CN104518106A - Organic light-emitting device and making method thereof - Google Patents

Organic light-emitting device and making method thereof Download PDF

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Publication number
CN104518106A
CN104518106A CN201310451695.0A CN201310451695A CN104518106A CN 104518106 A CN104518106 A CN 104518106A CN 201310451695 A CN201310451695 A CN 201310451695A CN 104518106 A CN104518106 A CN 104518106A
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layer
organic
metal
evaporation
oxide
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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
    • H10K50/10—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
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/82—Cathodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/302—Details of OLEDs of OLED structures

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  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

An organic light-emitting device comprises an anode, a hole injection layer, a hole transmission layer, a lighting layer, an electronic transmission layer, an electronic injection layer and a cathode stacked in sequence; the cathode layer comprises an organic electronic transmission dope layer, a VB group oxide layer, a metal layer and a metal sulfide layer; the organic electronic transmission dope layer comprises an organic electronic transmission material and a bipolar metal oxide doped in the organic electronic transmission material; the bipolar metal oxide is made of at least one material from a group formed by molybdenum trioxide, tungsten trioxide and vanadium pentoxide; the VB group oxide layer is made of at least one material from a group formed by tantalum pentoxide, niobium pentoxide and vanadium pentoxide; the metal layer material is selected from at least one from a group formed by silver, aluminum, platinum and gold; the metal sulfide layer material is selected from at least one from a group formed by zinc sulfide, cadmium sulfide, magnesium sulfide and copper sulfide; the organic light-emitting device is high in lighting efficiency; the invention also provides an organic light-emitting device making 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
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, comprises the anode stacked gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described cathode layer transmits doped layer by organic electronic, VB race oxide skin(coating), metal level and metal sulfide layer composition, described organic electronic transmission doped layer comprises Organic Electron Transport Material and is entrained in the bipolarity metal oxide in described Organic Electron Transport Material, described Organic Electron Transport Material is selected from 2, 2'-(1, 3-phenyl) two [5-(4-tert-butyl-phenyl)-1, 3,4-oxadiazoles], at least one in 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene and 2,8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] thiophene, described bipolarity metal oxide materials is selected from molybdenum trioxide, at least one in tungstic acid and vanadic oxide, described VB race oxide skin(coating) material is selected from tantalum pentoxide, at least one in niobium pentaoxide and vanadic oxide, described metal layer material is selected from silver, aluminium, at least one in platinum and gold, described metal sulfide layer material is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide.
The mass ratio of described Organic Electron Transport Material and described bipolarity metal oxide is 2:1 ~ 10:1.
Described organic electronic transmission doped layer thickness is 50nm ~ 150nm, and described VB race oxide layer thicknesses is 20nm ~ 60nm, and described metal layer thickness is 2nm ~ 10nm and described metal sulfide layer thickness is 50nm ~ 300nm.
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 molybdenum trioxide, at least one in 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, 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.
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
Organic electronic transmission doped layer is prepared by the method for thermal resistance evaporation on electron injecting layer surface, organic electronic transmission doped layer comprises Organic Electron Transport Material and is entrained in the bipolarity metal oxide in described Organic Electron Transport Material, described Organic Electron Transport Material is selected from 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 bipolarity metal oxide materials is selected from molybdenum trioxide, at least one in tungstic acid and vanadic oxide, adopt electron beam evaporation plating mode at described organic electronic transmission doped layer surface preparation described VB race oxide skin(coating), described VB race oxide skin(coating) material is selected from tantalum pentoxide, at least one in niobium pentaoxide and vanadic oxide, metal level is prepared at described VB race oxide layer surface evaporation by thermal resistance evaporation mode, described metal layer material is selected from silver, aluminium, at least one in platinum and gold, by thermal resistance evaporation mode metal sulfide layer described in described layer on surface of metal evaporation, described metal sulfide layer material is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide.
The mass ratio of described Organic Electron Transport Material and described bipolarity metal oxide is 2:1 ~ 10:1.
Described organic electronic transmission doped layer thickness is 50nm ~ 150nm, and described VB race oxide layer thicknesses is 20nm ~ 60nm, and described metal layer thickness is 2nm ~ 10nm and described metal sulfide layer thickness is 50nm ~ 300nm.
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.
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.
Above-mentioned organic electroluminescence device and preparation method thereof, by preparing the cathode construction of sandwich construction, this cathode construction layer transmits doped layer by organic electronic, VB race oxide skin(coating), metal level and metal sulfide layer composition, organic electron transport layer is that crystalline material and bipolarity metal oxide adulterate, crystallization can be molecule segment marshalling, film surface is made to form ripple struction, make the light scattering of Vertical Launch, no longer vertical, thus can not be coupled with the free electron of metal level (parallel free electron can be coupled with vertical photon and lose), improve photon utilance, bipolarity metal oxide can provide electronics, form n with crystalline material to adulterate, further raising electron transfer rate, prepare one deck VB race oxide skin(coating) again, VB family metal oxide refractive index is higher, and transmitance reaches about 80% ~ 85% in visible-range, the transmitance of device can be improved, metal level can improve the conductivity of organic electroluminescence device, finally prepare layer of metal sulfide, metal sulfide is by the adjustment of thickness, the reflection of light can be realized, the light to top-emission is made to reflect back into bottom, thus strengthen light extraction 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 current 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 60nm.
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 50nm.
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 30nm.
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 160nm.
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 0.7nm.
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 transmits doped layer 701 by organic electronic, VB race oxide skin(coating) 702, metal level 703 and metal sulfide layer 704 form, organic electronic transmission doped layer 701 comprises Organic Electron Transport Material and is entrained in the bipolarity metal oxide in described Organic Electron Transport Material, the HOMO energy level of 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 bipolarity metal oxide materials is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) middle at least one, described VB race oxide skin(coating) material is selected from tantalum pentoxide (Ta 2o 5), niobium pentaoxide (Nb 2o 5) and vanadic oxide (V 2o 5) middle at least one, described metal layer material is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au), and described metal sulfide layer material is selected from least one in zinc sulphide (ZnS), cadmium sulfide (CdS), magnesium sulfide (MgS) and copper sulfide (CuS).
The mass ratio of described Organic Electron Transport Material and described bipolarity metal oxide is 2:1 ~ 10:1.
Described organic electronic transmission doped layer 701 thickness is 50nm ~ 150nm, and described VB race oxide skin(coating) 702 thickness is 20nm ~ 60nm, and described metal level 703 thickness is 2nm ~ 10nm, and described metal sulfide layer 704 thickness is 50nm ~ 300nm.
Above-mentioned organic electroluminescence device 100 is by preparing the cathode construction of sandwich construction, this cathode construction layer transmits doped layer by organic electronic, VB race oxide skin(coating), metal level and metal sulfide layer composition, organic electron transport layer is that crystalline material and bipolarity metal oxide adulterate, crystallization can be molecule segment marshalling, film surface is made to form ripple struction, make the light scattering of Vertical Launch, no longer vertical, thus can not be coupled with the free electron of metal level (parallel free electron can be coupled with vertical photon and lose), improve photon utilance, bipolarity metal oxide can provide electronics, form n with crystalline material to adulterate, further raising electron transfer rate, prepare one deck VB race oxide skin(coating) again, VB family metal oxide refractive index is higher, and transmitance reaches about 80% ~ 85% in visible-range, the transmitance of device can be improved, metal level can improve the conductivity of organic electroluminescence device, finally prepare layer of metal sulfide, metal sulfide is by the adjustment of thickness, the reflection of light can be realized, the light to top-emission is made to reflect back into bottom, thus strengthen light extraction 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 60nm.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 50nm.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 30nm.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 160nm.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 0.7nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Step S120, organic electronic transmission doped layer 701 is prepared by the method for thermal resistance evaporation on electron injecting layer surface, organic electronic transmission doped layer 701 comprises Organic Electron Transport Material and is entrained in the bipolarity metal oxide in described Organic Electron Transport Material, the HOMO energy level of 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 bipolarity metal oxide materials is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) middle at least one, adopt electron beam evaporation plating mode at described organic electronic transmission doped layer 701 surface preparation described VB race oxide skin(coating) 702, described VB race oxide skin(coating) material is selected from tantalum pentoxide (Ta 2o 5), niobium pentaoxide (Nb 2o 5) and vanadic oxide (V 2o 5) middle at least one, metal level 703 is prepared at the described VB race surperficial evaporation of oxide skin(coating) 702 by thermal resistance evaporation mode, described metal level 703 material is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au), by thermal resistance evaporation mode metal sulfide layer 704 described in the surperficial evaporation of described metal level 703, described metal sulfide layer 704 material is selected from least one in zinc sulphide (ZnS), cadmium sulfide (CdS), magnesium sulfide (MgS) and copper sulfide (CuS).
The mass ratio of described Organic Electron Transport Material and described bipolarity metal oxide is 2:1 ~ 10:1.
Described organic electronic transmission doped layer 701 thickness is 50nm ~ 150nm, and described VB race oxide skin(coating) 702 thickness is 20nm ~ 60nm, and described metal level 703 thickness is 2nm ~ 10nm, and described metal sulfide layer 704 thickness is 50nm ~ 300nm.
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.
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.
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/WO 3/ NPB/Alq 3/ Bphen/LiF/TAZ:MoO 3/ Ta 2o 5the organic electroluminescence device of/Ag/ZnS/, "/" 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 WO 3, thickness is 35nm; Evaporation hole transmission layer, material is NPB, and thickness is 40nm; Evaporation luminescent layer, material is Alq 3, thickness is 15nm; Evaporation electron transfer layer, material is Bphen, and thickness is 250nm; Evaporation electron injecting layer, material is LiF, and thickness is 0.7nm; Evaporation negative electrode, adopt thermal resistance evaporation mode to prepare organic electronic transmission doped layer at described electron injecting layer surface evaporation, material is TAZ:MoO 3, TAZ and MoO 3mass ratio be 3:1, thickness is 100nm, then prepares VB race oxide skin(coating) by thermionic electron beam evaporation, and material is Ta 2o 5, thickness is 35nm, then prepares metal level by thermal resistance evaporation mode, and material is Ag, and thickness is 5nm, then prepares metal sulfide layer by thermal resistance evaporation mode, and material is ZnS, and thickness is 200nm.
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 1A, 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/WO 3/ NPB/Alq 3/ Bphen/LiF/TAZ:MoO 3/ Ta 2o 5structure prepared by organic electroluminescence device (curve 1) and the comparative example of/Ag/ZnS/ is ito glass/MoO 3/ NPB/Alq 3the current density of organic electroluminescence device (curve 2) of/Bphen/LiF/Ag and the relation of current efficiency.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 current efficiency of embodiment 1 is all larger than comparative example, the maximum current efficiency of embodiment 1 is 7.59cd/A, and comparative example be only 5.40cd/A, and the current density of comparative example declines fast along with the increase of current efficiency, this explanation, patent of the present invention is by preparing the cathode construction of sandwich construction, this cathode construction layer transmits doped layer by organic electronic, VB race oxide skin(coating), metal level and metal sulfide layer composition, organic electron transport layer is that crystalline material and bipolarity metal oxide adulterate, crystallization can be molecule segment marshalling, film surface is made to form ripple struction, make the light scattering of Vertical Launch, no longer vertical, thus can not be coupled with the free electron of metal level (parallel free electron can be coupled with vertical photon and lose), improve photon utilance, bipolarity metal oxide can provide electronics, form n with crystalline material to adulterate, further raising electron transfer rate, prepare one deck VB race oxide skin(coating) again, VB family metal oxide refractive index is higher, and transmitance reaches about 80% ~ 85% in visible-range, the transmitance of device can be improved, metal level can improve the conductivity of organic electroluminescence device, finally prepare layer of metal sulfide, metal sulfide is by the adjustment of thickness, the reflection of light can be realized, the light to top-emission is made to reflect back into bottom, thus strengthen light extraction efficiency thus improve luminous efficiency.
The current efficiency of organic electroluminescence device prepared of each embodiment is all similar with embodiment 1 below, and each organic electroluminescence device also has similar current efficiency, repeats no more below.
Embodiment 2
Structure prepared by the present embodiment is AZO/MoO 3/ NPB/ADN/TAZ/CsF/OXD-7:WO 3/ Nb 2o 5the organic electroluminescence device of/Al/CdS.
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 NPB, thickness is 60nm; Evaporation luminescent layer: selected materials is ADN, thickness is 5nm; Evaporation electron transfer layer, material is TAZ, and thickness is 75nm; Evaporation electron injecting layer, material is CsF, and thickness is 10nm; Evaporation negative electrode, adopt thermal resistance evaporation mode to prepare organic electronic transmission doped layer at described electron injecting layer surface evaporation, material is OXD-7:WO 3, OXD-7 and WO 3mass ratio be 2:1, thickness is 50nm, then prepares VB race oxide skin(coating) by thermionic electron beam evaporation, and material is Nb 2o 5, thickness is 60nm, then prepares metal level by thermal resistance evaporation mode, and material is Al, and thickness is 2nm, then prepares metal sulfide layer by thermal resistance evaporation mode, and material is CdS, and thickness is 50nm.
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 3A, 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/BCzVBi/TPBi/Cs 2cO 3/ BCP: v2O 5/ V 2o 5the organic electroluminescence device of/Pt/MgS.
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 BCzVBi, thickness is 40nm; Evaporation electron transfer layer, material is TPBi, 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 organic electronic transmission doped layer at described electron injecting layer surface evaporation, material is BCP:V 2o 5, BCP and V 2o 5mass ratio be 10:1, thickness is 150nm, then prepares VB race oxide skin(coating) by thermionic electron beam evaporation, and material is V 2o 5, thickness is 20nm, then prepares metal level by thermal resistance evaporation mode, and material is Pt, and thickness is 10nm, then prepares metal sulfide layer by thermal resistance evaporation mode, and material is MgS, and thickness is 300nm.
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/ PO15:MoO 3/ Ta 2o 5the organic electroluminescence device of/Au/CuS.
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 organic electronic transmission doped layer at described electron injecting layer surface evaporation, material is PO15:MoO 3, PO15 and MoO 3mass ratio be 4:1, thickness is 70nm, then prepares VB race oxide skin(coating) by thermionic electron beam evaporation, and material is Ta 2o 5, thickness is 50nm, then prepares metal level by thermal resistance evaporation mode, and material is Au, and thickness is 6nm, then prepares metal sulfide layer by thermal resistance evaporation mode, and material is CuS, and thickness is 100nm.
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 1.8A, 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 (9)

1. an organic electroluminescence device, is characterized in that, comprises the anode stacked gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described cathode layer transmits doped layer by organic electronic, VB race oxide skin(coating), metal level and metal sulfide layer composition, described organic electronic transmission doped layer comprises Organic Electron Transport Material and is entrained in the bipolarity metal oxide in described Organic Electron Transport Material, described Organic Electron Transport Material is selected from 2, 2'-(1, 3-phenyl) two [5-(4-tert-butyl-phenyl)-1, 3,4-oxadiazoles], at least one in 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene and 2,8-bis-(diphenyl phosphine oxygen base) dibenzo [b, d] thiophene, described bipolarity metal oxide materials is selected from molybdenum trioxide, at least one in tungstic acid and vanadic oxide, described VB race oxide skin(coating) material is selected from tantalum pentoxide, at least one in niobium pentaoxide and vanadic oxide, described metal layer material is selected from silver, aluminium, at least one in platinum and gold, described metal sulfide layer material is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide.
2. organic electroluminescence device according to claim 1, is characterized in that, the mass ratio of described Organic Electron Transport Material and described bipolarity metal oxide is 2:1 ~ 10:1.
3. organic electroluminescence device according to claim 1, it is characterized in that, described organic electronic transmission doped layer thickness is 50nm ~ 150nm, described VB race oxide layer thicknesses is 20nm ~ 60nm, and described metal layer thickness is 2nm ~ 10nm and described metal sulfide layer thickness is 50nm ~ 300nm.
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 molybdenum trioxide, at least one in 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, 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.
5. 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
Organic electronic transmission doped layer is prepared by the method for thermal resistance evaporation on electron injecting layer surface, organic electronic transmission doped layer comprises Organic Electron Transport Material and is entrained in the bipolarity metal oxide in described Organic Electron Transport Material, described Organic Electron Transport Material is selected from 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 bipolarity metal oxide materials is selected from molybdenum trioxide, at least one in tungstic acid and vanadic oxide, adopt electron beam evaporation plating mode at described organic electronic transmission doped layer surface preparation described VB race oxide skin(coating), described VB race oxide skin(coating) material is selected from tantalum pentoxide, at least one in niobium pentaoxide and vanadic oxide, metal level is prepared at described VB race oxide layer surface evaporation by thermal resistance evaporation mode, described metal layer material is selected from silver, aluminium, at least one in platinum and gold, by thermal resistance evaporation mode metal sulfide layer described in described layer on surface of metal evaporation, described metal sulfide layer material is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide.
6. the preparation method of organic electroluminescence device according to claim 5, is characterized in that: the mass ratio of described Organic Electron Transport Material and described bipolarity metal oxide is 2:1 ~ 10:1.
7. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that: described organic electronic transmission doped layer thickness is 50nm ~ 150nm, described VB race oxide layer thicknesses is 20nm ~ 60nm, and described metal layer thickness is 2nm ~ 10nm and described metal sulfide layer thickness is 50nm ~ 300nm.
8. the preparation method of organic electroluminescence device according to claim 5, 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.
9. the preparation method of organic electroluminescence device according to claim 5, 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.
CN201310451695.0A 2013-09-27 2013-09-27 Organic light-emitting device and making method thereof Pending CN104518106A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107851735A (en) * 2015-06-23 2018-03-27 诺瓦尔德股份有限公司 Organic luminescent device comprising polarity matrix and metal dopant

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107851735A (en) * 2015-06-23 2018-03-27 诺瓦尔德股份有限公司 Organic luminescent device comprising polarity matrix and metal dopant
US10749115B2 (en) 2015-06-23 2020-08-18 Novaled Gmbh N-doped semiconducting material comprising polar matrix and metal dopant

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