratio of Organic Electron Transport Material and metal is 2:1 ~ 5:1, and described in described metal sulfide doped layer 703, the doping mass ratio of metal sulfide and described titanium dioxide is 1:2 ~ 5:1.
Described doped metallic oxide layer 701 thickness is 20nm ~ 50nm, and described Organic Electron Transport Material doped layer 702 thickness is 50nm ~ 250nm, and described metal sulfide doped layer 703 thickness is 100nm ~ 200nm.
The concrete technology condition of described thermal resistance evaporation mode is: operating pressure is 2 × 10 -3pa ~ 5 × 10 -5pa, operating current is 1A ~ 3A, and the evaporation rate of organic material is 0.1nm/s ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s.
The concrete technology condition of described electron beam evaporation plating mode is: operating pressure is 2 × 10 -3~ 5 × 10 -5pa, the energy density of electron beam evaporation plating is 10W/cm 2~ l00W/cm 2, the evaporation rate of organic material is 0.1nm/s ~ 1nm/s, and the evaporation rate of metal and metallic compound 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 to organic electroluminescence device provided by the invention is described in detail.
The embodiment of the present invention and the preparation used by 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 of Keithley company of the U.S. tests electric property.。
Embodiment 1
Structure prepared by the present embodiment is ITO/MoO 3/ NPB/Alq 3/ Bphen/LiF/MoO 3: CdS/TAZ:Ag/ZnS:TiO 2organic electroluminescence device, "/" presentation layer in the present embodiment and following examples, ": " represents doping.
First ITO is carried out photoetching treatment, be cut into required size, use liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface; Clean up and carry out suitable process to conductive substrates afterwards: oxygen plasma treatment, the processing time is 5min, and power is 30W; Evaporation hole injection layer, material is MoO 3, thickness is 60nm; Evaporation hole transmission layer, material is NPB, and thickness is 50nm; Evaporation luminescent layer, material is BCzVBi, and thickness is 30nm; Evaporation electron transfer layer, material is Bphen, and thickness is 160nm; Evaporation electron injecting layer, material is LiF, and thickness is 0.7nm; Evaporation negative electrode, adopt thermal resistance evaporation mode to prepare doped metallic oxide layer at described electron injecting layer surface evaporation, material is MoO 3: CdS, MoO 3be 3:1 with CdS mass ratio, thickness is, 25nm, then prepare Organic Electron Transport Material doped layer by thermal resistance evaporation, material is the mass ratio of TAZ:Ag, TAZ and Ag is 4:1, thickness is 150nm, and then have metal sulfide doped layer by electron beam evaporation plating preparation, material is ZnS:TiO 2, ZnS and TiO 2mass ratio be 1:1, thickness is 150nm, and particle diameter is 50nm.
The concrete technology condition of electron beam evaporation plating mode is: operating pressure is 8 × 10 -5pa, the energy density of electron beam evaporation plating is 30W/cm 2, the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 3nm/s;
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 8 × 10 -5pa, operating current is 3A, and the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 3nm/s;
Refer to Fig. 3, the structure being depicted as preparation in embodiment 1 is ITO/MoO 3/ NPB/Alq 3/ Bphen/LiF/MoO 3: CdS/TAZ:Ag/ZnS:TiO 2the structure prepared of organic electroluminescence device (curve 1) and comparative example be the current density of organic electroluminescence device (curve 2) and the relation of luminous efficiency of ITO/MoO3/NPB/Alq3/Bphen/LiF/Ag.In organic electroluminescence device prepared by comparative example, each layer thickness is identical with each layer thickness in organic electroluminescence device prepared by embodiment 1.
Can see from Fig. 3, under different current densities, the luminous efficiency of embodiment 1 is all larger than comparative example, the maximum lumen efficiency of embodiment 1 is 8.89lm/W, and comparative example be only 6.24lm/W, and the luminous efficiency of comparative example declines fast along with the increase of current density, this explanation, patent of the present invention is by preparing the cathode construction of sandwich construction, this cathode construction layer is by doped metallic oxide layer, Organic Electron Transport Material doped layer and metal sulfide doped layer composition, metal oxide is the effect that bipolarity metal oxide can play electric transmission, electronic transmission performance can be strengthened, add the transmitance that metal sulfide can improve light, Organic Electron Transport Material in Organic Electron Transport Material doped layer has crystallinity, crystalline material and metal adulterate, film surface can be made to form ripple struction, make the light scattering of Vertical Launch, no longer vertical, thus not with the free electron generation coupling of metal level, improve photon utilance, metal can improve the conductivity of organic electroluminescence device, finally prepare layer of metal sulfide doped layer, metal sulfide and titanium dioxide form, metal sulfide can realize the reflection of light, the light to top-emission is made to be reflected back bottom, titanium dioxide can increase the scattering of light, thus strengthen reflection efficiency thus improve luminous efficiency.
The luminous efficiency of organic electroluminescence device prepared of each embodiment is all similar with embodiment 1 below, and each organic electroluminescence device also has similar luminous efficiency, repeats no more below.
Embodiment 2
Structure prepared by the present embodiment is AZO/MoO 3/ TCTA/ADN/Bphen/CsF/WO 3: ZnS/OXD-7:Al/CdS:TiO 2organic electroluminescence device.
First AZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface; Evaporation hole injection layer: material is MoO 3, thickness is 80nm; Evaporation hole transmission layer: material is TCTA, thickness is 60nm; Evaporation luminescent layer: selected materials is ADN, thickness is 5nm; Evaporation electron transfer layer, material is Bphen, and thickness is 200nm; Evaporation electron injecting layer, material is CsF, and thickness is 10nm; Evaporation negative electrode, adopt thermal resistance evaporation mode to prepare doped metallic oxide layer at described electron injecting layer surface evaporation, material is WO 3: ZnS, WO 3be 1:1 with ZnS mass ratio, thickness is 50nm, then prepares Organic Electron Transport Material doped layer by thermal resistance evaporation, material is the mass ratio of OXD-7:Al, OXD-7 and Al is 2:1, and thickness is 50nm, then have metal sulfide doped layer by electron beam evaporation plating preparation, material is CdS:TiO 2, CdS and TiO 2mass ratio be 1:2, thickness is 200nm, and particle diameter is 20nm.
The concrete technology condition of electron beam evaporation plating mode is: operating pressure is 2 × 10 -3pa, the energy density of electron beam evaporation plating is 10W/cm 2, the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of metal and metallic compound is 10nm/s;
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 2 × 10 -3pa, operating current is 1A, and the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of metal and metallic compound is 10nm/s.
Embodiment 3
Structure prepared by the present embodiment is IZO/WO 3/ TAPC/Alq 3/ TAZ/Cs 2cO 3/ V 2o 5: the organic electroluminescence device of MgS/BCP:Pt/ZnS/.
First IZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface; Evaporation hole injection layer: material is WO 3, thickness is 20nm; Evaporation hole transmission layer: material is TAPC, thickness is 30nm; Evaporation luminescent layer: selected materials is Alq 3, thickness is 40nm; Evaporation electron transfer layer, material is TAZ, and thickness is 60nm; Evaporation electron injecting layer, material is Cs 2cO 3, thickness is 0.5nm; Evaporation negative electrode, adopt thermal resistance evaporation mode to prepare doped metallic oxide layer at described electron injecting layer surface evaporation, material is V 2o 5: MgS, V 2o 5be 5:1 with MgS mass ratio, thickness is 20nm, then prepares Organic Electron Transport Material doped layer by thermal resistance evaporation, material is the mass ratio of BCP:Pt, BCP and Pt is 5:1, and thickness is 250nm, then have metal sulfide doped layer by electron beam evaporation plating preparation, material is MgS:TiO 2, MgS and TiO 2mass ratio be 5:1, thickness is 100nm, and particle diameter is 200nm.
The concrete technology condition of electron beam evaporation plating mode is: operating pressure is 5 × 10 -5pa, the energy density of electron beam evaporation plating is 100W/cm 2, the evaporation rate of organic material is 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s;
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 5 × 10 -5pa, operating current is 1.5A, and the evaporation rate of organic material is 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s.
Embodiment 4
Structure prepared by the present embodiment is IZO/V 2o 5/ TCTA/DCJTB/Bphen/CsN 3/ MoO 3: CuS/PO15:Au/CuS:TiO 2organic electroluminescence device.
First IZO substrate of glass is used liquid detergent successively, deionized water, ultrasonic 15min, remove the organic pollution of glass surface; Evaporation hole injection layer: material is V 2o 5, thickness is 30nm; Evaporation hole transmission layer: material is TCTA, thickness is 50nm; Evaporation luminescent layer: selected materials is DCJTB, thickness is 5nm; Evaporation electron transfer layer, material is Bphen, and thickness is 40nm; Evaporation electron injecting layer, material is CsN 3, thickness is 0.5nm; Evaporation negative electrode, adopt thermal resistance evaporation mode to prepare doped metallic oxide layer at described electron injecting layer surface evaporation, material is MoO 3: CuS, MoO 3be 3:2 with CuS mass ratio, thickness is 40nm, then prepares Organic Electron Transport Material doped layer by thermal resistance evaporation, material is the mass ratio of PO15:Au, PO15 and Au is 4:1, and thickness is 100nm, then have metal sulfide doped layer by electron beam evaporation plating preparation, material is CuS:TiO 2, CuS and TiO 2mass ratio be 7:2, thickness is 180nm, and particle diameter is 50nm.
The concrete technology condition of electron beam evaporation plating mode is: operating pressure is 5 × 10 -4pa, the energy density of electron beam evaporation plating is 50W/cm 2, the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 5nm/s;
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 5 × 10 -4pa, operating current is 2A, and the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 5nm/s.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not 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 stacked gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described cathode layer is by doped metallic oxide layer, Organic Electron Transport Material doped layer and metal sulfide doped layer composition, described doped metallic oxide layer comprises metal oxide and is entrained in the metal sulfide in described metal oxide, described metal oxide is selected from molybdenum trioxide, at least one in tungstic acid and vanadic oxide, described metal sulfide is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide, described Organic Electron Transport Material doped layer comprises Organic Electron Transport Material and is entrained in the metal in described Organic Electron Transport Material, described Organic Electron Transport Material is selected from 1, 2, 4-triazole derivative, 2, 2'-(1, 3-phenyl) two [5-(4-tert-butyl-phenyl)-1, 3, 4-oxadiazoles], 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene and 2, 8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] at least one in thiophene, described metal is selected from silver, aluminium, at least one in platinum and gold, described metal sulfide doped layer comprises metal sulfide and is entrained in the titanium dioxide in described metal sulfide, described metal sulfide is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide.
2. organic electroluminescence device according to claim 1, it is characterized in that, described in described doped metallic oxide layer, the mass ratio of metal oxide and described metal sulfide is 1:1 ~ 5:1, described in described Organic Electron Transport Material doped layer, the mass ratio of Organic Electron Transport Material and metal is 2:1 ~ 5:1, and described in described metal sulfide doped layer, the doping mass ratio of metal sulfide and described titanium dioxide is 1:2 ~ 5:1.
3. organic electroluminescence device according to claim 1, it is characterized in that, described doped metallic oxide layer thickness is 20nm ~ 50nm, and described Organic Electron Transport Material doped layer thickness is 50nm ~ 250nm, and described metal sulfide doped layer thickness is 100nm ~ 200nm.
4. organic electroluminescence device according to claim 1, it is characterized in that, the material of described luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river pyridine of a specified duration-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 hole injection layer is selected from least one in molybdenum trioxide, tungstic acid and vanadic oxide.
5. organic electroluminescence device according to claim 1, it is characterized in that, the material of described hole transmission layer is selected from 1, 1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane, 4, 4', 4''-tri-(carbazole-9-base) triphenylamine and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine, the material of described 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, the material of described electron injecting layer is selected from cesium carbonate, cesium fluoride, at least one in nitrine caesium and lithium fluoride.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
Hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer is formed successively at anode surface; And
Doped metallic oxide layer is prepared by the method for thermal resistance evaporation on electron injecting layer surface, described doped metallic oxide layer comprises metal oxide and is entrained in the metal sulfide in described metal oxide, described metal oxide is selected from molybdenum trioxide, at least one in tungstic acid and vanadic oxide, described metal sulfide is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide, then Organic Electron Transport Material doped layer is prepared on described doped metallic oxide layer surface by thermal resistance evaporation mode, described Organic Electron Transport Material doped layer comprises Organic Electron Transport Material and is entrained in the metal in described Organic Electron Transport Material, described Organic Electron Transport Material is selected from 1, 2, 4-triazole derivative, 2, 2'-(1, 3-phenyl) two [5-(4-tert-butyl-phenyl)-1, 3, 4-oxadiazoles], 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene and 2, 8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] at least one in thiophene, described metal is selected from silver, aluminium, at least one in platinum and gold, described metal sulfide doped layer is prepared at described Organic Electron Transport Material doped layer surface evaporation by the mode of electron beam evaporation plating, described metal sulfide doped layer comprises metal sulfide and is entrained in the titanium dioxide in described metal sulfide, described metal sulfide is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide.
7. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that: described in described doped metallic oxide layer, the mass ratio of metal oxide and described metal sulfide is 1:1 ~ 5:1, described in described Organic Electron Transport Material doped layer, the mass ratio of Organic Electron Transport Material and metal is 2:1 ~ 5:1, and described in described metal sulfide doped layer, the doping mass ratio of metal sulfide and described titanium dioxide is 1:2 ~ 5:1.
8. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that: described first metal sulfide layer thickness is 10nm ~ 30nm, described metal sulfide doped layer thickness is 5nm ~ 50nm, and described second metal sulfide layer thickness is 100nm ~ 300nm.
9. the preparation method of organic electroluminescence device according to claim 6, is characterized in that: the concrete technology condition of described thermal resistance evaporation mode is: operating pressure is 2 × 10 -3pa ~ 5 × 10 -5pa, operating current is 1A ~ 3A, and the evaporation rate of organic material is 0.1nm/s ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s.
10. the preparation method of organic electroluminescence device according to claim 6, is characterized in that: the concrete technology condition of described electron beam evaporation plating mode is: operating pressure is 2 × 10 -3~ 5 × 10 -5pa, the energy density of electron beam evaporation plating is 10W/cm 2~ l00W/cm 2, the evaporation rate of organic material is 0.1nm/s ~ 1nm/s, and the evaporation rate of metal and metallic compound is 1nm/s ~ 10nm/s.
CN201310452076.3A 2013-09-27 2013-09-27 Organic electroluminescent device and method for preparing same Pending CN104518145A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105226199A (en) * 2015-10-14 2016-01-06 上海大学 Be applied to the bielectron implanted layer structure of organic electroluminescence device, be inverted organic electroluminescence device and preparation method thereof
CN113044882A (en) * 2019-12-27 2021-06-29 Tcl集团股份有限公司 Nano material, preparation method thereof and quantum dot light-emitting diode

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105226199A (en) * 2015-10-14 2016-01-06 上海大学 Be applied to the bielectron implanted layer structure of organic electroluminescence device, be inverted organic electroluminescence device and preparation method thereof
CN113044882A (en) * 2019-12-27 2021-06-29 Tcl集团股份有限公司 Nano material, preparation method thereof and quantum dot light-emitting diode
CN113044882B (en) * 2019-12-27 2022-06-10 Tcl科技集团股份有限公司 Nano material and preparation method thereof, and quantum dot light-emitting diode

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