CN104078580A - Organic light-emitting diode and preparation method thereof - Google Patents
Organic light-emitting diode and preparation method thereof Download PDFInfo
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- CN104078580A CN104078580A CN201310110254.4A CN201310110254A CN104078580A CN 104078580 A CN104078580 A CN 104078580A CN 201310110254 A CN201310110254 A CN 201310110254A CN 104078580 A CN104078580 A CN 104078580A
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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
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- H10K50/841—Self-supporting sealing arrangements
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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
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
- H10K50/8445—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- 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
Abstract
An organic light-emitting diode comprises a positive pole, a light-emitting layer, a negative pole and a packaging cover which are stacked in sequence. The light-emitting layer and the negative pole are packaged on the positive pole through the packaging cover, and the packaging cover comprises a first organic barrier layer, a first inorganic barrier layer formed on the surface of the first organic barrier layer, a second organic barrier layer formed on the surface of the first inorganic barrier layer and a second inorganic barrier layer formed on the surface of the second organic barrier layer. Materials of the first organic barrier layer comprise a hole transport material and an electron transport material; materials of the first inorganic barrier layer comprise a metal oxide, a carbide and a sulfide; materials of the second organic barrier layer comprise a hole transport material and an electron transport material; and materials of the second inorganic barrier layer comprise a sulfide and a carbide. The organic light-emitting diode is long in service life. The invention further provides a preparation method for preparing the organic light-emitting diode.
Description
Technical field
The present invention relates to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) is a kind of current mode light emitting semiconductor device based on organic material.Its typical structure is that the luminous organic material of preparing one deck tens nanometer thickness on ito glass is made luminescent layer, and there is the metal electrode of one deck low work function luminescent layer top.While being added with voltage on electrode, luminescent layer just produces light radiation.
Organic electroluminescence device is subject to after moisture and moisture erosion, can cause that the material of organic electroluminescence device inner member occurs aging and then lost efficacy, thereby the life-span of described organic electroluminescence device is shorter.
Summary of the invention
Based on this, be necessary to provide longer organic electroluminescence device of a kind of life-span and preparation method thereof.
A kind of organic electroluminescence device, comprise the anode, luminescent layer and the negative electrode that stack gradually, described organic electroluminescence device also comprises cap, described cap is packaged in described luminescent layer and negative electrode on described anode, and described cap comprises first organic barrier layer, be formed at the first inorganic barrier layer of described first organic barrier layer surface, be formed at second organic barrier layer on described the first inorganic barrier layer surface and be formed at the second inorganic barrier layer of described second organic barrier layer surface;
The material on described first organic barrier layer comprises hole mobile material and electron transport material, and the material of described the first inorganic barrier layer comprises metal oxide, carbide and sulfide, the material on described second organic barrier layer comprises hole mobile material and electron transport material, the material of described the second inorganic barrier layer comprises sulfide and carbide, described hole mobile material is selected from N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-4,4'-benzidine, N, N '-bis-(Alpha-Naphthyl)-N, N '-diphenyl-4,4 '-diamines, 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, 2-methyl-9,10-bis-(imidazoles-2-yl) anthracene, 4,4', at least one in 4''-tri-(carbazole-9-yl) triphenylamine and 1,3-bis-(9H-carbazole-9-yl) benzene, described electron transport material is selected from 4,7-diphenyl Phen, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, oxine aluminium, two (2-methyl-8-quinoline)-(4-phenylphenol) aluminium and 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1, at least one in 2,4-triazole, described metal oxide is selected from meta-aluminic acid magnesium, bismuth titanates, chromic acid nickel, cobalt-chromate, at least one in lutetium acid iron and yttrium aluminate, described carbide is selected from carborundum, tungsten carbide, ramet, boron carbide, at least one in titanium carbide and hafnium carbide, described sulfide is selected from cadmium sulfide, vulcanized lead, ferrous disulfide, copper sulfide, at least one in zinc sulphide and nickel sulfide.
In an embodiment, the quantity of described cap is that 2～4,2～4 caps stack gradually therein.
In an embodiment, the thickness on described first organic barrier layer is 200nm～300nm therein; The thickness of described the first inorganic barrier layer is 100nm～200nm; The thickness on described second organic barrier layer is 200nm～300nm; The thickness of described the second inorganic barrier layer is 100nm～200nm.
In an embodiment, in described first organic barrier layer, the mol ratio of described hole mobile material and described electron transport material is 40:100～60:100 therein; Described in described the first inorganic barrier layer, the quality percentage composition of carbide is 10%～30%, and the quality percentage composition of described sulfide is 10%～30%; In described second organic barrier layer, the mol ratio of described hole mobile material and described electron transport material is 40:100～60:100; Described in described the second inorganic barrier layer, the quality percentage composition of carbide is 10%～30%.
In an embodiment, described cap coordinates and is formed with host cavity with described anode therein, and described luminescent layer and negative electrode are all contained in described host cavity.
A preparation method for organic electroluminescence device, comprises the following steps:
At anode surface, prepare luminescent layer;
On described luminescent layer surface, prepare negative electrode; And
At described cathode surface, prepare cap, described cap is packaged in described luminescent layer and negative electrode on described anode, and described cap comprises first organic barrier layer, be formed at the first inorganic barrier layer of described first organic barrier layer surface, be formed at second organic barrier layer on described the first inorganic barrier layer surface and be formed at the second inorganic barrier layer of described second organic barrier layer surface, the material on described first organic barrier layer comprises hole mobile material and electron transport material, and the material of described the first inorganic barrier layer comprises metal oxide, carbide and sulfide, the material on described second organic barrier layer comprises hole mobile material and electron transport material, the material of described the second inorganic barrier layer comprises sulfide and carbide, described hole mobile material is selected from N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-4,4'-benzidine, N, N '-bis-(Alpha-Naphthyl)-N, N '-diphenyl-4,4 '-diamines, 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, 2-methyl-9,10-bis-(imidazoles-2-yl) anthracene, 4,4', at least one in 4''-tri-(carbazole-9-yl) triphenylamine and 1,3-bis-(9H-carbazole-9-yl) benzene, described electron transport material is selected from 4,7-diphenyl Phen, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, oxine aluminium, two (2-methyl-8-quinoline)-(4-phenylphenol) aluminium and 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1, at least one in 2,4-triazole, described metal oxide is selected from meta-aluminic acid magnesium, bismuth titanates, chromic acid nickel, cobalt-chromate, at least one in lutetium acid iron and yttrium aluminate, described carbide is selected from carborundum, tungsten carbide, ramet, boron carbide, at least one in titanium carbide and hafnium carbide, described sulfide is selected from cadmium sulfide, vulcanized lead, ferrous disulfide, copper sulfide, at least one in zinc sulphide and nickel sulfide.
In an embodiment, in described first organic barrier layer, the mol ratio of described hole mobile material and described electron transport material is 40:100～60:100 therein; Described in described the first inorganic barrier layer, the quality percentage composition of carbide is 10%～30%, and the quality percentage composition of described sulfide is 10%～30%; In described second organic barrier layer, the mol ratio of described hole mobile material and described electron transport material is 40:100～60:100; Described in described the second inorganic barrier layer, the quality percentage composition of carbide is 10%～30%.
In an embodiment, the quantity of described cap is that 2～4,2～4 caps stack gradually therein.
In an embodiment, the thickness on described first organic barrier layer is 200nm～300nm therein; The thickness of described the first inorganic barrier layer is 100nm～200nm; The thickness on described second organic barrier layer is 200nm～300nm; The thickness of described the second inorganic barrier layer is 100nm～200nm.
In an embodiment, described cap coordinates and is formed with host cavity with described anode therein, and described luminescent layer and negative electrode are all contained in described host cavity.
Above-mentioned organic electroluminescence device and preparation method thereof, cap comprises first organic barrier layer, the first inorganic barrier layer, second organic barrier layer, the second inorganic barrier layer stacking gradually, four layers of effectively corrosion of block water oxygen of cooperation, improve waterproof oxygen ability, thereby the life-span of organic electroluminescence device is longer.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an embodiment;
Fig. 2 is preparation method's the flow chart of the organic electroluminescent of an embodiment.
Embodiment
Below in conjunction with the drawings and specific embodiments, organic electroluminescence device and preparation method thereof is further illustrated.
Refer to Fig. 1, the organic electroluminescence device 100 of an execution mode comprises the anode with anode pattern 10, functional layer 20, negative electrode 30 and the cap 40 stacking gradually.
Anode 10 is electro-conductive glass or organic PETG (PET) film substrate that conducts electricity.The ITO layer on anode 10 with the anode pattern of being prepared with.The thickness of ITO layer is 100nm～150nm.
Functional layer 20 is formed at substrate 10 surfaces.Functional layer 20 comprises hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, the electron injecting layer stacking gradually.Be appreciated that hole injection layer, hole transmission layer, electron transfer layer, electron injecting layer can omit, now functional layer 20 only comprises luminescent layer.
In present embodiment, the material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB
3).MoO
3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.
The material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of hole transmission layer is 30nm.
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy)
3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen
3).CsN
3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.
It should be noted that, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer also can adopt other materials as required.The thickness of hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer also can be adjusted as required.
Negative electrode 30 is formed at functional layer 20 surfaces.The thickness of negative electrode is 100nm.The material of negative electrode 30 is aluminium (Al).
Cap 40 is formed at the surface of negative electrode 30.In present embodiment, cap 40 covers at functional layer 20 and negative electrode 30, and the edge of cap 40 and anode 10 affixed, thereby functional layer 20 and negative electrode 30 are encapsulated on anode 10.Cap 40 is formed with host cavity.Host cavity is the groove from the surface of cap 40 depression.Cap 40 is contained in host cavity by functional layer 20 and negative electrode 30.
Cap 40 comprises first organic barrier layer 41, the first organic barrier layer 43 of inorganic barrier layer 42, second and the second inorganic barrier layer 44 stacking gradually.
First organic barrier layer 41 is formed at the surface of negative electrode 30, and the end face of covered cathode 30 and functional layer 20 and the part surface of anode 10, thereby just functional layer 20 and negative electrode 30 are encapsulated on anode 10.
The material on first organic barrier layer 41 comprises hole mobile material and electron transport material.Hole mobile material is selected from N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-4,4'-benzidine (TPD), N, N '-bis-(Alpha-Naphthyl)-N, N '-diphenyl-4,4 '-diamines (NPB), 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane (TAPC), 2-methyl-9,10-bis-(imidazoles-2-yl) anthracene (MADN), 4,4', at least one in 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and 1,3-bis-(9H-carbazole-9-yl) benzene (mCP).Electron transport material is selected from 4,7-diphenyl Phen (Bphen), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), oxine aluminium (Alq3), two (2-methyl-8-quinoline)-(4-phenylphenol) aluminium (Balq) and 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1, at least one in 2,4-triazole (TAZ).The thickness on first organic barrier layer 41 is 200nm～300nm.
Further, in first organic barrier layer 41, the mol ratio of hole mobile material and electron transport material is 40:100～60:100.
The first inorganic barrier layer 42 is formed at the surface of the first inorganic barrier layer 41.The material of the first inorganic barrier layer 42 comprises metal oxide, carbide and sulfide.Metal oxide is selected from meta-aluminic acid magnesium (MgAl
2o
4), bismuth titanates (Bi
2ti
4o
11), chromic acid nickel (CrNiO
4), cobalt-chromate (CoCr
2o
4), lutetium acid iron (Fe
2luO
4) and yttrium aluminate (Y
3al
5o
12) at least one.Carbide is selected from least one in carborundum (SiC), tungsten carbide (WC), ramet (TaC), boron carbide (BC), titanium carbide (TiC) and hafnium carbide (HfC).Sulfide is selected from cadmium sulfide (CdS), vulcanized lead (PbS), ferrous disulfide (FeS
2), at least one in copper sulfide (CuS), zinc sulphide (ZnS) and nickel sulfide (NiS).The thickness of the first inorganic barrier layer 42 is 100nm～200nm.
Further, in the first inorganic barrier layer, the quality percentage composition of carbide is 10%～30%, and the quality percentage composition of sulfide is 10%～30%, and all the other are metal oxide.
Second organic barrier layer 43 is formed at the surface of the first inorganic barrier layer 42.The material on second organic barrier layer 43 comprises hole mobile material and electron transport material.Hole mobile material is selected from N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-4,4'-benzidine (TPD), N, N '-bis-(Alpha-Naphthyl)-N, N '-diphenyl-4,4 '-diamines (NPB), 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane (TAPC), 2-methyl-9,10-bis-(imidazoles-2-yl) anthracene (MADN), 4,4', at least one in 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and 1,3-bis-(9H-carbazole-9-yl) benzene (mCP).Electron transport material is selected from 4,7-diphenyl Phen (Bphen), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), oxine aluminium (Alq3), two (2-methyl-8-quinoline)-(4-phenylphenol) aluminium (Balq) and 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1, at least one in 2,4-triazole (TAZ).The thickness on second organic barrier layer 43 is 200nm～300nm.
Further, in second organic barrier layer 43, the mol ratio of hole mobile material and electron transport material is 40:100～60:100.
The second inorganic barrier layer 44 is formed at the surface on second organic barrier layer 43.The material of the second inorganic barrier layer 44 comprises sulfide and carbide.Sulfide is selected from cadmium sulfide (CdS), vulcanized lead (PbS), ferrous disulfide (FeS
2), at least one in copper sulfide (CuS), zinc sulphide (ZnS) and nickel sulfide (NiS).Carbide is selected from least one in carborundum (SiC), tungsten carbide (WC), ramet (TaC), boron carbide (BC), titanium carbide (TiC) and hafnium carbide (HfC).The thickness of the second inorganic barrier layer 44 is 100nm～200nm.
Further, in the second inorganic barrier layer 44, the quality percentage composition of carbide is 10%～30%, and all the other are sulfide.
Preferably, the quantity of cap 40 is that 2～4,2～4 caps 40 stack gradually.2～4 caps 40 all cover at functional layer 20 and negative electrode 30, and the cap 40 that is positioned at outside covers on the cap 40 that is positioned at inner side, thereby a plurality of cap 40 forms following stepped construction: the first organic barrier layer 41/ first organic barrier layer of inorganic barrier layer 42/ second 43/ second inorganic barrier layer 44/ ... / the first organic barrier layer 41/ first organic barrier layer of inorganic barrier layer 42/ second 43/ second inorganic barrier layer 44.
In above-mentioned organic electroluminescence device 100, cap 40 comprises first organic barrier layer 41, the first organic barrier layer 43 of inorganic barrier layer 42, second and the second inorganic barrier layer 44 stacking gradually, four layers of effectively corrosion of block water oxygen of cooperation, cap 40 is encapsulated in functional layer 20 and negative electrode 30 on anode 10, can effectively improve waterproof oxygen ability, thereby the life-span of organic electroluminescence device 100 is longer.
The host cavity that is appreciated that cap 40 can omit, and now directly on anode 10, host cavity is set.
Please refer to Fig. 2, the preparation method of the organic electroluminescence device 100 of an execution mode, it comprises the following steps:
Step S110, on anode 10, form functional layer 20.
Functional layer 20 comprises hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, the electron injecting layer stacking gradually.
Anode 10 can be electro-conductive glass substrate or organic PETG (PET) film substrate that conducts electricity.Anode 10 has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm～150nm.
Preliminary treatment was first carried out to remove the pollutant on substrate 10 surfaces in anode 10 surfaces before forming functional layer 20, and the oxygen content of carrying out surface active increase anode 10 surfaces is to improve the work function on anode 10 surfaces.Be specially, anode 10 is adopted successively and removes each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min, dry up afterwards with nitrogen, baking box is dried.
In present embodiment, the material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB
3).MoO
3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy)
3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen
3), CsN
3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
It should be noted that, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer also can adopt other materials as required.Hole injection layer, hole transmission layer, electron transfer layer, electron injecting layer can omit, and now functional layer 20 only comprises luminescent layer.
Step S120, on functional layer 20 surface, form negative electrodes 30.
The material of negative electrode 30 is aluminium (Al).The thickness of negative electrode 30 is 100nm.Negative electrode 30 is formed by vacuum evaporation, and vacuum degree is 5 * 10
-5pa, evaporation rate is
Step S130, on negative electrode 30 surfaces, prepare cap 40.
Cap 40 is formed at the surface of negative electrode 30.In present embodiment, cap 40 covers at functional layer 20 and negative electrode 30, and the edge of cap 40 and anode 10 affixed, thereby functional layer 20 and negative electrode 30 are encapsulated on anode 10.Cap 40 is formed with host cavity.Host cavity is the groove from the surface of cap 40 depression.Cap 40 is contained in host cavity by functional layer 20 and negative electrode 30.
Cap 40 comprises first organic barrier layer 41, the first organic barrier layer 43 of inorganic barrier layer 42, second and the second inorganic barrier layer 44 stacking gradually.
First organic barrier layer 41 is formed at the surface of negative electrode 30, and the end face of covered cathode 30 and functional layer 20 and the part surface of anode 10, thereby just functional layer 20 and negative electrode 30 are encapsulated on anode 10.
The material on first organic barrier layer 41 comprises hole mobile material and electron transport material.Hole mobile material is selected from N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-4,4'-benzidine (TPD), N, N '-bis-(Alpha-Naphthyl)-N, N '-diphenyl-4,4 '-diamines (NPB), 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane (TAPC), 2-methyl-9,10-bis-(imidazoles-2-yl) anthracene (MADN), 4,4', at least one in 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and 1,3-bis-(9H-carbazole-9-yl) benzene (mCP).Electron transport material is selected from 4,7-diphenyl Phen (Bphen), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), oxine aluminium (Alq3), two (2-methyl-8-quinoline)-(4-phenylphenol) aluminium (Balq) and 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1, at least one in 2,4-triazole (TAZ).The thickness on first organic barrier layer 41 is 200nm～300nm.
Further, in first organic barrier layer 41, the mol ratio of hole mobile material and electron transport material is 40:100～60:100.
First organic barrier layer 41 is formed by vacuum evaporation, and vacuum degree is 1 * 10
-5pa～1 * 10
-3pa, the evaporation rate of electron transport material
The first inorganic barrier layer 42 is formed at the surface of the first inorganic barrier layer 41.The material of the first inorganic barrier layer 42 comprises metal oxide, carbide and sulfide.Metal oxide is selected from meta-aluminic acid magnesium (MgAl
2o
4), bismuth titanates (Bi
2ti
4o
11), chromic acid nickel (CrNiO
4), cobalt-chromate (CoCr
2o
4), lutetium acid iron (Fe
2luO
4) and yttrium aluminate (Y
3al
5o
12) at least one.Carbide is selected from least one in carborundum (SiC), tungsten carbide (WC), ramet (TaC), boron carbide (BC), titanium carbide (TiC) and hafnium carbide (HfC).Sulfide is selected from cadmium sulfide (CdS), vulcanized lead (PbS), ferrous disulfide (FeS
2), at least one in copper sulfide (CuS), zinc sulphide (ZnS) and nickel sulfide (NiS).The thickness of the first inorganic barrier layer 42 is 100nm～200nm.
Further, in the first inorganic barrier layer, the quality percentage composition of carbide is 10%～30%, and the quality percentage composition of sulfide is 10%～30%, and all the other are metal oxide.
The first inorganic barrier layer 42 is prepared by magnetron sputtering, and base vacuum degree is 1 * 10
-5pa～1 * 10
-3pa.
Second organic barrier layer 43 is formed at the surface of the first inorganic barrier layer 42.The material on second organic barrier layer 43 comprises hole mobile material and electron transport material.Hole mobile material is selected from N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-4,4'-benzidine (TPD), N, N '-bis-(Alpha-Naphthyl)-N, N '-diphenyl-4,4 '-diamines (NPB), 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane (TAPC), 2-methyl-9,10-bis-(imidazoles-2-yl) anthracene (MADN), 4,4', at least one in 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and 1,3-bis-(9H-carbazole-9-yl) benzene (mCP).Electron transport material is selected from 4,7-diphenyl Phen (Bphen), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), oxine aluminium (Alq3), two (2-methyl-8-quinoline)-(4-phenylphenol) aluminium (Balq) and 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1, at least one in 2,4-triazole (TAZ).The thickness on second organic barrier layer 43 is 200nm～300nm.
Further, in second organic barrier layer 43, the mol ratio of hole mobile material and electron transport material is 40:100～60:100.
Second organic barrier layer 43 is formed by vacuum evaporation, and vacuum degree is 1 * 10
-5pa～1 * 10
-3pa, evaporation rate
The second inorganic barrier layer 44 is formed at the surface on second organic barrier layer 43.The material of the second inorganic barrier layer 44 comprises sulfide and carbide.Sulfide is selected from cadmium sulfide (CdS), vulcanized lead (PbS), ferrous disulfide (FeS
2), at least one in copper sulfide (CuS), zinc sulphide (ZnS) and nickel sulfide (NiS).Carbide is selected from least one in carborundum (SiC), tungsten carbide (WC), ramet (TaC), boron carbide (BC), titanium carbide (TiC) and hafnium carbide (HfC).The thickness of the second inorganic barrier layer 44 is 100nm～200nm.
The second inorganic barrier layer 44 is prepared by magnetron sputtering, and base vacuum degree is 1 * 10
-5pa～1 * 10
-3pa.
Further, in the second inorganic barrier layer 44, the quality percentage composition of carbide is 10%～30%.
Preferably, the quantity of cap 40 is that 2～4,2～4 caps 40 stack gradually.2～4 caps 40 all cover at functional layer 20 and negative electrode 30, and the cap 40 that is positioned at outside covers on the cap 40 that is positioned at inner side, thereby a plurality of cap 40 forms following stepped construction: the first organic barrier layer 41/ first organic barrier layer of inorganic barrier layer 42/ second 43/ second inorganic barrier layer 44/ ... / the first organic barrier layer 41/ first organic barrier layer of inorganic barrier layer 42/ second 43/ second inorganic barrier layer 44.
Cap 40 is formed at the surface of negative electrode 30.In present embodiment, cap 40 covers at functional layer 20 and negative electrode 30, and the edge of cap 40 and anode 10 affixed, thereby functional layer 20 and negative electrode 30 are encapsulated on anode 10.Cap 40 is formed with host cavity.Host cavity is the groove from the surface of cap 40 depression.Cap 40 is contained in host cavity by functional layer 20 and negative electrode 30.
The host cavity that is appreciated that cap 40 can omit, and now directly on anode 10, host cavity is set.
The preparation method of above-mentioned organic electroluminescence device, preparation technology is simple, easily preparation in enormous quantities.
Below in conjunction with specific embodiment, organic electroluminescence device preparation method provided by the invention is elaborated.
Embodiment 1
The present embodiment is prepared structure: ITO/NPB:MoO
3/ TCTA/TPBI:Ir (ppy)
3/ Bphen/Bphen:CsN
3the organic electroluminescence device of/Al/ cap; Wherein, brace "/" represents layer structure, and colon ": " represents doping, lower same.
The preparation method of above-mentioned organic electroluminescence device, comprises the following steps:
1, on anode, form functional layer.
Anode 10 is electro-conductive glass.Anode 10 has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 150nm.
Preliminary treatment was first carried out to remove the pollutant on substrate 10 surfaces in anode 10 surfaces before forming functional layer 20, and the oxygen content of carrying out surface active increase anode 10 surfaces is to improve the work function on anode 10 surfaces.Be specially, anode 10 is adopted successively and removes each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB
3).MoO
3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy)
3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen
3), CsN
3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
2, on functional layer surface, form negative electrode.
The material of negative electrode is aluminium.The thickness of negative electrode is 100nm.Negative electrode is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
3, at cathode surface, prepare cap.
Cap is formed at the surface of negative electrode, and the end face of covered cathode and functional layer and the part surface of anode, thereby just functional layer and negative electrode are encapsulated on anode.
Cap comprises first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer stacking gradually.
First organic barrier layer adopts vacuum evaporation preparation, and material comprises TPD and Bphen, and the mol ratio of TPD and Bphen is 55:100, vacuum degree 1 * 10
-5pa, the evaporation rate of Bphen
thickness 300nm;
The first inorganic barrier layer is prepared by magnetron sputtering, and material comprises MgAl
2o
4, SiC and CdS, base vacuum degree 1 * 10
-5pa, the quality percentage composition that the quality percentage composition of SiC is 20%, CdS is 15%, all the other are MgAl
2o
4, thickness 170nm;
Second organic barrier layer adopts vacuum evaporation preparation, and material comprises TPD and Bphen, and the mol ratio of TPD and Bphen is 55:100, vacuum degree 1 * 10
-5pa, the evaporation rate of Bphen
thickness 300nm;
The second inorganic barrier layer is prepared by magnetron sputtering, and material comprises SiC and CdS, base vacuum degree 1 * 10
-5pa, the quality percentage composition of SiC is 30%, all the other are CdS, thickness 200nm;
The quantity of cap is that 4,4 caps stack gradually.The structure of cap is (TPD:Bphen/MgAl
2o
4: SiC:CdS/TPD:Bphen/SiC:CdS)
4
Embodiment 2
The present embodiment is prepared structure: ITO/NPB:MoO
3/ TCTA/TPBI:Ir (pp
y)
3/ Bphen/Bphen:CsN
3the organic electroluminescence device of/Al/ cap.
The preparation method of above-mentioned organic electroluminescence device, comprises the following steps:
1, on anode, form functional layer.
Anode 10 is electro-conductive glass.Anode 10 has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 120nm.
Preliminary treatment was first carried out to remove the pollutant on substrate 10 surfaces in anode 10 surfaces before forming functional layer 20, and the oxygen content of carrying out surface active increase anode 10 surfaces is to improve the work function on anode 10 surfaces.Be specially, anode 10 is adopted successively and removes each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB
3).MoO
3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy)
3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen
3), CsN
3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
2, on functional layer surface, form negative electrode.
The material of negative electrode is aluminium.The thickness of negative electrode is 100nm.Negative electrode is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
3, at cathode surface evaporation protective layer.
The material of protective layer is NPB.The thickness of protective layer 40 is 300nm.Protective layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
4, at protective layer, prepare cap.
Cap is formed at the surface of negative electrode, and the end face of covered cathode and functional layer and the part surface of anode, thereby just functional layer and negative electrode are encapsulated on anode.
Cap comprises first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer stacking gradually.
First organic barrier layer adopts vacuum evaporation preparation, and material comprises NPB and BCP, and the mol ratio of NPB and BCP is 50:100, vacuum degree 5 * 10
-5pa, the evaporation rate of BCP
thickness 250nm;
The first inorganic barrier layer is prepared by magnetron sputtering, and material comprises Bi
2ti
4o
11, WC and PbS, base vacuum degree 1 * 10
-5pa, the quality percentage composition that the quality percentage composition of WC is 30%, PbS is 10%, all the other are Bi
2ti
4o
11, thickness 200nm;
Second organic barrier layer adopts vacuum evaporation preparation, and material comprises NPB and BCP, and the mol ratio of NPB and BCP is 50:100, vacuum degree 5 * 10
-5pa, the evaporation rate of BCP
thickness 250nm;
The second inorganic barrier layer is prepared by magnetron sputtering, and material comprises WC:PbS, base vacuum degree 1 * 10
-4pa, the quality percentage composition of WC is 20%, all the other are PbS, thickness 150nm;
The quantity of cap is that 3,3 caps stack gradually.The structure of cap is (NPB:BCP/Bi
2ti
4o
11: WC:PbS/NPB:BCP/WC:PbS)
3
Embodiment 3
The present embodiment is prepared structure: ITO/NPB:MoO
3/ TCTA/TPBI:Ir (ppy)
3/ Bphen/Bphen:CsN
3the organic electroluminescence device of/Al/ cap.
The preparation method of above-mentioned organic electroluminescence device, comprises the following steps:
1, on anode, form functional layer.
Anode 10 is electro-conductive glass.Anode 10 has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Preliminary treatment was first carried out to remove the pollutant on substrate 10 surfaces in anode 10 surfaces before forming functional layer 20, and the oxygen content of carrying out surface active increase anode 10 surfaces is to improve the work function on anode 10 surfaces.Be specially, anode 10 is adopted successively and removes each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB
3).MoO
3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy)
3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen
3), CsN
3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
2, on functional layer surface, form negative electrode.
The material of negative electrode is aluminium.The thickness of negative electrode is 100nm.Negative electrode is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
3, at cathode surface, prepare cap.
Cap is formed at the surface of negative electrode, and the end face of covered cathode and functional layer and the part surface of anode, thereby just functional layer and negative electrode are encapsulated on anode.
Cap comprises first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer stacking gradually.
First organic barrier layer adopts vacuum evaporation preparation, and material comprises TAPC and TPBi, and the mol ratio of TAPC and TPBi is 50:100, vacuum degree 5 * 10
-5pa, the evaporation rate of TPBi
thickness 200nm;
The first inorganic barrier layer is prepared by magnetron sputtering, and material comprises CrNiO
4, TaC and FeS
2, base vacuum degree 1 * 10
-5pa, the quality percentage composition of TaC is 10%, FeS
2quality percentage composition be 30%, all the other are CrNiO
4, thickness 100nm;
Second organic barrier layer adopts vacuum evaporation preparation, and material comprises TAPC and TPBi, and the mol ratio of TAPC and TPBi is 50:100, vacuum degree 5 * 10
-5pa, the evaporation rate of TPBi
thickness 200nm;
The second inorganic barrier layer is prepared by magnetron sputtering, and material comprises TaC and FeS
2, base vacuum degree 1 * 10
-4pa, the quality percentage composition of TaC is 25%, all the other are FeS
2, thickness 150nm;
The quantity of cap is that 3,3 caps stack gradually.The structure of cap is (TAPC:TPBi/CrNiO
4: TaC:FeS
2/ TAPC:TPBi/TaC:FeS
2)
3
Embodiment 4
The present embodiment is prepared structure: ITO/NPB:MoO
3/ TCTA/TPBI:Ir (ppy)
3/ Bphen/Bphen:CsN
3the organic electroluminescence device of/Al/ cap.
The preparation method of above-mentioned organic electroluminescence device, comprises the following steps:
1, on anode, form functional layer.
Anode 10 is electro-conductive glass.Anode 10 has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Preliminary treatment was first carried out to remove the pollutant on substrate 10 surfaces in anode 10 surfaces before forming functional layer 20, and the oxygen content of carrying out surface active increase anode 10 surfaces is to improve the work function on anode 10 surfaces.Be specially, anode 10 is adopted successively and removes each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB
3).MoO
3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy)
3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen
3), CsN
3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
2, on functional layer surface, form negative electrode.
The material of negative electrode is aluminium.The thickness of negative electrode is 100nm.Negative electrode is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
3, at cathode surface evaporation protective layer.
The material of protective layer is SiO.The thickness of protective layer 40 is 200nm.Protective layer is formed by vacuum evaporation, and vacuum degree is 5 * 10
-5pa, evaporation rate is
4, at protective layer, prepare cap.
Cap is formed at the surface of negative electrode, and the end face of covered cathode and functional layer and the part surface of anode, thereby just functional layer and negative electrode are encapsulated on anode.
Cap comprises first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer stacking gradually.
First organic barrier layer adopts vacuum evaporation preparation, and material comprises MADN and Alq3, and the mol ratio of MADN and Alq3 is 60:100, vacuum degree 5 * 10
-5pa, the evaporation rate of Alq3
thickness 250nm;
The first inorganic barrier layer is prepared by magnetron sputtering, and material comprises CoCr
2o
4, BC and CuS, base vacuum degree 5 * 10
-5pa, the quality percentage composition that the quality percentage composition of BC is 18%, CuS is 25%, all the other are CoCr
2o
4, thickness 170nm;
Second organic barrier layer adopts vacuum evaporation preparation, and material comprises MADN and Alq3, and the mol ratio of MADN and Alq3 is 60:100, vacuum degree 5 * 10
-5pa, the evaporation rate of Alq3
thickness 250nm;
The second inorganic barrier layer is prepared by magnetron sputtering, and material comprises BC and CuS, base vacuum degree 1 * 10
-4pa, the quality percentage composition of BC is 10%, all the other are CuS, thickness 100nm;
The quantity of cap is that 3,3 caps stack gradually.The structure of cap is (MADN:Alq3/CoCr
2o
4: BC:CuS/MADN:Alq3/BC:CuS)
3
Embodiment 5
The present embodiment is prepared structure: ITO/NPB:MoO
3/ TCTA/TPBI:Ir (ppy)
3/ Bphen/Bphen:CsN
3the organic electroluminescence device of/Al/ cap.
The preparation method of above-mentioned organic electroluminescence device, comprises the following steps:
1, on anode, form functional layer.
Anode 10 is electro-conductive glass.Anode 10 has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Preliminary treatment was first carried out to remove the pollutant on substrate 10 surfaces in anode 10 surfaces before forming functional layer 20, and the oxygen content of carrying out surface active increase anode 10 surfaces is to improve the work function on anode 10 surfaces.Be specially, anode 10 is adopted successively and removes each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB
3).MoO
3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy)
3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen
3), CsN
3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
2, on functional layer surface, form negative electrode.
The material of negative electrode is aluminium.The thickness of negative electrode is 100nm.Negative electrode is formed by vacuum evaporation, and vacuum degree is 5 * 10
-5pa, evaporation rate is
3, at cathode surface, prepare cap.
Cap is formed at the surface of negative electrode, and the end face of covered cathode and functional layer and the part surface of anode, thereby just functional layer and negative electrode are encapsulated on anode.
Cap comprises first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer stacking gradually.
First organic barrier layer adopts vacuum evaporation preparation, and material comprises TCTA and Balq, and the mol ratio of TCTA and Balq is 50:100, vacuum degree 5 * 10
-5pa, the evaporation rate of Balq
thickness 250nm;
The first inorganic barrier layer is prepared by magnetron sputtering, and material comprises Fe
2luO
4, TiC and ZnS, base vacuum degree 5 * 10
-5pa, the quality percentage composition that the quality percentage composition of TiC is 25%, ZnS is 20%, all the other are Fe
2luO
4, thickness 160nm;
Second organic barrier layer adopts vacuum evaporation preparation, and material comprises TCTA and Balq, and the mol ratio of TCTA and Balq is 50:100, vacuum degree 1 * 10
-5pa, vacuum degree 5 * 10
-5pa, the evaporation rate of Balq
thickness 250nm;
The second inorganic barrier layer is prepared by magnetron sputtering, and material comprises TiC and ZnS, base vacuum degree 1 * 10
-4pa, the quality percentage composition of TiC is 15%, all the other are ZnS, thickness 120nm;
The quantity of cap is that 3,3 caps stack gradually.The structure of cap is (TCTA:Balq/Fe
2luO
4: TiC:ZnS/TCTA:Balq/TiC:ZnS)
3
Embodiment 6
The present embodiment is prepared structure: ITO/NPB:MoO
3/ TCTA/TPBI:Ir (ppy)
3/ Bphen/Bphen:CsN
3the organic electroluminescence device of/Al/ cap.
The preparation method of above-mentioned organic electroluminescence device, comprises the following steps:
1, on anode, form functional layer.
Anode 10 is electro-conductive glass.Anode 10 has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Preliminary treatment was first carried out to remove the pollutant on substrate 10 surfaces in anode 10 surfaces before forming functional layer 20, and the oxygen content of carrying out surface active increase anode 10 surfaces is to improve the work function on anode 10 surfaces.Be specially, anode 10 is adopted successively and removes each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB
3).MoO
3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy)
3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen
3), CsN
3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
2, on functional layer surface, form negative electrode.
The material of negative electrode is aluminium.The thickness of negative electrode is 100nm.Negative electrode is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
3, at cathode surface, prepare cap.
Cap is formed at the surface of negative electrode, and the end face of covered cathode and functional layer and the part surface of anode, thereby just functional layer and negative electrode are encapsulated on anode.
Cap comprises first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer stacking gradually.
First organic barrier layer adopts vacuum evaporation preparation, and material comprises mCP and TAZ, and the mol ratio of mCP and TAZ is 40:100, vacuum degree 1 * 10
-3pa, the evaporation rate of TAZ
thickness 250nm;
The first inorganic barrier layer is prepared by magnetron sputtering, and material comprises Y
3al
5o
12, HfC and NiS, base vacuum degree 1 * 10
-3pa, the quality percentage composition that the quality percentage composition of HfC is 14%, NiS is 19%, all the other are Y
3al
5o
12, thickness 150nm;
Second organic barrier layer adopts vacuum evaporation preparation, and material comprises mCP and TAZ, and the mol ratio of mCP and TAZ is 40:100, vacuum degree 1 * 10
-3pa, the evaporation rate of TAZ
thickness 250nm;
The second inorganic barrier layer is prepared by magnetron sputtering, and material comprises HfC and NiS, base vacuum degree 1 * 10
-3pa, the quality percentage composition of HfC is 15%, all the other are NiS, thickness 100nm;
The quantity of cap is that 2,2 caps stack gradually.The structure that 2 caps stack gradually is (mCP:TAZ/Y
3al
5o
12: HfC:NiS/mCP:TAZ/HfC:NiS)
2
Comparative example
The present embodiment is prepared structure: ITO/NPB:MoO
3/ TCTA/TPBI:Ir (ppy)
3/ Bphen/Bphen:CsN
3the organic electroluminescence device of/Al/ cap.
The preparation method of above-mentioned organic electroluminescence device, comprises the following steps:
1, on anode, form functional layer.
Anode 10 is electro-conductive glass.Anode 10 has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Preliminary treatment was first carried out to remove the pollutant on substrate 10 surfaces in anode 10 surfaces before forming functional layer 20, and the oxygen content of carrying out surface active increase anode 10 surfaces is to improve the work function on anode 10 surfaces.Be specially, anode 10 is adopted successively and removes each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB
3).MoO
3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy)
3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen
3), CsN
3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
2, on functional layer surface, form negative electrode.
The material of negative electrode is aluminium.The thickness of negative electrode is 100nm.Negative electrode is formed by vacuum evaporation, and vacuum degree is 3 * 10
-5pa, evaporation rate is
3, at cathode surface, prepare cap.
Cap is formed at the surface of negative electrode, and the end face of covered cathode and functional layer and the part surface of anode, thereby just functional layer and negative electrode are encapsulated on anode.
Cap comprises first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer stacking gradually.
First organic barrier layer adopts vacuum evaporation preparation, and material is TPD, vacuum degree 1 * 10
-5pa, the evaporation rate of electron transport material
thickness 300nm;
The first inorganic barrier layer is prepared by magnetron sputtering, and material is MgAl
2o
4, base vacuum degree 1 * 10
-5pa, thickness 170nm;
Second organic barrier layer adopts vacuum evaporation preparation, and material is TPD, vacuum degree 1 * 10
-5pa, the evaporation rate of electron transport material
thickness 300nm;
The second inorganic barrier layer is prepared by magnetron sputtering, and material is SiC, base vacuum degree 1 * 10
-5pa, thickness 200nm;
The quantity of cap is that 4,4 caps stack gradually.The structure of cap is (TPD/MgAl
2o
4/ TPD/SiC)
4
The preparation used of the embodiment of the present invention and comparative example and tester are: high vacuum coating equipment (scientific instrument development center, Shenyang Co., Ltd, pressure <1 * 10-3Pa), magnetron sputtering apparatus (scientific instrument development center, Shenyang Co., Ltd), current-voltage tester (U.S. Keithly company, 2400), chroma-luminance meter (Konica Minolta, model: CS-100A) model:.
Refer to table 1, table 1 is depicted as the test result of the aqueous vapor penetrance (Water Vapor Transmission Rate) of organic electroluminescence device prepared by embodiment 1～embodiment 6 and comparative example.The aqueous vapor penetrance of the organic electroluminescence device of embodiment 1～embodiment 6 preparations is all less than 5.2 * 10 as can be seen from Table 1
-4g/m
2/ day, the aqueous vapor penetrance (6.7 * 10 of the organic electroluminescence device of preparing much smaller than comparative example
-3g/m
2/ day) waterproof effect is better, can effectively reduce the erosion of outside aqueous vapor to organic electroluminescence device, thereby improves the life-span of organic electroluminescence device.
Table 1
| ? | WVTR(g/m 2/day) |
| Embodiment 1 | 3.0×10 -4 |
| Embodiment 2 | 3.4×10 -4 |
| Embodiment 3 | 3.6×10 -4 |
| Embodiment 4 | 3.9×10 -4 |
| Embodiment 5 | 4.0×10 -4 |
| Embodiment 6 | 4.7×10 -4 |
| Comparative example | 6.7×10 -3 |
Refer to table 2, it is 1000cd/m at original intensity that table 2 is depicted as organic electroluminescence device prepared by embodiment 1～embodiment 6 and comparative example
2condition under life-span (brightness is reduced to original intensity 70% time used).
Table 2
As can be seen from Table 2, the initial brightness of the organic electroluminescence device of embodiment 1～embodiment 6 preparations is 1000cd/m
2time, the life-span reaches more than 6301 hours, and the life-span is longer.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore 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, comprise the anode, luminescent layer and the negative electrode that stack gradually, it is characterized in that: described organic electroluminescence device also comprises cap, described cap is packaged in described luminescent layer and negative electrode on described anode, and described cap comprises first organic barrier layer, be formed at the first inorganic barrier layer of described first organic barrier layer surface, be formed at second organic barrier layer on described the first inorganic barrier layer surface and be formed at the second inorganic barrier layer of described second organic barrier layer surface;
The material on described first organic barrier layer comprises hole mobile material and electron transport material, and the material of described the first inorganic barrier layer comprises metal oxide, carbide and sulfide, the material on described second organic barrier layer comprises hole mobile material and electron transport material, the material of described the second inorganic barrier layer comprises sulfide and carbide, described hole mobile material is selected from N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-4,4'-benzidine, N, N '-bis-(Alpha-Naphthyl)-N, N '-diphenyl-4,4 '-diamines, 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, 2-methyl-9,10-bis-(imidazoles-2-yl) anthracene, 4,4', at least one in 4''-tri-(carbazole-9-yl) triphenylamine and 1,3-bis-(9H-carbazole-9-yl) benzene, described electron transport material is selected from 4,7-diphenyl Phen, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, oxine aluminium, two (2-methyl-8-quinoline)-(4-phenylphenol) aluminium and 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1, at least one in 2,4-triazole, described metal oxide is selected from meta-aluminic acid magnesium, bismuth titanates, chromic acid nickel, cobalt-chromate, at least one in lutetium acid iron and yttrium aluminate, described carbide is selected from carborundum, tungsten carbide, ramet, boron carbide, at least one in titanium carbide and hafnium carbide, described sulfide is selected from cadmium sulfide, vulcanized lead, ferrous disulfide, copper sulfide, at least one in zinc sulphide and nickel sulfide.
2. organic electroluminescence device according to claim 1, is characterized in that, the quantity of described cap is that 2～4,2～4 caps stack gradually.
3. organic electroluminescence device according to claim 1, is characterized in that, the thickness on described first organic barrier layer is 200nm～300nm; The thickness of described the first inorganic barrier layer is 100nm～200nm; The thickness on described second organic barrier layer is 200nm～300nm; The thickness of described the second inorganic barrier layer is 100nm～200nm.
4. organic electroluminescence device according to claim 1, is characterized in that, in described first organic barrier layer, the mol ratio of described hole mobile material and described electron transport material is 40:100～60:100; Described in described the first inorganic barrier layer, the quality percentage composition of carbide is 10%～30%, and the quality percentage composition of described sulfide is 10%～30%; In described second organic barrier layer, the mol ratio of described hole mobile material and described electron transport material is 40:100～60:100; Described in described the second inorganic barrier layer, the quality percentage composition of carbide is 10%～30%.
5. organic electroluminescence device according to claim 1, is characterized in that, described cap coordinates and is formed with host cavity with described anode, and described luminescent layer and negative electrode are all contained in described host cavity.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
At anode surface, prepare luminescent layer;
On described luminescent layer surface, prepare negative electrode; And
At described cathode surface, prepare cap, described cap is packaged in described luminescent layer and negative electrode on described anode, and described cap comprises first organic barrier layer, be formed at the first inorganic barrier layer of described first organic barrier layer surface, be formed at second organic barrier layer on described the first inorganic barrier layer surface and be formed at the second inorganic barrier layer of described second organic barrier layer surface, the material on described first organic barrier layer comprises hole mobile material and electron transport material, and the material of described the first inorganic barrier layer comprises metal oxide, carbide and sulfide, the material on described second organic barrier layer comprises hole mobile material and electron transport material, the material of described the second inorganic barrier layer comprises sulfide and carbide, described hole mobile material is selected from N, N'-diphenyl-N, N'-bis-(3-aminomethyl phenyl)-4,4'-benzidine, N, N '-bis-(Alpha-Naphthyl)-N, N '-diphenyl-4,4 '-diamines, 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, 2-methyl-9,10-bis-(imidazoles-2-yl) anthracene, 4,4', at least one in 4''-tri-(carbazole-9-yl) triphenylamine and 1,3-bis-(9H-carbazole-9-yl) benzene, described electron transport material is selected from 4,7-diphenyl Phen, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, oxine aluminium, two (2-methyl-8-quinoline)-(4-phenylphenol) aluminium and 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1, at least one in 2,4-triazole, described metal oxide is selected from meta-aluminic acid magnesium, bismuth titanates, chromic acid nickel, cobalt-chromate, at least one in lutetium acid iron and yttrium aluminate, described carbide is selected from carborundum, tungsten carbide, ramet, boron carbide, at least one in titanium carbide and hafnium carbide, described sulfide is selected from cadmium sulfide, vulcanized lead, ferrous disulfide, copper sulfide, at least one in zinc sulphide and nickel sulfide.
7. the preparation method of organic electroluminescence device according to claim 6, is characterized in that, in described first organic barrier layer, the mol ratio of described hole mobile material and described electron transport material is 40:100～60:100; Described in described the first inorganic barrier layer, the quality percentage composition of carbide is 10%～30%, and the quality percentage composition of described sulfide is 10%～30%; In described second organic barrier layer, the mol ratio of described hole mobile material and described electron transport material is 40:100～60:100; Described in described the second inorganic barrier layer, the quality percentage composition of carbide is 10%～30%.
8. the preparation method of organic electroluminescence device according to claim 6, is characterized in that, the quantity of described cap is that 2～4,2～4 caps stack gradually.
9. the preparation method of organic electroluminescence device according to claim 6, is characterized in that: the thickness on described first organic barrier layer is 200nm～300nm; The thickness of described the first inorganic barrier layer is 100nm～200nm; The thickness on described second organic barrier layer is 200nm～300nm; The thickness of described the second inorganic barrier layer is 100nm～200nm.
10. the preparation method of organic electroluminescence device according to claim 6, is characterized in that: described cap coordinates and is formed with host cavity with described anode, and described luminescent layer and negative electrode are all contained in described host cavity.
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