CN104638153A - Organic electroluminescent device and preparation method thereof - Google Patents

Organic electroluminescent device and preparation method thereof Download PDF

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Publication number
CN104638153A
CN104638153A CN201310548269.9A CN201310548269A CN104638153A CN 104638153 A CN104638153 A CN 104638153A CN 201310548269 A CN201310548269 A CN 201310548269A CN 104638153 A CN104638153 A CN 104638153A
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zinc
layer
compound
evaporation
sulfide
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周明杰
黄辉
张娟娟
王平
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • H10K50/82—Cathodes
    • H10K50/826—Multilayers, e.g. opaque multilayers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass

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  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

An organic electroluminescent device comprises an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode, all of which are sequentially stacked. The cathode layer is composed of a film layer, a zinc compound doped layer, and a metal sulfide layer. The film layer is made of at least one material selected from an indium tin oxide target, an aluminum zinc oxide target, and an indium zinc oxide target. The zinc compound doped layer includes a zinc compound and a hole injection material doped in the zinc compound, wherein the zinc compound includes at least one selected from zinc oxide, zinc sulfide, zinc selenide, and zinc chloride. The metal sulfide layer includes at least one material selected from zinc sulfide, cadmium sulfide, magnesium sulfate and copper sulfide. The organic electroluminescent device has high luminous efficiency. The invention further provides a method for preparing the organic electroluminescent device.

Description

Organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Under the principle of luminosity of organic electroluminescence device is based on the effect of extra electric field, electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Meet at luminescent layer in electronics and hole, compound, formation exciton, and exciton moves under electric field action, and by energy transferring to luminescent material, and excitation electron is from ground state transition to excitation state, and excited energy, by Radiation-induced deactivation, produces photon, release luminous energy.
The negative electrode of traditional organic electroluminescence device is generally the metal such as silver (Ag), gold (Au), and after preparation, negative electrode very easily penetrates into organic layer, damage, electronics easy cancellation near negative electrode, thus luminous efficiency is lower to organic layer.
Summary of the invention
Based on this, be necessary to provide organic electroluminescence device that a kind of luminous efficiency is higher and preparation method thereof.
A kind of organic electroluminescence device, comprise the anode stacked gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described cathode layer is by thin layer, the compound doped layer of zinc and metal sulfide layer composition, described film layer material is selected from indium-tin oxide target material, at least one in aluminium zinc oxide target and indium-zinc oxide target, the compound that the compound doped layer of described zinc comprises zinc and the hole-injecting material be entrained in the compound of described zinc, the compound of described zinc is selected from zinc oxide, zinc sulphide, at least one in zinc selenide and zinc chloride, described hole-injecting material is selected from 2, 3, 5, 6-tetra-fluoro-7, 7, 8, 8,-four cyano-benzoquinone's bismethane, 4, 4, 4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine and dinaphthyl-N, N '-diphenyl-4, at least one in 4 '-benzidine, described metal sulfide is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide.
The compound of zinc described in the compound doped layer of described zinc and the mass ratio of hole-injecting material are 0.1:1 ~ 0.5:1.
Described thin film layer thickness is 50nm ~ 100nm, and the compound doped layer thickness of zinc is 20nm ~ 100nm, and described metal sulfide layer thickness is 200nm ~ 400nm.
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
Thin layer is prepared by the method for magnetron sputtering on electron injecting layer surface, described film layer material is selected from indium-tin oxide target material, at least one in aluminium zinc oxide target and indium-zinc oxide target, then the compound doped layer of zinc is prepared at described thin-film surface by electron beam mode, the compound that the compound doped layer of described zinc comprises zinc and the hole-injecting material be entrained in the compound of described zinc, the compound of described zinc is selected from zinc oxide, zinc sulphide, at least one in zinc selenide and zinc chloride, described hole-injecting material is selected from 2, 3, 5, 6-tetra-fluoro-7, 7, 8, 8,-four cyano-benzoquinone's bismethane, 4, 4, 4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine and dinaphthyl-N, N '-diphenyl-4, at least one in 4 '-benzidine, described metal sulfide layer is prepared at the compound doped layer surface evaporation of described zinc by the mode of thermal resistance evaporation, described metal sulfide is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide.
The compound of zinc described in the compound doped layer of described zinc and the mass ratio of hole-injecting material are 0.1:1 ~ 0.5:1.
Described thin film layer thickness is 50nm ~ 100nm, and the compound doped layer thickness of zinc is 20nm ~ 100nm, and described metal sulfide layer thickness is 200nm ~ 400nm.
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 thin layer, the compound doped layer of zinc and metal sulfide layer composition, thin layer can improve the conductivity of negative electrode, the compound that the compound doped layer of zinc comprises zinc and the hole-injecting material be entrained in the compound of described zinc, the compound of zinc is that ordered crystal structure has scattering process to light, in visible-range, transmitance reaches about 80%, hole-injecting material HOMO energy level higher, can effective the passing through of blocking hole, avoid hole and electronics compound cancellation in the cathode, the thickness of metal sulfide layer is that 200nm ~ 400nm has stronger reflex to light, improve the reflection of light thus improve luminous efficiency.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is the cathode construction schematic diagram of the organic electroluminescence device of an execution mode;
Fig. 3 is current density and the luminous efficiency graph of a relation of organic electroluminescence device prepared by embodiment 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, organic electroluminescence device and preparation method thereof is illustrated further.
Refer to Fig. 1, the organic electroluminescence device 100 of an execution mode comprises the anode 10, hole injection layer 20, hole transmission layer 30, luminescent layer 40, electron transfer layer 50, electron injecting layer 60 and the negative electrode 70 that stack gradually.
Anode 10 is indium tin oxide glass (ITO), mixes the tin oxide glass (FTO) of fluorine, mixes the zinc oxide glass (AZO) of aluminium or mixes the zinc oxide glass (IZO) of indium, is preferably ITO.
Hole injection layer 20 is formed at anode 10 surface.The material of hole injection layer 20 is selected from molybdenum trioxide (MoO 3), tungstic acid (WO 3) and vanadic oxide (V 2o 5) at least one, be preferably MoO 3.The thickness of hole injection layer 20 is 20nm ~ 80nm, is preferably 30nm.
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 7nm.
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 220nm.
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 1.2nm.
Negative electrode 70 is formed at electron injecting layer 60 surface.Cathode layer 70 is by thin layer 701, compound doped layer 702 and the metal sulfide layer 703 of zinc form, described thin layer 701 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), the compound that the compound doped layer 702 of described zinc comprises zinc and the hole-injecting material be entrained in the compound of described zinc, the compound-material of described zinc is selected from zinc oxide (ZnO), zinc sulphide (ZnS), zinc selenide (ZnSe) and the middle at least one of zinc chloride (ZnCl), described hole-injecting material is selected from 2, 3, 5, 6-tetra-fluoro-7, 7, 8, 8,-four cyano-benzoquinone's bismethane (F4-TCNQ), 4, 4, 4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine (1T-NATA) and dinaphthyl-N, N '-diphenyl-4, at least one in 4 '-benzidine (2T-NATA), described metal sulfide is selected from zinc sulphide (ZnS), cadmium sulfide (CdS), magnesium sulfide (MgS) and the middle at least one of copper sulfide (CuS).
The compound of zinc described in the compound doped layer 702 of described zinc and the mass ratio of hole-injecting material are 0.1:1 ~ 0.5:1.
Described thin layer 701 thickness is 50nm ~ 100nm, and compound doped layer 702 thickness of zinc is 20nm ~ 100nm, and described metal sulfide layer 703 thickness is 200nm ~ 400nm.
Fig. 2 is that above-mentioned organic electroluminescence device 100 is by preparing the cathode construction schematic diagram of sandwich construction, this cathode construction layer is by thin layer 701, compound doped layer 702 and the metal sulfide layer 703 of zinc form, thin layer can improve the conductivity of negative electrode, the compound that the compound doped layer of zinc comprises zinc and the hole-injecting material be entrained in the compound of described zinc, the compound of zinc is that ordered crystal structure has scattering process to light, in visible-range, transmitance reaches about 80%, hole-injecting material HOMO energy level higher, can effective the passing through of blocking hole, avoid hole and electronics compound cancellation in the cathode, the thickness of metal sulfide layer is that 200nm ~ 400nm has stronger reflex to light, improve the reflection of light 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 30nm.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 7nm.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 220nm.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 1.2nm.Evaporation is 5 × 10 at vacuum pressure -3~ 2 × 10 -4carry out under Pa, evaporation rate is 0.1nm/s ~ 1nm/s.
Step S120, thin layer 701 is prepared by the method for magnetron sputtering on electron injecting layer surface, described film layer material is selected from indium-tin oxide target material, at least one in aluminium zinc oxide target and indium-zinc oxide target, then prepared the compound doped layer 702 of zinc by electron beam mode on described thin layer 701 surface, the compound that the compound doped layer of described zinc comprises zinc and the hole-injecting material be entrained in the compound of described zinc, the compound of described zinc is selected from zinc oxide, zinc sulphide, at least one in zinc selenide and zinc chloride, described hole-injecting material is selected from 2, 3, 5, 6-tetra-fluoro-7, 7, 8, 8,-four cyano-benzoquinone's bismethane, 4, 4, 4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine and dinaphthyl-N, N '-diphenyl-4, at least one in 4 '-benzidine, described metal sulfide layer 703 is prepared at the surperficial evaporation of compound doped layer 702 of described zinc by the mode of thermal resistance evaporation, described metal sulfide is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide.
The compound of zinc described in the compound doped layer of described zinc and the mass ratio of hole-injecting material are 0.1:1 ~ 0.5:1.
Described thin film layer thickness is 50nm ~ 100nm, and the compound doped layer thickness of zinc is 20nm ~ 100nm, and described metal sulfide layer thickness is 200nm ~ 400nm.
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/MoO 3/ NPB/Alq 3the organic electroluminescence device of/Bphen/LiF/ITO/ZnSe:F4-TCNQ/MgS, "/" presentation layer in the present embodiment and following examples, ": " represents doping.
First ITO is carried out photoetching treatment, be cut into required size, use liquid detergent successively, deionized water, acetone, ethanol, each ultrasonic 15min of isopropyl alcohol, remove the organic pollution of glass surface; Clean up and carry out suitable process to conductive substrates afterwards: oxygen plasma treatment, the processing time is 5min, and power is 30W; Evaporation hole injection layer, material is MoO 3, thickness is 60nm; Evaporation hole transmission layer, material is NPB, and thickness is 50nm; Evaporation luminescent layer, material is BCzVBi, and thickness is 30nm; Evaporation electron transfer layer, material is Bphen, and thickness is 160nm; Evaporation electron injecting layer, material is LiF, and thickness is 0.7nm; Evaporation negative electrode, magnetron sputtering mode is adopted to prepare thin layer at described electron injecting layer surface evaporation, material is ITO, and thickness is 70nm, is then prepared the compound doped layer of zinc by electron beam evaporation plating, material is ZnSe:F4-TCNQ, the mass ratio of ZnSe and F4-TCNQ is respectively 1:5, and thickness is 80nm, then has metal sulfide layer by the preparation of thermal resistance evaporation, material is MgS, and thickness is 300nm.
The concrete technology condition of electron beam evaporation plating mode is: operating pressure is 8 × 10 -5pa, the energy density of electron beam evaporation plating is 30W/cm 2, the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 3nm/s;
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 8 × 10 -5pa, operating current is 3A, and the evaporation rate of organic material is 0.2nm/s, and the evaporation rate of metal and metallic compound is 3nm/s.
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/MoO 3/ NPB/Alq 3structure prepared by organic electroluminescence device (curve 1) and the comparative example of/Bphen/LiF/ITO/ZnSe:F4-TCNQ/MgS is ITO/MoO 3/ NPB/Alq 3the current density 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 figure, under different current densities, the luminous efficiency of embodiment 1 is all larger than comparative example, the maximum lumen efficiency of embodiment 1 is 8.58lm/W, and comparative example be only 6.11lm/W, and the luminous efficiency of comparative example declines fast along with the increase of current density, this explanation, patent of the present invention is by preparing the cathode construction of sandwich construction, this cathode construction layer is by thin layer 701, compound doped layer 702 and the metal sulfide layer 703 of zinc form, thin layer can improve the conductivity of negative electrode, the compound that the compound doped layer of zinc comprises zinc and the hole-injecting material be entrained in the compound of described zinc, the compound of zinc is that ordered crystal structure has scattering process to light, in visible-range, transmitance reaches about 80%, hole-injecting material HOMO energy level higher, can effective the passing through of blocking hole, avoid hole and electronics compound cancellation in the cathode, the thickness of metal sulfide layer is that 200nm ~ 400nm has stronger reflex to light, improve the reflection of light thus improve luminous efficiency.
The luminous efficiency of organic electroluminescence device prepared of each embodiment is all similar with embodiment 1 below, and each organic electroluminescence device also has similar luminous efficiency, repeats no more below.
Embodiment 2
Structure prepared by the present embodiment is AZO/MoO 3the organic electroluminescence device of/TCTA/ADN/Bphen/CsF/AZO/ZnO:1T-NATA/ZnS.
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, magnetron sputtering mode is adopted to prepare thin layer at described electron injecting layer surface evaporation, material is AZO, and thickness is 50nm, is then prepared the compound doped layer of zinc by electron beam evaporation plating, material is ZnO:1T-NATA, the mass ratio of ZnO and 1T-NATA is respectively 1:10, and thickness is 100nm, then has metal sulfide layer by the preparation of thermal resistance evaporation, material is ZnS, and thickness is 200nm.
The concrete technology condition of electron beam evaporation plating mode is: operating pressure is 2 × 10 -3pa, the energy density of electron beam evaporation plating is 10W/cm 2, the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of metal and metallic compound is 10nm/s;
The concrete technology condition of thermal resistance evaporation mode is: operating pressure is 2 × 10 -3pa, operating current is 1A, and the evaporation rate of organic material is 0.1nm/s, and the evaporation rate of metal and metallic compound is 10nm/s;
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 3the organic electroluminescence device of/IZO/ZnS:2T-NATA/CdS.
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, magnetron sputtering mode is adopted to prepare thin layer at described electron injecting layer surface evaporation, material is IZO, and thickness is 100nm, is then prepared the compound doped layer of zinc by electron beam evaporation plating, material is ZnS:2T-NATA, the mass ratio of ZnS and 2T-NATA is respectively 1:2, and thickness is 20nm, then has metal sulfide layer by the preparation of thermal resistance evaporation, material is CdS, and thickness is 400nm.
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 3the organic electroluminescence device of/ITO/ZnCl:F4-TCNQ/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, magnetron sputtering mode is adopted to prepare thin layer at described electron injecting layer surface evaporation, material is ITO, and thickness is 70nm, is then prepared the compound doped layer of zinc by electron beam evaporation plating, material is ZnCl:F4-TCNQ, the mass ratio of ZnCl and F4-TCNQ is respectively 3:10, and thickness is 40nm, then has metal sulfide layer by the preparation of thermal resistance evaporation, material is CuS, 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 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 (9)

1. an organic electroluminescence device, it is characterized in that, comprise the anode stacked gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described cathode layer is by thin layer, the compound doped layer of zinc and metal sulfide layer composition, described film layer material is selected from indium-tin oxide target material, at least one in aluminium zinc oxide target and indium-zinc oxide target, the compound that the compound doped layer of described zinc comprises zinc and the hole-injecting material be entrained in the compound of described zinc, the compound of described zinc is selected from zinc oxide, zinc sulphide, at least one in zinc selenide and zinc chloride, described hole-injecting material is selected from 2, 3, 5, 6-tetra-fluoro-7, 7, 8, 8,-four cyano-benzoquinone's bismethane, 4, 4, 4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine and dinaphthyl-N, N '-diphenyl-4, at least one in 4 '-benzidine, described metal sulfide is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide.
2. organic electroluminescence device according to claim 1, is characterized in that, the compound of zinc described in the compound doped layer of described zinc and the mass ratio of hole-injecting material are 0.1:1 ~ 0.5:1.
3. organic electroluminescence device according to claim 1, is characterized in that, described thin film layer thickness is 50nm ~ 100nm, and the compound doped layer thickness of zinc is 20nm ~ 100nm, and described metal sulfide layer thickness is 200nm ~ 400nm.
4. 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
Thin layer is prepared by the method for magnetron sputtering on electron injecting layer surface, described film layer material is selected from indium-tin oxide target material, at least one in aluminium zinc oxide target and indium-zinc oxide target, then the compound doped layer of zinc is prepared at described thin-film surface by electron beam mode, the compound that the compound doped layer of described zinc comprises zinc and the hole-injecting material be entrained in the compound of described zinc, the compound of described zinc is selected from zinc oxide, zinc sulphide, at least one in zinc selenide and zinc chloride, described hole-injecting material is selected from 2, 3, 5, 6-tetra-fluoro-7, 7, 8, 8,-four cyano-benzoquinone's bismethane, 4, 4, 4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine and dinaphthyl-N, N '-diphenyl-4, at least one in 4 '-benzidine, described metal sulfide layer is prepared at the compound doped layer surface evaporation of described zinc by the mode of thermal resistance evaporation, described metal sulfide is selected from zinc sulphide, cadmium sulfide, at least one in magnesium sulfide and copper sulfide.
5. the preparation method of organic electroluminescence device according to claim 4, is characterized in that: the compound of zinc described in the compound doped layer of described zinc and the mass ratio of hole-injecting material are 0.1:1 ~ 0.5:1.
6. the preparation method of organic electroluminescence device according to claim 4, is characterized in that: described thin film layer thickness is 50nm ~ 100nm, and the compound doped layer thickness of zinc is 20nm ~ 100nm, and described metal sulfide layer thickness is 200nm ~ 400nm.
7. the preparation method of organic electroluminescence device according to claim 4, 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.
8. the preparation method of organic electroluminescence device according to claim 4, 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.
9. the preparation method of organic electroluminescence device according to claim 4, 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.
CN201310548269.9A 2013-11-06 2013-11-06 Organic electroluminescent device and preparation method thereof Pending CN104638153A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105977397A (en) * 2016-05-26 2016-09-28 京东方科技集团股份有限公司 Organic light-emitting diode device and preparation method thereof, array substrate, and display device

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105977397A (en) * 2016-05-26 2016-09-28 京东方科技集团股份有限公司 Organic light-emitting diode device and preparation method thereof, array substrate, and display device
WO2017202082A1 (en) * 2016-05-26 2017-11-30 京东方科技集团股份有限公司 Organic light-emitting diode device and preparation method therefor, and array substrate and display apparatus
CN105977397B (en) * 2016-05-26 2018-09-18 京东方科技集团股份有限公司 Organic light emitting diode device and preparation method thereof, array substrate, display device
US10381591B2 (en) 2016-05-26 2019-08-13 Boe Technology Group Co., Ltd. Organic light emitting diode device with a photoinduced electron film layer and method for manufacturing the same

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