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CN104518138A - Organic electroluminescent device and preparation method thereof - Google Patents

Organic electroluminescent device and preparation method thereof Download PDF

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Publication number
CN104518138A
CN104518138A CN201310451506.XA CN201310451506A CN104518138A CN 104518138 A CN104518138 A CN 104518138A CN 201310451506 A CN201310451506 A CN 201310451506A CN 104518138 A CN104518138 A CN 104518138A
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layer
organic
metal sulfide
doped layer
metal
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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
    • 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
    • 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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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention provides an organic electroluminescent device. The organic electroluminescent device comprises an anode, a cavity implantation layer, a cavity transmission layer, a luminescent layer, an electron transmission layer, an electron injecting layer and a cathode which are successively stacked. A cathode layer is composed of a metal sulfide doping layer, an organic electron transmission layer and a film material layer. The material of the metal sulfide doping layer comprises metal sulfide and metal doped in the metal sulfide. An organic electron transmission doping layer comprises an organic electron transmission material and titanium dioxide doped in the organic electron transmission material. The material of the organic electron transmission doping layer is selected from at least one from 2,2'-(1,3-pheyl)bis[5-(4- tert-butyl phenyl)-1,3,4-oxadiazol], 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline and 2,8-bis(diphenylphosphinoxy) dibenzo[b,d] thiophene. The material of the film material layer is selected from at least one from an indium tin oxide target material, an aluminum zinc oxide target material and an indium zinc oxide target material.

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 is by metal sulfide doped layer, organic electronic transmission doped layer and film material plies composition, described metal sulfide doped layer comprises metal sulfide and is entrained in the metal in described metal sulfide, and described metal sulfide layer material is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide, metal layer material is selected from silver, aluminium, at least one in platinum and gold, the titanium dioxide that described organic electronic transmission doped layer comprises described Organic Electron Transport Material and is entrained in described Organic Electron Transport Material, described organic electron transport layer 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, thin-film material layer material is selected from indium-tin oxide target material, at least one in aluminium zinc oxide target and indium-zinc oxide target.
Described in described metal sulfide doped layer, the doping mass ratio of metal sulfide and described metal is 5:1 ~ 10:1, and described in described organic electronic transmission doped layer, Organic Electron Transport Material and described titanium dioxide mass ratio are 20:1 ~ 5:1.
Described metal sulfide doped layer thickness is 10nm ~ 60nm, and described organic electronic transmission doped layer thickness is 50nm ~ 100nm and thin-film material layer thickness is 100nm ~ 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
Metal sulfide doped layer is prepared by the method for thermal resistance evaporation on electron injecting layer surface, described metal sulfide doped layer comprises metal sulfide and is entrained in the metal in described metal sulfide, 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, described organic electronic transmission doped layer is prepared at described metal sulfide doped layer surface evaporation by the mode of electron beam evaporation plating, the titanium dioxide that described organic electronic transmission doped layer comprises described Organic Electron Transport Material and is entrained in described Organic Electron Transport Material, described organic electron transport layer 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, by magnetron sputtering mode in described organic electronic transmission doped layer surface preparation membrane layers, thin-film material layer material is selected from indium-tin oxide target material, at least one in aluminium zinc oxide target and indium-zinc oxide target, adopt thermal resistance evaporation mode at the described metal level of described film material plies surface preparation, described metal layer material is selected from silver, aluminium, at least one in platinum and gold.
Described in described metal sulfide doped layer, the doping mass ratio of metal sulfide and described metal is 5:1 ~ 10:1, and described in described organic electronic transmission doped layer, Organic Electron Transport Material and described titanium dioxide mass ratio are 20:1 ~ 5:1.
Described metal sulfide doped layer thickness is 10nm ~ 60nm, and described organic electronic transmission doped layer thickness is 50nm ~ 100nm and thin-film material 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 magnetron sputtering mode is: operating pressure is 2 × 10 -3~ 5 × 10 -5pa, the accelerating voltage of magnetron sputtering: 300V ~ 800V, magnetic field about: 50G ~ 200G, power density: 1W/cm 2~ 40W/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 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 metal sulfide doped layer, organic electronic transmission doped layer and film material plies composition, metal sulfide doped layer can improve rete evenness, refractive index height effectively can avoid total reflection, improve transmitance in visible-range, organic electronic transmission doped layer is that crystalline material mixes with titanium dioxide, 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, titanium dioxide particle diameter effectively can improve more greatly the scattering of light, prepare thin film material layer layer again, the transmitance of light can be strengthened, improve carrier concentration strengthen light extraction efficiency thus improve luminous efficiency simultaneously.
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 luminous efficiency and the brightness relationship figure 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 50nm.
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 20nm.
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 100nm.
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 is by metal sulfide layer 701, organic electron transport layer 702, film material plies 703 and metal level 704 form, described metal sulfide doped layer 701, described metal sulfide doped layer 701 comprises metal sulfide and is entrained in the metal 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 metal material is selected from silver, aluminium, at least one in platinum and gold, the titanium dioxide that described organic electronic transmission doped layer 702 comprises described Organic Electron Transport Material and is entrained in described Organic Electron Transport Material, the HOMO energy level of organic electron transport layer 702 is at-6.5eV ~-7.5eV, glass transition temperature is at 50 DEG C ~ 100 DEG C, concrete material is selected from 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), titanium dioxide particle diameter is 50nm ~ 200nm, film material plies 703 material is selected from indium-tin oxide target material (ITO), aluminium zinc oxide target (AZO) and the middle at least one of indium-zinc oxide target (IZO).
Described in described metal sulfide doped layer 701, the doping mass ratio of metal sulfide and described metal is 5:1 ~ 10:1, and described in described organic electronic transmission doped layer 702, Organic Electron Transport Material and described titanium dioxide mass ratio are 20:1 ~ 5:1.
Described metal sulfide doped layer 701 thickness is 10nm ~ 60nm, and described organic electronic transmission doped layer 702 thickness is 50nm ~ 100nm, and film material plies 703 thickness is 100nm ~ 300nm.
Above-mentioned organic electroluminescence device 100 is by preparing the cathode construction of sandwich construction, this cathode construction layer is by metal sulfide doped layer, organic electronic transmission doped layer and film material plies composition, metal sulfide doped layer can improve rete evenness, refractive index height effectively can avoid total reflection, improve transmitance in visible-range, organic electronic transmission doped layer is that crystalline material mixes with titanium dioxide, 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, titanium dioxide particle diameter effectively can improve more greatly the scattering of light, prepare thin film material layer layer again, the transmitance of light can be strengthened, improve carrier concentration strengthen light extraction efficiency thus improve luminous efficiency simultaneously.
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 50nm.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 20nm.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 100nm.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, metal sulfide doped layer 701 is prepared by the method for thermal resistance evaporation on electron injecting layer surface, described metal sulfide doped layer 701 comprises metal sulfide and is entrained in the metal in described metal sulfide, described metal sulfide layer 701 material is selected from zinc sulphide (ZnS), cadmium sulfide (CdS), magnesium sulfide (MgS) and the middle at least one of copper sulfide (CuS), metal material work function is-4.0 ~-5.5eV, specifically be selected from silver (Ag), aluminium (Al), platinum (Pt) and the middle at least one of gold (Au), adopt electron beam evaporation plating mode at described metal sulfide doped layer 701 surface preparation described organic electronic transmission doped layer 702, the titanium dioxide that described organic electronic transmission doped layer 702 comprises described Organic Electron Transport Material and is entrained in described Organic Electron Transport Material, the HOMO energy level of described organic electron transport layer 702 is at-6.5eV ~-7.5eV, glass transition temperature is at 50 DEG C ~ 100 DEG C, concrete material is selected from 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 titanium dioxide particle diameter is 50nm ~ 200nm, film material plies 703 is prepared at the surperficial evaporation of described organic electronic transmission doped layer 702 by magnetron sputtering mode, film material plies 703 material is selected from indium-tin oxide target material (ITO), aluminium zinc oxide target (AZO) and the middle at least one of indium-zinc oxide target (IZO).
Described in described metal sulfide doped layer 701, the doping mass ratio of metal sulfide and described metal is 5:1 ~ 10:1, and described in described organic electronic transmission doped layer 702, Organic Electron Transport Material and described titanium dioxide mass ratio are 20:1 ~ 5:1.
Described metal sulfide doped layer 701 thickness is 10nm ~ 60nm, and described organic electronic transmission doped layer 702 thickness is 50nm ~ 100nm, and film material plies 703 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 magnetron sputtering mode is: operating pressure is 2 × 10 -3~ 5 × 10 -5pa, the accelerating voltage of magnetron sputtering: 300V ~ 800V, magnetic field about: 50G ~ 200G, power density: 1W/cm 2~ 40W/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 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/WO 3/ NPB/Alq 3/ Bphen/LiF/ZnS:Ag/TAZ:TiO 2the organic electroluminescence device of/ITO, "/" 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 60nm; Evaporation hole transmission layer, material is NPB, and thickness is 30nm; Evaporation luminescent layer, material is BCzVBi, and thickness is 30nm; Evaporation electron transfer layer, material is Bphen, and thickness is 50nm; Evaporation electron injecting layer, material is LiF, and thickness is 0.7nm; Evaporation negative electrode, adopt thermal resistance evaporation mode to prepare metal sulfide doped layer at described electron injecting layer surface evaporation, material is ZnS:Ag, the mass ratio of ZnS and Ag is 7:1, thickness is 25nm, and then prepare organic electronic transmission doped layer by electron beam evaporation plating, material is TAZ:TiO 2, TAZ and TiO 2mass ratio is 15:1, and thickness is 150nm, and titanium dioxide particle diameter is 80nm, and then by Magnetron Sputtering Thin Film material layer, material is ITO, and thickness is 150nm, prepares metal level finally by thermal resistance evaporation, and material is Ag, 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;
The concrete technology condition of magnetron sputtering mode is: operating pressure is 8 × 10 -5pa, the accelerating voltage of magnetron sputtering: 400V, magnetic field about: 100G, power density: 15W/cm 2, the evaporation rate of organic material is 0.3nm/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/ZnS:Ag/TAZ:TiO 2structure prepared by organic electroluminescence device (curve 1) and the comparative example of/ITO is ito glass/MoO 3/ NPB/Alq 3the brightness of organic electroluminescence device (curve 2) of/Bphen/LiF/Ag and the relation of luminous 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 brightness, the luminous efficiency of embodiment 1 is all larger than comparative example, the maximum lumen efficiency of embodiment 1 is 13.62lm/W, and comparative example be only 8.31lm/W, and the luminous efficiency of comparative example declines fast along with the increase of brightness, this explanation, patent of the present invention is by preparing the cathode construction of sandwich construction, this cathode construction layer is by metal sulfide doped layer, organic electronic transmission doped layer and film material plies composition, metal sulfide doped layer can improve rete evenness, refractive index height effectively can avoid total reflection, improve transmitance in visible-range, organic electronic transmission doped layer is that crystalline material mixes with titanium dioxide, 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, titanium dioxide particle diameter effectively can improve more greatly the scattering of light, prepare thin film material layer layer again, the transmitance of light can be strengthened, improve carrier concentration strengthen light extraction efficiency thus improve luminous efficiency simultaneously.
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/CdS:Al/OXD-7:TiO 2the organic electroluminescence device of/AZO.
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 metal sulfide doped layer at described electron injecting layer surface evaporation, material is CdS:Al, the mass ratio of CdS and Al is 5:1, thickness is 10nm, and then prepare organic electronic transmission doped layer by electron beam evaporation plating, material is OXD-7:TiO 2, OXD-7 and TiO 2mass ratio is 20:1, and titanium dioxide particle diameter is 200nm, and thickness is 100nm, and then by Magnetron Sputtering Thin Film material layer, material is AZO, and thickness is 300nm.
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;
The concrete technology condition of magnetron sputtering mode is: operating pressure is 2 × 10 -3pa, the accelerating voltage of magnetron sputtering: 300V, magnetic field about: 200G, power density: 1W/cm 2, 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/ MgS:Pt/BCP:TiO 2the organic electroluminescence device of/IZO/.
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 metal sulfide doped layer at described electron injecting layer surface evaporation, material is MgS:Pt, MgS and Pt mass ratio is 10:1, and thickness is, 60nm, then prepare organic electronic transmission doped layer by thermal resistance evaporation, material is BCP:TiO 2, BCP and TiO 2mass ratio is 5:1, and thickness is, 50nm, and titanium dioxide particle diameter is 50nm, and then by Magnetron Sputtering Thin Film material layer, material is IZO, and thickness is 100nm.
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;
The concrete technology condition of magnetron sputtering mode is: operating pressure is 5 × 10 -5pa, the accelerating voltage of magnetron sputtering: 800V, magnetic field about: 50G, power density: 40W/cm 2, 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/ CuS:Au/PO15:TiO 2the organic electroluminescence device of/ITO.
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 metal sulfide doped layer at described electron injecting layer surface evaporation, material is CuS:Au, CuS and Au mass ratio is 10:1, thickness is 10nm, and then prepare organic electronic transmission doped layer by thermal resistance evaporation, material is PO15:TiO 2, PO15 and TiO 2mass ratio is 10:1, and thickness is, 60nm, and titanium dioxide particle diameter is 200nm, and then by Magnetron Sputtering Thin Film material layer, material is ITO, and thickness is 250nm.
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 concrete technology condition of magnetron sputtering mode is: operating pressure is 5 × 10 -4pa, the accelerating voltage of magnetron sputtering: 500V, magnetic field about: 150G, power density: 10W/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 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, 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 is by metal sulfide doped layer, organic electronic transmission doped layer and film material plies composition, described metal sulfide doped layer comprises metal sulfide and is entrained in the metal in described metal sulfide, and described metal sulfide layer material is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide, metal layer material is selected from silver, aluminium, at least one in platinum and gold, the titanium dioxide that described organic electronic transmission doped layer comprises described Organic Electron Transport Material and is entrained in described Organic Electron Transport Material, described organic electron transport layer 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, thin-film material layer material is selected from indium-tin oxide target material, at least one in aluminium zinc oxide target and indium-zinc oxide target.
2. organic electroluminescence device according to claim 1, it is characterized in that, described in described metal sulfide doped layer, the doping mass ratio of metal sulfide and described metal is 5:1 ~ 10:1, and described in described organic electronic transmission doped layer, Organic Electron Transport Material and described titanium dioxide mass ratio are 20:1 ~ 5:1.
3. organic electroluminescence device according to claim 1, is characterized in that, described metal sulfide doped layer thickness is 10nm ~ 60nm, and described organic electronic transmission doped layer thickness is 50nm ~ 100nm and thin-film material layer thickness is 100nm ~ 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
Metal sulfide doped layer is prepared by the method for thermal resistance evaporation on electron injecting layer surface, described metal sulfide doped layer comprises metal sulfide and is entrained in the metal in described metal sulfide, 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, described organic electronic transmission doped layer is prepared at described metal sulfide doped layer surface evaporation by the mode of electron beam evaporation plating, the titanium dioxide that described organic electronic transmission doped layer comprises described Organic Electron Transport Material and is entrained in described Organic Electron Transport Material, described organic electron transport layer 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, by magnetron sputtering mode in described organic electronic transmission doped layer surface preparation membrane layers, thin-film material layer material is selected from indium-tin oxide target material, at least one in aluminium zinc oxide target and indium-zinc oxide target, adopt thermal resistance evaporation mode at the described metal level of described film material plies surface preparation, described metal layer material is selected from silver, aluminium, at least one in platinum and gold.
6. the preparation method of organic electroluminescence device according to claim 5, it is characterized in that: described in described metal sulfide doped layer, the doping mass ratio of metal sulfide and described metal is 5:1 ~ 10:1, described in described organic electronic transmission doped layer, Organic Electron Transport Material and described titanium dioxide mass ratio are 20:1 ~ 5:1.
7. the preparation method of organic electroluminescence device according to claim 5, it is characterized in that: described metal sulfide doped layer thickness is 10nm ~ 60nm, described organic electronic transmission doped layer thickness is 50nm ~ 100nm and thin-film material layer thickness is 100nm ~ 300nm.
8. 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.
9. the preparation method of organic electroluminescence device according to claim 5, is characterized in that: the concrete technology condition of described magnetron sputtering mode is: operating pressure is 2 × 10 -3~ 5 × 10 -5pa, the accelerating voltage of magnetron sputtering: 300V ~ 800V, magnetic field about: 50G ~ 200G, power density: 1W/cm 2~ 40W/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.
10. 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.
CN201310451506.XA 2013-09-27 2013-09-27 Organic electroluminescent device and preparation method thereof Pending CN104518138A (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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