CN103594635A - Organic electroluminescent device and preparation method thereof - Google Patents

Organic electroluminescent device and preparation method thereof Download PDF

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Publication number
CN103594635A
CN103594635A CN201210295734.8A CN201210295734A CN103594635A CN 103594635 A CN103594635 A CN 103594635A CN 201210295734 A CN201210295734 A CN 201210295734A CN 103594635 A CN103594635 A CN 103594635A
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layer
anode
biphenyl
organic electroluminescence
electroluminescence device
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周明杰
王平
冯小明
陈吉星
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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
    • H10K50/81—Anodes
    • H10K50/814—Anodes combined with auxiliary electrodes, e.g. ITO layer combined with metal lines
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition

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  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
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  • Electroluminescent Light Sources (AREA)

Abstract

The invention belongs to the field of organic semiconductor materials and discloses an organic electroluminescent device and a preparation method thereof. The organic electroluminescent device comprises a substrate, an anode layer, an anode modification layer, a hole transmission layer, an electronic barrier layer, a luminescent layer, a hole barrier layer, an electronic transmission layer and a cathode layer which are successively stacked. The anode layer is made of silver, gold, aluminum, nickel or platinum. The anode modification layer is made of a doped mixing material composed of a meal diode and a metal doping agent. The metal diode in the anode modification layer can improve the work function of the surface of the anode layer; the anode layer is made of metals, can provide the conductivity of the anode modification layer and can eliminate or reduce the interface rampart between the anode layer and the hole transmission layer so as to improve the carrier injection efficiency, therefore, the starting voltage of the organic electroluminescent device is reduced, and the luminescence efficiency of the device is improved.

Description

A kind of organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to organic semiconducting materials field, relate in particular to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescent (Organic Light Emission Diode), hereinafter to be referred as OLED, have that brightness is high, material range of choice is wide, driving voltage is low, entirely solidify the characteristics such as active illuminating, have high definition, wide viewing angle simultaneously, and the advantage such as fast response time, be a kind of Display Technique and light source that has potentiality, meet the development trend that information age mobile communication and information show, and the requirement of green lighting technique, be current lot of domestic and foreign researcher's focal point.
Organic electroluminescent LED has a kind of structure of similar sandwich, it is respectively negative electrode and anode up and down, between two electrodes, clip the organic material functional layer of single or multiple lift different materials kind and different structure, be followed successively by hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer.Organic electroluminescence device is carrier injection type luminescent device, at anode and negative electrode, add after operating voltage, hole is from anode, electronics is injected into respectively the organic material layer of device work from negative electrode, it is luminous that two kinds of charge carriers form hole-duplet in luminous organic material, and then light sends from electrode one side.
Up to the present, although the scientific research personnel of various countries, the whole world is by selecting suitable organic material and rational device structure design, made the indices of device performance be greatly improved, but at present owing to driving the electric current of luminescent device larger, luminous efficiency is low.
Summary of the invention
One of problem to be solved by this invention is to provide the organic electroluminescence device that a kind of drive current is little, luminous efficiency is high.
Technical scheme of the present invention is as follows:
, comprise the substrate, anode layer, anode modification layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and the cathode layer that stack gradually; Wherein, the material of described anode layer is metal silver, gold, aluminium, nickel or platinum; The material of described anode modification layer is the doping composite material that metal oxide and metal dopant form, and the mass ratio of described metal oxide and metal dopant is 0.1:1 ~ 1:1.
In the anode modification layer of described organic electroluminescence device, described metal oxide is rhenium trioxide, rhenium heptoxide, tungsten oxide, molybdenum oxide or vanadic oxide; Described metal dopant is the metal nanoparticle of silver, gold, aluminium or magnesium.
Described organic electroluminescence device, wherein, the material of described hole transmission layer is selected from N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, (4,4', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, N, N'-diphenyl-N; N'-bis-(3-aminomethyl phenyl)-1; 1'-biphenyl-4,4'-diamines, (N, N; N'; N '-tetramethoxy phenyl)-benzidine, 1,1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane; Or
Described in the material of described hole transmission layer, the material of hole transmission layer is that dopant material is doped to the doping composite material forming in material of main part according to the mass ratio of 1-10%, wherein, dopant material is 2, 3, 5, 6-tetrafluoro-7, 7 ', 8, 8 '-tetra-cyanogen quinone-bismethanes, 1, 3, 4, 5, 7, 8-hexafluoro-tetra-cyanogen-diformazan is to naphthoquinones or 2, 2'-(2, 5-dicyano-3, 6-difluoro cyclohexane-2, 5-diene-1, 4-bis-subunits) two malononitrile, material of main part is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines, (4, 4', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1, 1'-biphenyl-4, 4'-diamines, (N, N, N', N '-tetramethoxy phenyl)-benzidine or 1, 1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane.
Described organic electroluminescence device, wherein, the material of described electronic barrier layer is selected from N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, (4,4', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, N, N'-diphenyl-N; N'-bis-(3-aminomethyl phenyl)-1; 1'-biphenyl-4,4'-diamines, (N, N; N'; N '-tetramethoxy phenyl)-benzidine or 1,1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexanes.
Described organic electroluminescence device, wherein, to be dopant material be doped to according to 2 ~ 8% mass ratio the doping composite material forming in material of main part to the material of described luminescent layer; Described material of main part is (oxine)-aluminium, 4,4'-bis-(9-carbazole) biphenyl, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4 '; 4 "-tri-(carbazole-9-yl)-triphenylamines or the 4-4-dicyano methylene-2-tert-butyl group-6-(1,1,7,7-tetramethyl-julolidine-9-vinyl)-4H-pyrans; Described dopant material is that two (4,6-difluorophenyl pyridine-N, C2) pyridine carboxylic acids close iridium, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione), three (2-phenylpyridine) and close iridium or (oxine)-aluminium.
Described organic electroluminescence device, wherein, the material of described hole blocking layer is selected from 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, 1,2,4-triazole derivative or two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium;
Described organic electroluminescence device, wherein, the material of described electron transfer layer is selected from 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, 1,2,4-triazole derivative or two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium; Or
To be alkali metal compound be doped to according to 5 ~ 30% mass ratio the doping composite material forming in electric transmission host material to the material of described electron transfer layer; Wherein, described alkali metal compound is selected from lithium carbonate, Lithium Azide, lithium fluoride, cesium azide, cesium carbonate; Described electric transmission host material is selected from, 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, 1,2,4-triazole derivative and two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) at least one in aluminium.
Described organic electroluminescence device, wherein, described substrate is glass.
Described organic electroluminescence device, wherein, the material of described cathode layer is selected silver, aluminium, silver-colored magnesium alloy or magnadure.
Two preparation methods that are to provide above-mentioned organic electroluminescence device that the present invention will deal with problems, comprise the steps:
S1, cleaning substrate;
S2, utilize vacuum coating system, prepare anode layer cleaning substrate surface evaporation later;
S3, subsequently, then in vacuum coating system, utilize evaporation coating method, on anode layer surface, stack gradually and prepare anode modification layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and cathode layer; Wherein, the material of described anode layer is metal silver, gold, aluminium, nickel or platinum; The material of described anode modification layer is the doping composite material that metal oxide and metal dopant form, and the mass ratio of described metal oxide and metal dopant is 0.1:1 ~ 1:1;
Organic electronic light emitting device provided by the invention, between anode layer and hole transmission layer, prepare one deck anode modification layer, the material of this anode modification layer is the doping composite material that metal oxide and metal dopant form, and its metal oxide can improve the work function on anode layer surface; And anode layer adopts metal material, the conductivity of anode modification layer can be provided, and can eliminate or reduce the interface barrier between anode layer and hole transmission layer, thereby improved the injection efficiency of charge carrier, thereby reduced the starting resistor of organic electroluminescence device, improved the luminous efficiency of device.
Accompanying drawing explanation
Fig. 1 is organic electroluminescence device structural representation of the present invention;
Fig. 2 is current density and the voltage curve of the organic electroluminescence device that makes respectively of embodiment 1 and comparative example 1.
Embodiment
Organic electroluminescence device provided by the invention, as shown in Figure 1, comprise substrate 100, anode layer 101, anode modification layer 102, hole transmission layer 103, electronic barrier layer 104, luminescent layer 105, hole blocking layer 106, electron transfer layer 107 and the cathode layer 108 stacking gradually; The structure of this organic electroluminescence device is: substrate 100/ anode layer 101/ anode modification layer 102/ hole transmission layer 103/ electronic barrier layer 104/ luminescent layer 105/ hole blocking layer 106/ electron transfer layer 107/ cathode layer 108.In this device, the silver that the material of described anode layer 101 is metal (Ag), gold (Au), aluminium (Al), nickel (Ni) or platinum (Pt), and the thickness of this anode layer is 70-120nm, preferred thickness is 100nm; The material of described anode modification layer 102 is the doping composite material that metal oxide and metal dopant form, and the mass ratio of described metal oxide and metal dopant is 0.1:1 ~ 1: 1; The thickness of anode modification layer 102 is 2 ~ 10nm.
In the anode modification layer 102 of organic electroluminescence device, metal oxide is that metal oxide is rhenium trioxide (ReO 3), rhenium heptoxide (Re 2o 7), tungsten oxide (WO 3), molybdenum oxide (MoO 3) or vanadic oxide (V 2o 5); Described metal dopant is silver (Ag), gold (Au), aluminium (Al) or magnesium (Mg) nano particle.
In above-mentioned organic electroluminescence device, the material of other each function, thickness and role is as follows separately:
Substrate 101 adopts common glass;
The material of described hole transmission layer 103 is selected from dopant material and according to the mass ratio of 1-10%, is doped to the doping composite material forming in material of main part; Wherein, dopant material is 2,3,5,6-tetrafluoro-7,7 ', 8,8 '-tetra-cyanogen quinone-bismethanes (F4-TCNQ), 1,3,4,5,7,8-hexafluoro-tetra-cyanogen-diformazan is to naphthoquinones (F6-TNAP) or 2,2'-(2,5-dicyano-3,6-difluoro cyclohexane-2,5-diene-Isosorbide-5-Nitrae-bis-subunit) two malononitrile (F2-HCNQ); Material of main part is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), (4,4', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), N, N'-diphenyl-N; N'-bis-(3-aminomethyl phenyl)-1; 1 '-biphenyl-4,4'-diamines (TPD), (N, N; N'; N '-tetramethoxy phenyl)-benzidine (MeO-TPD) or 1,1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC); The thickness of hole transmission layer 103 is 30-80nm, and preferred thickness is 60nm; The preferred F6-TNAP of material of hole transmission layer 103 is doped to the doping composite material forming in MeO-TPD, and F6-TNAP doping quality is frequently 5%.
The material of electronic barrier layer 104 is selected from N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), (4,4', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), N; N'-diphenyl-N; N'-bis-(3-aminomethyl phenyl)-1,1'-biphenyl-4,4'-diamines (TPD), (N; N; N', N '-tetramethoxy phenyl)-benzidine or 1,1-bis-(4-(N; N '-bis-(p-tolyl) amino) phenyl) cyclohexane (TAPC) etc., the thickness of electronic barrier layer 104 is 5 ~ 30nm; The preferred TPD of material of this electronic barrier layer 104, the preferred 10nm of thickness;
To be dopant material be doped to according to 2 ~ 8% mass ratio the doping composite material forming in material of main part to the material of luminescent layer 105; Described material of main part is (oxine)-aluminium (Alq 3), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4 '; 4 "-tri-(carbazole-9-yl)-triphenylamines (TCTA) or the 4-4-dicyano methylene-2-tert-butyl group-6-(1,1,7,7-tetramethyl-julolidine-9-vinyl)-4H-pyrans (DCJTB); Described dopant material is that two (4,6-difluorophenyl pyridine-N, C2) pyridine carboxylic acids close iridium (FIrPic), two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) (Ir (MDQ) 2(acac)), three (2-phenylpyridines) close iridium (Ir (ppy) 3) or (oxine)-aluminium (Alq 3);
The preferred Ir of material (ppy) of luminescent layer 105 3be doped in TCTA Ir (ppy) 3doping mass ratio is 3%; The thickness of luminescent layer 105 is for being 5-20nm, and preferred thickness is 15nm
The material of hole blocking layer 106 is selected from 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), 1,2,4-triazole derivative (as TAZ) or two (2-methyl-oxine-N1, O8)-materials such as (1,1'-biphenyl-4-hydroxyl) aluminium (BAlq), the thickness of hole blocking layer 106 is 5 ~ 30nm, and preferred thickness is 10nm; The preferred BAlq of material of hole blocking layer 106;
The material of described electron transfer layer 107 is 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), 1,2,4-triazole derivative (as TAZ) or two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium (BAlq); Or
To be alkali metal compound (be doped to the doping composite material forming in electric transmission host material according to 5 ~ 30% mass ratio to the material of described electron transfer layer 107; Wherein, alkali metal compound is selected from lithium carbonate (Li 2cO 3), Lithium Azide (LiN 3), lithium fluoride (LiF), cesium azide (CsN 3), cesium carbonate (Cs 2cO 3) or the material such as cesium fluoride (CsF); Electric transmission host material, 4,7-diphenyl-o-phenanthroline (Bphen), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP), 1,2,4-triazole derivative (as TAZ) and two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) at least one in aluminium (BAlq);
The thickness of described electron transfer layer 107 is 30 ~ 120nm, and preferred thickness is 60nm; The material of described electron transfer layer 107 is preferably selected CsN 3be doped to the doping composite material forming in Bphen, CsN 3doping quality be frequently 15%.
The material of cathode layer 108 is selected from argent (Ag), aluminium (Al), silver-colored magnesium alloy (Ag-Mg) or magnadure (Al-Mg), preferably Ag; The thickness of cathode layer 108 is 18-35nm, and preferred thickness is 25nm.
Above-mentioned organic electroluminescence device, its manufacture method comprises the following steps:
S1, cleaning substrate, main flow process is: use washing agent, deionized water, isopropyl alcohol, acetone are distinguished ultrasonic cleaning substrate 20 minutes, and then dried up with nitrogen successively;
S2, utilize vacuum coating system, prepare anode layer cleaning substrate surface later;
S3, in vacuum coating system, utilize evaporation coating method, on the anode layer surface preparing, stack gradually and prepare anode modification layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and cathode layer; Wherein, the silver (Ag) that the material of described anode layer is metal, gold (Au), aluminium (Al), nickel (Ni) or platinum (Pt); The material of described anode modification layer is the doping composite material that metal oxide and metal dopant form, and the mass ratio of described metal oxide and metal dopant is 0.1:1 ~ 1:1;
After above-mentioned processing step completes, make described organic electroluminescence device.
Organic electronic light emitting device provided by the invention, between anode layer and hole transmission layer, prepare one deck anode modification layer, the material of this anode modification layer is the doping composite material that metal oxide and metal dopant form, and its metal oxide can improve the work function on anode layer surface; And anode layer adopts metal material, the conductivity of anode modification layer can be provided, and can eliminate or reduce the interface barrier between anode layer and hole transmission layer, thereby improved the injection efficiency of charge carrier, thereby reduced the starting resistor of organic electroluminescence device, improved the luminous efficiency of device.
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
Embodiment 1
The organic electroluminescence device of the present embodiment, its structure is: glass/Au/Au:ReO 3/ F6-TNAP:MeO-TPD/TPD/TCTA:Ir (ppy) 3/ BAlq/CsN 3: BPhen/Ag
The manufacture method of this organic electroluminescence device is as follows:
1, use washing agent, deionized water, isopropyl alcohol, acetone are distinguished ultrasonic cleaning glass substrate 20 minutes, and then are dried up with nitrogen successively;
2, glass cleaning clean after, insert in vacuum coating system, (material is Au at its surperficial evaporation, to prepare anode layer; Thickness is 100nm);
3,, in vacuum thermal evaporation system, (material is Au and ReO on anode layer surface, to stack gradually evaporation anode modification layer 3the doping composite material forming according to the mass ratio of 0.1:1, is expressed as Au:ReO 3,, thickness is 2nm), (material is that F6-TNAP is doped in MeO-TPD material of main part as dopant material to hole transmission layer, is expressed as F6-TNAP:MeO-TPD; The doping mass ratio of F6-TNAP is 2%, and thickness is 60nm), electronic barrier layer (material is TPD, and thickness is 10nm), (material is Ir (ppy) to luminescent layer 3as dopant material, be doped in TCTA material of main part, be expressed as TCTA:Ir (ppy) 3; Ir (ppy) 3doping mass ratio be 3%, thickness is 15nm), hole blocking layer (material is BAlq, and thickness is 10nm), (material is CsN to electron transfer layer 3be doped in BPhen, be expressed as CsN 3: BPhen, CsN 3doping mass ratio be 10%, thickness 60nm) and cathode layer (material is Ag, and thickness is 25nm).
Embodiment 2
The organic electroluminescence device of the present embodiment, its structure is: glass/Al/Al:Re 2o 7/ F4-TCNQ:NPB/TAPC/CBP:FIrPic/TPBi/LiN 3: TPBi/Al
The manufacture method of this organic electroluminescence device is as follows:
1, use washing agent, deionized water, isopropyl alcohol, acetone are distinguished ultrasonic cleaning glass substrate 20 minutes, and then are dried up with nitrogen successively;
2, glass cleaning clean after, insert in vacuum coating system, (material is Al at its surperficial evaporation, to prepare anode layer; Thickness is 70nm);
3,, in vacuum thermal evaporation system, (material is Al and Re on anode layer surface, to stack gradually evaporation anode modification layer 2o 7the doping composite material that mass ratio according to 0.2 forms, is expressed as Al:Re 2o 7, thickness is 2nm), (material is that F4-TCNQ is doped in NPB material of main part as dopant material to hole transmission layer, is expressed as F6-TNAP:MeO-TPD; The doping mass ratio of F4-TCNQ is 10%, and thickness is 30nm), electronic barrier layer (material is TAPC, and thickness is 5nm), (material is that FIrPic is doped in CBP material of main part as dopant material to luminescent layer, is expressed as CBP:FIrPic; Ir (ppy) 3doping mass ratio be 2%, thickness is 20nm), hole blocking layer (material is TPBi, and thickness is 5nm), (material is LiN to electron transfer layer 3be doped in TPBi, be expressed as LiN 3: TPBi, LiN 3doping mass ratio be 5%, thickness 30nm) and cathode layer (material is Al, and thickness is 18nm).
Embodiment 3
The organic electroluminescence device of the present embodiment, its structure is: glass/Ni/Mg:WO 3/ F2-HCNQ:m-MTDATA/NPB/NPB:Ir (MDQ) 2(acac)/Bphen/Cs 2cO 3: TAZ/Ag-Mg
The manufacture method of this organic electroluminescence device is as follows:
1, use washing agent, deionized water, isopropyl alcohol, acetone are distinguished ultrasonic cleaning glass substrate 20 minutes, and then are dried up with nitrogen successively;
2, glass cleaning clean after, insert in vacuum coating system, (material is Ni at its surperficial evaporation, to prepare anode layer; Thickness is 120nm);
3,, in vacuum thermal evaporation system, (material is Mg and WO on anode layer surface, to stack gradually evaporation anode modification layer 3the doping composite material forming according to the mass ratio of 0.5:1, is expressed as Mg:WO 3,, thickness is 5nm), (material is that F2-HCNQ is doped in m-MTDATA material of main part as dopant material to hole transmission layer, is expressed as F4-TCNQ:m-MTDATA; The doping mass ratio of F4-TCNQ is 5%, and thickness is 80nm), electronic barrier layer (material is TAPC, and thickness is 10nm), (material is Ir (MDQ) to luminescent layer 2(acac) as dopant material, be doped in NPB material of main part, be expressed as NPB:Ir (MDQ) 2(acac); Ir (MDQ) 2(acac) doping mass ratio is 5%, and thickness is 20nm), hole blocking layer (material is Bphen, and thickness is 10nm), (material is Cs to electron transfer layer 2cO 3be doped in TAZ, be expressed as Cs 2cO 3: TAZ, Cs 2cO 3doping mass ratio be 15%, thickness 120nm) and cathode layer (material is Ag-Mg, and thickness is 35nm).
Embodiment 4
The organic electroluminescence device of the present embodiment, its structure is: glass/Pt/Ag:MoO 3/ F6-TNAP:TPD/TPD/DCJTB:Alq 3/ BAlq/Li 2cO 3bCP/Al-Mg
The manufacture method of this organic electroluminescence device is as follows:
1, use washing agent, deionized water, isopropyl alcohol, acetone are distinguished ultrasonic cleaning glass substrate 20 minutes, and then are dried up with nitrogen successively;
2, glass cleaning clean after, insert in vacuum coating system, (material is Pt at its surperficial evaporation, to prepare anode layer; Thickness is 120nm);
3,, in vacuum thermal evaporation system, (material is Ag and MoO on anode layer surface, to stack gradually evaporation anode modification layer 3the doping composite material forming according to the mass ratio of 1:1, is expressed as Ag:MoO 3,, thickness is 10nm), (material is that F6-TNAP is doped in TPD material of main part as dopant material to hole transmission layer, is expressed as F6-TNAP:TPD; The doping mass ratio of F6-TNAP is 5%, and thickness is 40nm), electronic barrier layer (material is TPD, and thickness is 10nm), (material is that DCJTB is doped to Alq as dopant material to luminescent layer 3in material of main part, be expressed as DCJTB:Alq 3; The doping mass ratio of DCJTB is 1%, and thickness is 10nm), hole blocking layer (material is BAlq, and thickness is 10nm), (material is Li to electron transfer layer 2cO 3be doped in BCP, represent Li 2cO 3: BCP, Li 2cO 3doping mass ratio be 8%, thickness 40nm) and cathode layer (material is Mg-Ag, and thickness is 18nm).
Embodiment 5
The organic electroluminescence device of the present embodiment, its structure is: glass/Ag/Ag:V 2o 5/ F6-TNAP:TAPC/TAPC/Alq 3: Ir (MDQ) 2(acac)/BAlq/LiF:BAlq/Al.
The manufacture method of this organic electroluminescence device is as follows:
1, use washing agent, deionized water, isopropyl alcohol, acetone are distinguished ultrasonic cleaning glass substrate 20 minutes, and then are dried up with nitrogen successively;
2, glass cleaning clean after, insert in vacuum coating system, (material is Ag at its surperficial evaporation, to prepare anode layer; Thickness is 80nm);
3,, in vacuum thermal evaporation system, (material is Ag and V on anode layer surface, to stack gradually evaporation anode modification layer 2o 5the doping composite material that mass ratio according to 0.1 forms, is expressed as Ag:V 2o 5,, thickness is 10nm), (material is that F6-TNAP is doped in TAPC material of main part as dopant material to hole transmission layer, is expressed as F6-TNAP:TAPC; The doping mass ratio of F6-TNAP is 2%, and thickness is 50nm), electronic barrier layer (material is TAPC, and thickness is 10nm), (material is Ir (MDQ) to luminescent layer 2(acac) as dopant material, be doped to Alq 3in material of main part, be expressed as Alq 3: Ir (MDQ) 2(acac); Ir (MDQ) 2(acac) doping mass ratio is 6%, thickness is 15nm), (material is BAlq to hole blocking layer, thickness is 10nm), (material is that LiF is doped in BAlq to electron transfer layer, be expressed as LiF:BAlq, the doping mass ratio of LiF is 15%, thickness 50nm) and cathode layer (material is Al, and thickness is 20nm).
Comparative example 1
The organic electroluminescence device of this comparative example, its structure is: glass/ITO/F6-TNAP:MeO-TPD/TPD/TCTA:Ir (ppy) 3/ BAlq/CsN 3: BPhen/Ag.
The manufacture method of this organic electroluminescence device is as follows:
1, use washing agent, deionized water, isopropyl alcohol, acetone are distinguished ultrasonic cleaning glass substrate 20 minutes, and then are dried up with nitrogen successively;
2, glass cleaning clean after, insert in vacuum sputter system, at its surface sputtering, prepare indium doped stannum oxide (ITO) film of thickness 100nm, as anode layer; Then use plasma treatment;
3, in vacuum thermal evaporation system, (material is that F6-TNAP is doped in MeO-TPD material of main part as dopant material on ito thin film surface, to stack gradually evaporation hole transmission layer, be expressed as F6-TNAP:MeO-TPD, the doping mass ratio of F6-TNAP is 2%, thickness is 60nm), electronic barrier layer (material is TPD, and thickness is 10nm), (material is Ir (ppy) to luminescent layer 3be doped in TCTA, be expressed as TCTA:Ir (ppy) 3, Ir (ppy) 3doping mass ratio be 3%, thickness is 15nm), hole blocking layer (material is BAlq, and thickness is 40nm), (material is CsN to electron transfer layer 3as dopant material, be doped in BPhen material of main part, be expressed as CsN 3: BPhen, CsN 3doping mass ratio be 10%, thickness is 60nm) and cathode layer (material is Al, and thickness is 20nm).
The luminescent properties of the organic electroluminescence device that the present invention also makes embodiment 1 to 5 and comparative example 1 is tested, and test data result is as shown in table 1.
The luminescent properties of table 1 organic electroluminescence device
Starting resistor (V) Brightness during 8V (cd/m2) Luminous efficiency (lm/W)
Embodiment 1 2.5 22130 21.4
Embodiment 2 2.5 22010 20.9
Embodiment 3 2.5 24610 26.5
Embodiment 4 2.5 21900 20.1
Embodiment 5 2.5 21870 19.7
Comparative example 1 3.4 14980 10.1
As can be seen from Table 1, organic electroluminescence device provided by the invention, owing to having adopted anode modification layer, this decorative layer can improve the injection efficiency in hole, therefore the starting resistor of device is obviously reduced.Because Carrier Injection Efficiency has improved, thereby brightness and light efficiency can be greatly improved.
Fig. 2 is current density and the voltage curve of the organic electroluminescence device that makes respectively of embodiment 1 and comparative example 1.
As can be seen from Figure 2, under identical driving voltage, embodiment 1 has higher Carrier Injection Efficiency, therefore under identical starting resistor, embodiment 1 has higher current density, thereby just can embody in table 1, embodiment 1 has higher luminous efficiency, has confirmed beneficial effect of the present invention.
Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.

Claims (10)

1. an organic electroluminescence device, is characterized in that, comprises the substrate, anode layer, anode modification layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and the cathode layer that stack gradually; The material of described anode layer is silver, gold, aluminium, nickel or the platinum of metal; The material of described anode modification layer is the doping composite material that metal oxide and metal dopant form, and the mass ratio of described metal oxide and metal dopant is 0.1:1 ~ 1:1.
2. organic electroluminescence device according to claim 1, is characterized in that, described metal oxide is rhenium trioxide, rhenium heptoxide, tungsten oxide, molybdenum oxide or vanadic oxide; Described metal dopant is the metal nanoparticle of gold, silver, aluminium or magnesium.
3. organic electroluminescence device according to claim 1, is characterized in that, the material of hole transmission layer is that dopant material is doped to the doping composite material forming in material of main part according to the mass ratio of 1-10% described in the material of described hole transmission layer; Wherein, dopant material is 2,3,5,6-tetrafluoro-7,7 ', 8,8 '-tetra-cyanogen quinone-bismethanes, 1,3,4,5,7, and 8-hexafluoro-tetra-cyanogen-diformazan is to naphthoquinones or 2,2'-(2,5-dicyano-3,6-difluoro cyclohexane-2,5-diene-Isosorbide-5-Nitrae-bis-subunit), two malononitrile; Material of main part is, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, (4,4', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-1; 1'-biphenyl-4,4'-diamines, (N, N; N'; N '-tetramethoxy phenyl)-benzidine or 1,1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexane.
4. organic electroluminescence device according to claim 1, it is characterized in that, the material of described electronic barrier layer is selected from N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, (4,4', 4 " tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, N, N'-diphenyl-N; N'-bis-(3-aminomethyl phenyl)-1; 1'-biphenyl-4,4'-diamines, (N, N; N'; N '-tetramethoxy phenyl)-benzidine or 1,1-bis-(4-(N, N '-bis-(p-tolyl) amino) phenyl) cyclohexanes.
5. organic electroluminescence device according to claim 1, is characterized in that, to be dopant material be doped to according to 2 ~ 8% mass ratio the doping composite material forming in material of main part to the material of described luminescent layer; Described material of main part is (oxine)-aluminium, 4,4'-bis-(9-carbazole) biphenyl, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4 '; 4 "-tri-(carbazole-9-yl)-triphenylamines or the 4-4-dicyano methylene-2-tert-butyl group-6-(1,1,7,7-tetramethyl-julolidine-9-vinyl)-4H-pyrans; Described dopant material is that two (4,6-difluorophenyl pyridine-N, C2) pyridine carboxylic acids close iridium, two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione), three (2-phenylpyridine) and close iridium or (oxine)-aluminium.
6. organic electroluminescence device according to claim 1, is characterized in that, the material of described hole blocking layer is selected from 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, 1,2,4-triazole derivative or two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium.
7. organic electroluminescence device according to claim 1, is characterized in that, the material of described electron transfer layer is selected from 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, 1,2,4-triazole derivative or two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) aluminium.
8. organic electroluminescence device according to claim 1, is characterized in that, to be alkali metal compound be doped to according to 5 ~ 30% mass ratio the doping composite material forming in electric transmission host material to the material of described electron transfer layer; Described alkali metal compound is selected from lithium carbonate, Lithium Azide, lithium fluoride, cesium azide, cesium carbonate or described electric transmission host material and is selected from 4,7-diphenyl-o-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene, 1,2,4-triazole derivative and two (2-methyl-oxine-N1, O8)-(1,1'-biphenyl-4-hydroxyl) at least one in aluminium.
9. organic electroluminescence device according to claim 1, is characterized in that, described substrate is glass; The material of described cathode layer is selected silver, aluminium, silver-colored magnesium alloy or magnadure.
10. the preparation method of organic electroluminescence device as claimed in claim 1, is characterized in that, comprises the steps:
S1, cleaning substrate;
S2, utilize vacuum coating system, prepare anode layer cleaning substrate surface later;
S3, subsequently, then in vacuum coating system, utilize evaporation coating method, on anode layer surface, stack gradually and prepare anode modification layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and cathode layer; Wherein, the material of described anode layer is metal silver, gold, aluminium, nickel or platinum; The material of described anode modification layer is the doping composite material that metal oxide and metal dopant form, and the mass ratio of described metal oxide and metal dopant is 0.1:1 ~ 1:1;
After above-mentioned processing step completes, make described organic electroluminescence device.
CN201210295734.8A 2012-08-17 2012-08-17 Organic electroluminescent device and preparation method thereof Pending CN103594635A (en)

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CN107948358A (en) * 2017-11-29 2018-04-20 李国强 A kind of smart mobile phone with organic light-emitting diode (OLED) display screen
CN107948359A (en) * 2017-11-29 2018-04-20 李国强 A kind of smart mobile phone with OLED display screen
WO2020108068A1 (en) * 2018-11-26 2020-06-04 Tcl科技集团股份有限公司 Quantum dot light-emitting diode and preparation method therefor
CN114497408A (en) * 2022-02-11 2022-05-13 吉林大学 Paper-based organic electroluminescent device and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107948358A (en) * 2017-11-29 2018-04-20 李国强 A kind of smart mobile phone with organic light-emitting diode (OLED) display screen
CN107948359A (en) * 2017-11-29 2018-04-20 李国强 A kind of smart mobile phone with OLED display screen
WO2020108068A1 (en) * 2018-11-26 2020-06-04 Tcl科技集团股份有限公司 Quantum dot light-emitting diode and preparation method therefor
US11744098B2 (en) 2018-11-26 2023-08-29 Tcl Technology Group Corporation Quantum dot light-emitting diode and preparation method therefor
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