CN104103762A - Organic light-emitting display and preparation method thereof - Google Patents
Organic light-emitting display and preparation method thereof Download PDFInfo
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- CN104103762A CN104103762A CN201310121393.7A CN201310121393A CN104103762A CN 104103762 A CN104103762 A CN 104103762A CN 201310121393 A CN201310121393 A CN 201310121393A CN 104103762 A CN104103762 A CN 104103762A
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Abstract
The invention discloses an organic light-emitting display which includes an anode conductive substrate, a hole injection layer, a hole transport layer, a light-emitting layer, an electronic transmission layer, an electronic injection layer, a cathode layer and mixed barrier layers, which are sequentially laminated. Each mixed barrier layer is formed through sequential lamination of a first organic barrier layer, a second organic barrier layer, a first inorganic barrier layer, a third organic barrier layer, a forth organic barrier layer and a second inorganic barrier layer, and a layer of first organic barrier layer is in direct contact with the cathode layer. The mixed barrier layers of the organic light-emitting display are excellent in flexibility, high in compactness, and capable of preventing moisture and oxygen from entering the organic light-emitting display. Compared with traditional organic light-emitting displays, the organic light-emitting display is longer in service life. The invention also discloses a preparation method for the organic light-emitting display.
Description
Technical field
The present invention relates to organic electroluminescent field, particularly relate to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (Organic Light Emitting Display, OLED) be a kind of current mode light emitting semiconductor device based on organic material, its typical structure is that the luminous organic material of making 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.In the time being added with voltage on electrode, luminescent layer just produces light radiation.
OLED have active illuminating, luminous efficiency high, low in energy consumption, light, thin, without advantages such as angle limitations, thought to be most likely at by insider the device of new generation that occupies dominance on following illumination and display device market.As a brand-new illumination and Display Technique, the ten years development in the past of OLED technology is swift and violent, has obtained huge achievement.Throw light on because the whole world is increasing and show that producer drops into research and development one after another, having promoted greatly the industrialization process of OLED, making the growth rate of OLED industry surprising, having arrived the eve of scale of mass production at present.
Traditional organic electroluminescence device, adopt metal material as cathode layer, because metal is time prepared by evaporation, easily there is pin hole and defect, cause like this steam and oxygen easily from pin hole and fault location to luminescent device internal penetration, organic electroluminescence device was lost efficacy, thereby make the life-span of traditional organic electroluminescence device shorter.
Summary of the invention
Based on this, be necessary to provide organic electroluminescence device of growing a kind of useful life and preparation method thereof.
A kind of organic electroluminescence device, comprises anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, the cathode layer stacking gradually and mixes barrier layer; Described mixing barrier layer is stacked gradually and is formed by first organic barrier layer, second organic barrier layer, the first inorganic barrier layer, the 3rd organic barrier layer, the 4th organic barrier layer and the second inorganic barrier layer, and described in one deck, first organic barrier layer directly contacts with described cathode layer;
The material on described first organic barrier layer is 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene;
The material on described second organic barrier layer is 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 or 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1,2,4-triazole;
The material of described the first inorganic barrier layer is Si
3n
4, AlN, BN, HfN, TaN or TiN;
The material on described the 3rd organic barrier layer is 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene;
The material on described the 4th organic barrier layer is 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 or 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1,2,4-triazole;
The material of described the second inorganic barrier layer is AlB
2, LaB
6, VB
2, NbB, TiB
2or MoB.
In one embodiment, described organic electroluminescence device comprises 2～4 layers of described mixing barrier layer stacking gradually.
In one embodiment, the thickness on described first organic barrier layer is 200nm～300nm; The thickness on described second organic barrier layer is 200nm～300nm; The thickness on described the 3rd organic barrier layer is 200nm～300nm; The thickness on described the 4th organic barrier layer is 200nm～300nm.
In one embodiment, the thickness of described the first inorganic barrier layer is 50nm～100nm; The thickness of described the second inorganic barrier layer is 50nm～100nm.
In one embodiment, the material of described hole injection layer is the N of molybdenum trioxide of having adulterated, N'-diphenyl-N, and N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, the percentage by weight that described molybdenum trioxide accounts for described hole injection layer is 30%;
The material of described hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine;
The material of described luminescent layer is closed 1,3 of iridium for three (the 2-phenylpyridines) that adulterated, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, and it is 5% that described three (2-phenylpyridines) close the percentage by weight that iridium accounts for described luminescent layer;
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline;
The material of described electron injecting layer is 4 of the cesium azide that adulterated, 7-diphenyl Phen, and the percentage by weight that described cesium azide accounts for described electron injecting layer is 30%.
A preparation method for organic electroluminescence device, comprises the steps:
Anode conducting substrate is provided;
On the anode conductive layer of described anode conducting substrate, vacuum evaporation forms hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer successively;
On described cathode layer, preparation mixes barrier layer; Described mixing barrier layer is stacked gradually and is formed by first organic barrier layer, second organic barrier layer, the first inorganic barrier layer, the 3rd organic barrier layer, the 4th organic barrier layer and the second inorganic barrier layer, and described first organic barrier layer directly contacts with described cathode layer; Prepare by vacuum evaporation on described first organic barrier layer, second organic barrier layer, the 3rd organic barrier layer and the 4th organic barrier layer, and described the first inorganic barrier layer and described the second inorganic barrier layer are prepared by magnetron sputtering; The material on described first organic barrier layer is 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene; The material on described second organic barrier layer is 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 or 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1,2,4-triazole; The material of described the first inorganic barrier layer is Si
3n
4, AlN, BN, HfN, TaN or TiN; The material on described the 3rd organic barrier layer is 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene; The material on described the 4th organic barrier layer is 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 or 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1,2,4-triazole; The material of described the second inorganic barrier layer is AlB
2, LaB
6, VB
2, NbB, TiB
2or MoB.
In one embodiment, described organic electroluminescence device comprises 2～4 layers of described mixing barrier layer stacking gradually.
In one embodiment, when described first organic barrier layer is prepared in vacuum evaporation, vacuum degree is 1 × 10
-5pa～1 × 10
-3pa, evaporation rate is
when described second organic barrier layer is prepared in vacuum evaporation, vacuum degree is 1 × 10
-5pa～1 × 10
-3pa, evaporation rate is
when described the 3rd organic barrier layer is prepared in vacuum evaporation, vacuum degree is 1 × 10
-5pa～1 × 10
-3pa, evaporation rate is
when described the 4th organic barrier layer is prepared in vacuum evaporation, vacuum degree is 1 × 10
-5pa～1 × 10
-3pa, evaporation rate is
When magnetron sputtering is prepared described the first inorganic barrier layer, base vacuum degree is 1 × 10
-5pa～1 × 10
-3pa; When magnetron sputtering is prepared the second inorganic barrier layer, base vacuum degree is 1 × 10
-5pa～1 × 10
-3pa.
In one embodiment, the thickness on described first organic barrier layer is 200nm～300nm; The thickness on described second organic barrier layer is 200nm～300nm; The thickness on described the 3rd organic barrier layer is 200nm～300nm; The thickness on described the 4th organic barrier layer is 200nm～300nm.
In one embodiment, the thickness of described the first inorganic barrier layer is 50nm～100nm; The thickness of described the second inorganic barrier layer is 50nm～100nm.
Above-mentioned organic electroluminescence device comprises by first organic barrier layer, second organic barrier layer, the first inorganic barrier layer, the 3rd organic barrier layer, the 4th organic barrier layer and the second inorganic barrier layer stack gradually the mixing barrier layer of composition, first organic barrier layer, second organic barrier layer, the 3rd organic barrier layer and the 4th organic barrier layer can be alleviated the stress between the first inorganic barrier layer and the second inorganic barrier layer well, increase the pliability of organic electroluminescence device, and the first inorganic barrier layer and the second inorganic barrier layer have very high compactness, therefore, mix barrier layer and can prevent that steam and oxygen from entering organic electroluminescence device.With respect to traditional organic electroluminescence device, this organic electroluminescence device has longer useful life.
Brief description of the drawings
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is the structural representation on the mixing barrier layer of organic electroluminescence device as shown in Figure 1;
Fig. 3 is organic electroluminescence device preparation method flow chart as shown in Figure 1.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details are set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, and therefore the present invention is not subject to the restriction of following public concrete enforcement.
The organic electroluminescence device of an execution mode as shown in Figure 1, comprises anode conducting substrate 110, hole injection layer 120, hole transmission layer 130, luminescent layer 140, electron transfer layer 150, electron injecting layer 160, the cathode layer 170 stacking gradually and mixes barrier layer 180.
Anode conducting substrate 110 comprises anode conductive layer and substrate.Substrate can be glass substrate or organic film substrate.The material of anode conductive layer can be conductive oxide, as, tin indium oxide (ITO), Al-Doped ZnO (AZO), mix indium zinc oxide (IZO) or fluorine doped tin oxide (FTO).These conductive oxides are prepared on glass substrate, are called for short ito glass, AZO glass, IZO glass, FTO glass.Anode conducting substrate can be made by oneself, also can buy from the market acquisition.Certainly, also can select as required other suitable materials as anode conducting substrate 110.In addition can also on anode conducting substrate 110, prepare, the anode pattern of required organic electroluminescence device.
The thickness of anode conducting substrate 110 can be 70nm～200nm.
The material of hole injection layer 120 can be the molybdenum trioxide (MoO that adulterated
3) N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB).The percentage by weight that molybdenum trioxide accounts for hole injection layer 120 can be 30%.The thickness of hole injection layer 120 can be 10nm～40nm.
The material of hole transmission layer 130 can be 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of hole transmission layer 130 can be 20nm～60nm.
The material of luminescent layer 140 can be closed iridium (Ir (ppy) for three (the 2-phenylpyridines) that adulterated
3) 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).It can be 5% that three (2-phenylpyridines) close the percentage by weight that iridium accounts for luminescent layer 140.The thickness of luminescent layer 140 can be 10nm～30nm.
The material of electron transfer layer 150 can be 4,7-diphenyl Phen (Bphen).The thickness of electron transfer layer 150 can be 10nm～60nm.
The material of electron injecting layer 160 can be the cesium azide (CsN that adulterated
3) 4,7-diphenyl Phen (Bphen).The percentage by weight that cesium azide accounts for electron injecting layer 160 can be 30%.The thickness of electron injecting layer 160 can be 10nm～40nm.
The material of cathode layer 170 can be lithium (Li), magnesium (Mg), calcium (Ca), silver (Ag), samarium (Sm), ytterbium (Yb), aluminium (Al) or its alloy.Cathode layer 170 thickness can be 20nm～100nm.
In conjunction with Fig. 2, in present embodiment, organic electroluminescence device comprises 2 layers of mixing barrier layer 180 stacking gradually.Every layer of mixing barrier layer 180 stacked gradually and formed by first organic barrier layer 181, second organic barrier layer 182, the first inorganic barrier layer 183, the 3rd organic barrier layer 184, the 4th organic barrier layer 185 and the second inorganic barrier layer 186, and the organic barrier layer 181 of one deck first directly contacts with cathode layer 170.
In other embodiments, organic electroluminescence device can comprise that 1 layer is mixed barrier layer 180, also can comprise 3 layers or the more multi-layered mixing barrier layer 180 stacking gradually.
One preferred embodiment in, organic electroluminescence device can comprise 2 layers～4 layers mixing barrier layer 180 stacking gradually.
Concrete, in present embodiment, 2 layers are mixed barrier layer 180 and stack gradually in the following order on cathode layer 170: first organic barrier layer 181, second organic barrier layer 182, the first inorganic barrier layer 183, the 3rd organic barrier layer 184, the 4th organic barrier layer 185, the second inorganic barrier layer 186, first organic barrier layer 181, second organic barrier layer 182, the first inorganic barrier layer 183, the 3rd organic barrier layer 184, the 4th organic barrier layer 185, the second inorganic barrier layer 186.When organic electroluminescence device comprises 3 layers, 4 layers,, the rest may be inferred when on even more multi-layered mixing the barrier layer 180.
The material on first organic barrier layer 181 can be 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane (TAPC), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), oxine aluminium (Alq3), 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).
The thickness on first organic barrier layer 181 can be 200nm～300nm.
The material on second organic barrier layer 182 can be 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 or 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1,2,4-triazole (TAZ).
The thickness on second organic barrier layer 182 can be 200nm～300nm.
The material of the first inorganic barrier layer 183 can be Si
3n
4, AlN, BN, HfN, TaN or TiN.
The thickness of the first inorganic barrier layer 183 can be 50nm～100nm.
The material on the 3rd organic barrier layer 184 can be 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene.
The thickness on the 3rd organic barrier layer 184 can be 200nm～300nm.
The material on the 4th organic barrier layer 185 can be 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 or 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1,2,4-triazole.
The thickness on the 4th organic barrier layer 185 can be 200nm～300nm.
The material of the second inorganic barrier layer 186 can be AlB
2, LaB
6, VB
2, NbB, TiB
2or MoB.
The thickness of the second inorganic barrier layer 186 can be 50nm～100nm.
The first inorganic barrier layer and the second inorganic barrier layer have good water oxygen barrier performance, first organic barrier layer, second organic barrier layer, the 3rd organic barrier layer and the 4th organic barrier layer can absorb and disperse the stress between the first inorganic barrier layer and the second inorganic barrier layer, avoid fine and close the first inorganic barrier layer and the second inorganic barrier layer produce slight crack and reduce barrier.First organic barrier layer, second organic barrier layer, the first inorganic barrier layer, the 3rd organic barrier layer, the 4th organic barrier layer, the second inorganic barrier layer stack gradually, can make wherein certain one deck barrier layer have hole to produce time, because the covering of multilayer barrier layer, the probability that hole is directly communicated with atmosphere subtracts greatly, and the path of water oxygen infiltration becomes complications and slows down and be even blocked.Material meetings different from thickness between the first inorganic barrier layer and the second inorganic barrier layer make water oxygen infiltration direction different with effect, can improve like this blocking effect.
Above-mentioned organic electroluminescence device comprise by first organic barrier layer, second organic barrier layer, the first inorganic barrier layer, the 3rd organic barrier layer, the 4th organic barrier layer and the second inorganic barrier layer stack gradually form mix barrier layer, first organic barrier layer, second organic barrier layer, the 3rd organic barrier layer and the 4th organic barrier layer can be alleviated the stress between the first inorganic barrier layer and the second inorganic barrier layer well, the pliability that increases organic electroluminescence device, makes organic electroluminescence device be not easy to crack or space.And the first inorganic barrier layer and the second inorganic barrier layer have very high compactness.Therefore, mix barrier layer and can prevent that steam and oxygen from entering organic electroluminescence device.With respect to traditional organic electroluminescence device, this organic electroluminescence device has longer useful life.
As shown in Figure 3, the preparation method of above-mentioned organic electroluminescence device, comprises the steps:
S10, provide anode conducting substrate 110.
The material of anode conducting substrate 110 comprises anode conductive layer and substrate.Substrate can be glass substrate or organic film substrate.The material of anode conductive layer can be conductive oxide, as, tin indium oxide (ITO), Al-Doped ZnO (AZO), mix indium zinc oxide (IZO) or fluorine doped tin oxide (FTO).These conductive oxides are prepared on glass substrate, are called for short ito glass, AZO glass, IZO glass, FTO glass.Anode conducting substrate can be made by oneself, also can buy from the market acquisition.Certainly, also can select as required other suitable materials as anode conducting substrate 110.In actual applications, can on anode conducting substrate 110, prepare the anode pattern of required organic electroluminescence device.The thickness of anode conducting substrate 110 can be 70nm～200nm.
Anode conducting substrate 110 is handled as follows successively: acetone cleaning → ethanol cleaning → washed with de-ionized water → ethanol cleans, each cleaning all adopts supersonic wave cleaning machine to clean 5 minutes, then dries up with nitrogen, and stove-drying is stand-by.Can also carry out surface activation process to the anode conducting substrate 110 after cleaning, to increase the oxygen content of conductive layer surface of anode conducting substrate 110, improve the work function of conductive layer surface.
S20, on the anode conductive layer of anode conducting substrate 110, vacuum evaporation forms hole injection layer 120, hole transmission layer 130, luminescent layer 140, electron transfer layer 150, electron injecting layer 160 and cathode layer 170 successively.
The material of hole injection layer 120 can be the N of the molybdenum trioxide that adulterated, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines.The percentage by weight that molybdenum trioxide accounts for hole injection layer 120 can be 30%.The thickness of hole injection layer 120 can be 10nm～40nm.
The vacuum degree that vacuum vapour deposition is prepared hole injection layer 120 can be 1 × 10
-3pa～1 × 10
-5pa, evaporation rate can be
The material of hole transmission layer 130 can be 4,4', 4''-tri-(carbazole-9-yl) triphenylamine.The thickness of hole transmission layer 130 can be 20nm～60nm.
The vacuum degree that vacuum vapour deposition is prepared hole transmission layer 130 can be 1 × 10
-3pa～1 × 10
-5pa, evaporation rate can be
The material of luminescent layer 140 can be closed 1,3 of iridium, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene for three (the 2-phenylpyridines) that adulterated.It can be 5% that three (2-phenylpyridines) close the percentage by weight that iridium accounts for luminescent layer 140.The thickness of luminescent layer 140 can be 10nm～30nm.。
The vacuum degree that vacuum vapour deposition is prepared luminescent layer 140 can be 1 × 10
-3pa～1 × 10
-5pa, evaporation rate can be
The material of electron transfer layer 150 can be 4,7-diphenyl-Phen.The thickness of electron transfer layer 150 can be 10nm～60nm.
The vacuum degree that vacuum vapour deposition is prepared electron transfer layer 150 can be 1 × 10
-3pa～1 × 10
-5pa, evaporation rate can be
The material of electron injecting layer 160 can be for having adulterated 4 of cesium azide, 7-diphenyl-1,10-phenanthroline.The percentage by weight that cesium azide accounts for electron injecting layer 160 can be 30%.The thickness of electron injecting layer 160 can be 10nm～40nm.。
The vacuum degree that vacuum vapour deposition is prepared electron injecting layer 160 can be 1 × 10
-3pa～1 × 10
-5pa, evaporation rate can be
The material of cathode layer 170 can be Li, Mg, Ca, Ag, Sm, Yb, Al or its alloy.The thickness of cathode layer 170 can be 20nm～100nm.In practice, can select as required material and the thickness of suitable cathode layer 170.
The vacuum degree that vacuum vapour deposition is prepared cathode layer 170 can be 1 × 10
-3pa～1 × 10
-5pa, evaporation rate can be
S30, on cathode layer 170 preparation mix barrier layer 180.
In conjunction with Fig. 1 and Fig. 2, in present embodiment, on cathode layer 170, prepare 2 layers of mixing barrier layer 180 stacking gradually.Every layer of mixing barrier layer 180 stacked gradually and formed by first organic barrier layer 181, second organic barrier layer 182, the first inorganic barrier layer 183, the 3rd organic barrier layer 184, the 4th organic barrier layer 185 and the second inorganic barrier layer 186, and the organic barrier layer 181 of one deck first directly contacts with cathode layer 170.
In other execution mode, organic electroluminescence device can comprise that 1 layer is mixed barrier layer 180, also can comprise 3 layers or the more multi-layered mixing barrier layer 180 stacking gradually.
One preferred embodiment in, organic electroluminescence device can comprise 2 layers～4 layers mixing barrier layer 180 stacking gradually.
Concrete, in present embodiment, 2 layers are mixed barrier layer 180 and stack gradually in the following order on cathode layer 170: first organic barrier layer 181, second organic barrier layer 182, the first inorganic barrier layer 183, the 3rd organic barrier layer 184, the 4th organic barrier layer 185, the second inorganic barrier layer 186, first organic barrier layer 181, second organic barrier layer 182, the first inorganic barrier layer 183, the 3rd organic barrier layer 184, the 4th organic barrier layer 185, the second inorganic barrier layer 186.When organic electroluminescence device comprises 3 layers, 4 layers,, the rest may be inferred when on even more multi-layered mixing the barrier layer 180.
The material on first organic barrier layer 181 can be 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene.The thickness on first organic barrier layer 181 can be 200nm～300nm.
When first organic barrier layer 181 is prepared in vacuum evaporation, vacuum degree can be 1 × 10
-5pa～1 × 10
-3pa, evaporation rate can be
The material on second organic barrier layer 182 can be 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 or 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1,2,4-triazole.The thickness on second organic barrier layer 182 can be 200nm～300nm.
When second organic barrier layer 182 is prepared in vacuum evaporation, vacuum degree can be 1 × 10
-5pa～1 × 10
-3pa, evaporation rate can be
The material of the first inorganic barrier layer 183 can be Si
3n
4, AlN, BN, HfN, TaN or TiN.The thickness of the first inorganic barrier layer 183 can be 50nm～100nm.
When magnetron sputtering is prepared the first inorganic barrier layer 183, base vacuum degree can be 1 × 10
-5pa～1 × 10
-3pa.
The material on the 3rd organic barrier layer 184 can be 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene.The thickness on the 3rd organic barrier layer 184 can be 200nm～300nm.
When the 3rd organic barrier layer 184 is prepared in vacuum evaporation, vacuum degree can be 1 × 10
-5pa～1 × 10
-3pa, evaporation rate can be
The material on the 4th organic barrier layer 185 can be 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 or 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1,2,4-triazole.The thickness on the 4th organic barrier layer 185 can be 200nm～300nm.
When the 4th organic barrier layer 185 is prepared in vacuum evaporation, vacuum degree can be 1 × 10
-5pa～1 × 10
-3pa, evaporation rate can be
The material of the second inorganic barrier layer 186 can be AlB
2, LaB
6, VB
2, NbB, TiB
2or MoB.The thickness of the second inorganic barrier layer 186 can be 50nm～100nm.
When magnetron sputtering is prepared the second inorganic barrier layer 186, base vacuum degree can be 1 × 10
-5pa～1 × 10
-3pa.
The organic electroluminescence device that the preparation method of above-mentioned organic electroluminescence device is applicable to prepare with substrate of glass and the preparation taking plastics or metal as the flexible organic electroluminescent device of substrate.
The preparation method of above-mentioned organic electroluminescence device has encapsulating material cheapness, and preparation technology is simple, and easily large area such as prepares at the advantage.The organic electroluminescence device waterproof oxygen ability (water vapor transmission rate, WVTR) preparing is strong, and WVTR can reach 10
-4g/m
2day increases significantly to the life-span of organic electroluminescence device simultaneously, can reach 5000 hours above (T70@1000cd/m useful life
2).
Be specific embodiment part below.
Embodiment 1
The preparation process of organic electroluminescence device is as follows:
(1) providing thickness is that the ito glass substrate of 100nm is as anode conducting substrate, and ito glass substrate is handled as follows: acetone cleaning → ethanol cleaning → washed with de-ionized water → ethanol cleans, each cleaning all adopts supersonic wave cleaning machine to clean 5 minutes, then dry up with nitrogen, stove-drying is stand-by.Ito glass substrate after cleaning is carried out to surface activation process, to increase the oxygen content of conductive layer surface, improve the work function of conductive layer surface.
(2) be 3 × 10 in vacuum degree
-5under the condition of Pa, with
evaporation rate, adopt vacuum vapour deposition on ito glass substrate, form hole injection layer.The material that hole is injected is the MoO that adulterated
3nPB, wherein MoO
3the percentage by weight that accounts for hole injection layer is 30%, and the thickness of the hole injection layer of formation is 10nm.
(3) be 1 × 10 in vacuum degree
-5under the condition of Pa, with
evaporation rate, adopt vacuum vapour deposition on hole injection layer, form hole transmission layer.The material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), and the thickness of the hole transmission layer of formation is 30nm.
(4) be 1 × 10 in vacuum degree
-5under the condition of Pa, with
evaporation rate, adopt vacuum vapour deposition on hole transmission layer, form luminescent layer.The material of luminescent layer is closed iridium (Ir (ppy) for three (the 2-phenylpyridines) that adulterated
3) 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).Wherein, Ir (ppy)
3the percentage by weight that accounts for luminescent layer is 5%, and the thickness of the luminescent layer of formation is 20nm.
(5) be 1 × 10 in vacuum degree
-5under the condition of Pa, with
evaporation rate, adopt vacuum vapour deposition on luminescent layer, form electron transfer layer.The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), and the thickness of the electron transfer layer of formation is 10nm.
(6) be 1 × 10 in vacuum degree
-5under the condition of Pa, with
evaporation rate, adopt vacuum vapour deposition on electron transfer layer, form electron injecting layer.The material of electron injecting layer is the cesium azide (CsN that adulterated
3) Bphen, wherein, CsN
3the percentage by weight that accounts for electron injecting layer is 30%, and the thickness of the electron injecting layer of formation is 20nm.
(7) be 1 × 10 in vacuum degree
-5under the condition of Pa, with
evaporation rate, adopt vacuum vapour deposition on electron injecting layer, form cathode layer.The material of cathode layer is aluminium (Al), and the thickness of the cathode layer of formation is 100nm.
(8) be 1 × 10 in vacuum degree
-5under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on cathode layer, to form first organic barrier layer.The material on first organic barrier layer is TAPC, and the thickness on first organic barrier layer of formation is 200nm.
(9) be 1 × 10 in vacuum degree
-5under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on first organic barrier layer, to form second organic barrier layer.The material on second organic barrier layer is Bphen, and the thickness on second organic barrier layer of formation is 200nm.
(10) be 1 × 10 at base vacuum degree
-5under the condition of Pa, adopt magnetron sputtering method to form the first inorganic barrier layer on second organic barrier layer.The material of the first inorganic barrier layer is Si
3n
4.The thickness of the first inorganic barrier layer is 80nm.
(11) be 1 × 10 in vacuum degree
-5under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on the first inorganic barrier layer, to form the 3rd organic barrier layer.The material on the 3rd organic barrier layer is TAPC, and the thickness on the 3rd organic barrier layer of formation is 200nm.
(12) be 1 × 10 in vacuum degree
-5under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on the 3rd organic barrier layer, to form the 4th organic barrier layer.The material on the 4th organic barrier layer is Bphen, and the thickness on the 4th organic barrier layer of formation is 200nm.
(13) be 1 × 10 at base vacuum degree
-5under the condition of Pa, adopt magnetron sputtering method to form the second inorganic barrier layer on the 4th organic barrier layer.The material of the second inorganic barrier layer is AlB
2.The thickness of the second inorganic barrier layer is 70nm.
Repeat successively above-mentioned steps (8)～(13) 4 times, obtain organic electroluminescence device.
Embodiment 2
The preparation process of organic electroluminescence device is as follows:
Step (1)～(7) of step (1)～(7) and embodiment 1 are identical.
(8) be 1 × 10 in vacuum degree
-4under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on cathode layer, to form first organic barrier layer.The material on first organic barrier layer is NPB, and the thickness on first organic barrier layer of formation is 300nm.
(9) be 1 × 10 in vacuum degree
-4under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on first organic barrier layer, to form second organic barrier layer.The material on second organic barrier layer is BCP, and the thickness on second organic barrier layer of formation is 300nm.
(10) be 1 × 10 at base vacuum degree
-4under the condition of Pa, adopt magnetron sputtering method to form the first inorganic barrier layer on second organic barrier layer.The material of the first inorganic barrier layer is AlN.The thickness of the first inorganic barrier layer is 100nm.
(11) be 1 × 10 in vacuum degree
-4under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on the first inorganic barrier layer, to form the 3rd organic barrier layer.The material on the 3rd organic barrier layer is NPB, and the thickness on the 3rd organic barrier layer of formation is 300nm.
(12) be 1 × 10 in vacuum degree
-4under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on the 3rd organic barrier layer, to form the 4th organic barrier layer.The material on the 4th organic barrier layer is BCP, and the thickness on the 4th organic barrier layer of formation is 300nm.
(13) be 1 × 10 at base vacuum degree
-4under the condition of Pa, adopt magnetron sputtering method to form the second inorganic barrier layer on the 4th organic barrier layer.The material of the second inorganic barrier layer is LaB
6.The thickness of the second inorganic barrier layer is 60nm.
Repeat successively above-mentioned steps (8)～(13) 3 times, obtain organic electroluminescence device.
Embodiment 3
The preparation process of organic electroluminescence device is as follows:
Step (1)～(7) of step (1)～(7) and embodiment 1 are identical.
(8) be 1 × 10 in vacuum degree
-4under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on cathode layer, to form first organic barrier layer.The material on first organic barrier layer is Alq3, and the thickness on first organic barrier layer of formation is 250nm.
(9) be 1 × 10 in vacuum degree
-4under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on first organic barrier layer, to form second organic barrier layer.The material on second organic barrier layer is TPBi, and the thickness on second organic barrier layer of formation is 250nm.
(10) be 1 × 10 at base vacuum degree
-4under the condition of Pa, adopt magnetron sputtering method to form the first inorganic barrier layer on second organic barrier layer.The material of the first inorganic barrier layer is BN.The thickness of the first inorganic barrier layer is 50nm.
(11) be 1 × 10 in vacuum degree
-4under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on the first inorganic barrier layer, to form the 3rd organic barrier layer.The material on the 3rd organic barrier layer is Alq3, and the thickness on the 3rd organic barrier layer of formation is 250nm.
(12) be 1 × 10 in vacuum degree
-4under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on the 3rd organic barrier layer, to form the 4th organic barrier layer.The material on the 4th organic barrier layer is TPBi, and the thickness on the 4th organic barrier layer of formation is 250nm.
(13) be 1 × 10 at base vacuum degree
-4under the condition of Pa, adopt magnetron sputtering method to form the second inorganic barrier layer on the 4th organic barrier layer.The material of the second inorganic barrier layer is VB
2.The thickness of the second inorganic barrier layer is 100nm.
Repeat successively above-mentioned steps (8)～(13) 3 times, obtain organic electroluminescence device.
Embodiment 4
The preparation process of organic electroluminescence device is as follows:
Step (1)～(7) of step (1)～(7) and embodiment 1 are identical.
(8) be 1 × 10 in vacuum degree
-4under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on cathode layer, to form first organic barrier layer.The material on first organic barrier layer is m-MTDATA, and the thickness on first organic barrier layer of formation is 220nm.
(9) be 1 × 10 in vacuum degree
-4under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on first organic barrier layer, to form second organic barrier layer.The material on second organic barrier layer is Alq3, and the thickness on second organic barrier layer of formation is 240nm.
(10) be 1 × 10 at base vacuum degree
-4under the condition of Pa, adopt magnetron sputtering method to form the first inorganic barrier layer on second organic barrier layer.The material of the first inorganic barrier layer is HfN.The thickness of the first inorganic barrier layer is 60nm.
(11) be 1 × 10 in vacuum degree
-4under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on the first inorganic barrier layer, to form the 3rd organic barrier layer.The material on the 3rd organic barrier layer is m-MTDATA, and the thickness on the 3rd organic barrier layer of formation is 220nm.
(12) be 1 × 10 in vacuum degree
-4under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on the 3rd organic barrier layer, to form the 4th organic barrier layer.The material on the 4th organic barrier layer is Alq3, and the thickness on the 4th organic barrier layer of formation is 240nm.
(13) be 1 × 10 at base vacuum degree
-4under the condition of Pa, adopt magnetron sputtering method to form the second inorganic barrier layer on the 4th organic barrier layer.The material of the second inorganic barrier layer is NbB.The thickness of the second inorganic barrier layer is 50nm.
Repeat successively above-mentioned steps (8)～(13) 2 times, obtain organic electroluminescence device.
Embodiment 5
The preparation process of organic electroluminescence device is as follows:
Step (1)～(7) of step (1)～(7) and embodiment 1 are identical.
(8) be 1 × 10 in vacuum degree
-4under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on cathode layer, to form first organic barrier layer.The material on first organic barrier layer is BCP, and the thickness on first organic barrier layer of formation is 260nm.
(9) be 1 × 10 in vacuum degree
-4under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on first organic barrier layer, to form second organic barrier layer.The material on second organic barrier layer is Balq, and the thickness on second organic barrier layer of formation is 200nm.
(10) be 1 × 10 at base vacuum degree
-4under the condition of Pa, adopt magnetron sputtering method to form the first inorganic barrier layer on second organic barrier layer.The material of the first inorganic barrier layer is TaN.The thickness of the first inorganic barrier layer is 70nm.
(11) be 1 × 10 in vacuum degree
-4under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on the first inorganic barrier layer, to form the 3rd organic barrier layer.The material on the 3rd organic barrier layer is BCP, and the thickness on the 3rd organic barrier layer of formation is 260nm.
(12) be 1 × 10 in vacuum degree
-4under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on the 3rd organic barrier layer, to form the 4th organic barrier layer.The material on the 4th organic barrier layer is Balq, and the thickness on the 4th organic barrier layer of formation is 200nm.
(13) be 1 × 10 at base vacuum degree
-4under the condition of Pa, adopt magnetron sputtering method to form the second inorganic barrier layer on the 4th organic barrier layer.The material of the second inorganic barrier layer is TiB
2.The thickness of the second inorganic barrier layer is 80nm.
Repeat successively above-mentioned steps (8)～(13) 2 times, obtain organic electroluminescence device.
Embodiment 6
The preparation process of organic electroluminescence device is as follows:
Step (1)～(7) of step (1)～(7) and embodiment 1 are identical.
(8) be 1 × 10 in vacuum degree
-3under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on cathode layer, to form first organic barrier layer.The material on first organic barrier layer is TPBi, and the thickness on first organic barrier layer of formation is 200nm.
(9) be 1 × 10 in vacuum degree
-3under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on first organic barrier layer, to form second organic barrier layer.The material on second organic barrier layer is TAZ, and the thickness on second organic barrier layer of formation is 220nm.
(10) be 1 × 10 at base vacuum degree
-3under the condition of Pa, adopt magnetron sputtering method to form the first inorganic barrier layer on second organic barrier layer.The material of the first inorganic barrier layer is TiN.The thickness of the first inorganic barrier layer is 65nm.
(11) be 1 × 10 in vacuum degree
-3under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on the first inorganic barrier layer, to form the 3rd organic barrier layer.The material on the 3rd organic barrier layer is TPBi, and the thickness on the 3rd organic barrier layer of formation is 200nm.
(12) be 1 × 10 in vacuum degree
-3under the condition of Pa, with
evaporation rate, adopt the mode of vacuum evaporation on the 3rd organic barrier layer, to form the 4th organic barrier layer.The material on the 4th organic barrier layer is TAZ, and the thickness on the 4th organic barrier layer of formation is 220nm.
(13) be 1 × 10 at base vacuum degree
-3under the condition of Pa, adopt magnetron sputtering method to form the second inorganic barrier layer on the 4th organic barrier layer.The material of the second inorganic barrier layer is MoB.The thickness of the second inorganic barrier layer is 50nm.
Repeat successively above-mentioned steps (8)～(13) 2 times, obtain organic electroluminescence device.
Following table is the moisture-vapor transmission (WVTR) of the organic electroluminescence device prepared of embodiment 1～embodiment 6 and the data in useful life.
As can be seen from the above table, the anti-oxygen ability of organic electroluminescence device waterproof that adopts said method to prepare is strong, and WVTR can reach 10
-4g/m
2day, than the WVTR(10 of general organic electroluminescence device
-3g/m
2day left and right) low.Can reach 5200 hours above (T70@1000cd/m the useful life of the organic electroluminescence device simultaneously preparing
2).
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, is characterized in that, comprises anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, the cathode layer stacking gradually and mixes barrier layer; Described mixing barrier layer is stacked gradually and is formed by first organic barrier layer, second organic barrier layer, the first inorganic barrier layer, the 3rd organic barrier layer, the 4th organic barrier layer and the second inorganic barrier layer, and described in one deck, first organic barrier layer directly contacts with described cathode layer;
The material on described first organic barrier layer is 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene;
The material on described second organic barrier layer is 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 or 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1,2,4-triazole;
The material of described the first inorganic barrier layer is Si3N4, AlN, BN, HfN, TaN or TiN;
The material on described the 3rd organic barrier layer is 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene;
The material on described the 4th organic barrier layer is 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 or 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1,2,4-triazole;
The material of described the second inorganic barrier layer is AlB
2, LaB
6, VB
2, NbB, TiB
2or MoB.
2. organic electroluminescence device according to claim 1, is characterized in that, described organic electroluminescence device comprises 2～4 layers of described mixing barrier layer stacking 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 on described second organic barrier layer is 200nm～300nm; The thickness on described the 3rd organic barrier layer is 200nm～300nm; The thickness on described the 4th organic barrier layer is 200nm～300nm.
4. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described the first inorganic barrier layer is 50nm～100nm; The thickness of described the second inorganic barrier layer is 50nm～100nm.
5. organic electroluminescence device according to claim 1, it is characterized in that, the material of described hole injection layer is the N of molybdenum trioxide of having adulterated, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, the percentage by weight that described molybdenum trioxide accounts for described hole injection layer is 30%;
The material of described hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine;
The material of described luminescent layer is closed 1,3 of iridium for three (the 2-phenylpyridines) that adulterated, 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, and it is 5% that described three (2-phenylpyridines) close the percentage by weight that iridium accounts for described luminescent layer;
The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline;
The material of described electron injecting layer is 4 of the cesium azide that adulterated, 7-diphenyl Phen, and the percentage by weight that described cesium azide accounts for described electron injecting layer is 30%.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the steps:
Anode conducting substrate is provided;
On the anode conductive layer of described anode conducting substrate, vacuum evaporation forms hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer successively;
On described cathode layer, preparation mixes barrier layer; Described mixing barrier layer is stacked gradually and is formed by first organic barrier layer, second organic barrier layer, the first inorganic barrier layer, the 3rd organic barrier layer, the 4th organic barrier layer and the second inorganic barrier layer, and described first organic barrier layer directly contacts with described cathode layer; Prepare by vacuum evaporation on described first organic barrier layer, second organic barrier layer, the 3rd organic barrier layer and the 4th organic barrier layer, and described the first inorganic barrier layer and described the second inorganic barrier layer are prepared by magnetron sputtering; The material on described first organic barrier layer is 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene; The material on described second organic barrier layer is 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 or 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1,2,4-triazole; The material of described the first inorganic barrier layer is Si
3n
4, AlN, BN, HfN, TaN or TiN; The material on described the 3rd organic barrier layer is 1,1-bis-((4-N, N '-bis-(p-methylphenyl) amine) phenyl) cyclohexane, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, oxine aluminium, 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene; The material on described the 4th organic barrier layer is 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 or 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1,2,4-triazole; The material of described the second inorganic barrier layer is AlB
2, LaB
6, VB
2, NbB, TiB
2or MoB.
7. the preparation method of organic electroluminescence device according to claim 6, is characterized in that, described organic electroluminescence device comprises 2～4 layers of described mixing barrier layer stacking gradually.
8. the preparation method of organic electroluminescence device according to claim 6, is characterized in that, when described first organic barrier layer is prepared in vacuum evaporation, vacuum degree is 1 × 10
-5pa～1 × 10
-3pa, evaporation rate is
when described second organic barrier layer is prepared in vacuum evaporation, vacuum degree is 1 × 10
-5pa～1 × 10
-3pa, evaporation rate is
when described the 3rd organic barrier layer is prepared in vacuum evaporation, vacuum degree is 1 × 10
-5pa～1 × 10
-3pa, evaporation rate is
when described the 4th organic barrier layer is prepared in vacuum evaporation, vacuum degree is 1 × 10
-5pa～1 × 10
-3pa, evaporation rate is
When magnetron sputtering is prepared described the first inorganic barrier layer, base vacuum degree is 1 × 10
-5pa～1 × 10
-3pa; When magnetron sputtering is prepared the second inorganic barrier layer, base vacuum degree is 1 × 10
-5pa～1 × 10
-3pa.
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 on described second organic barrier layer is 200nm～300nm; The thickness on described the 3rd organic barrier layer is 200nm～300nm; The thickness on described the 4th organic barrier layer is 200nm～300nm.
10. the preparation method of organic electroluminescence device according to claim 6, is characterized in that, the thickness of described the first inorganic barrier layer is 50nm～100nm; The thickness of described the second inorganic barrier layer is 50nm～100nm.
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Application publication date: 20141015 |