CN104103768A - Organic light-emitting display and manufacturing method thereof - Google Patents

Organic light-emitting display and manufacturing method thereof Download PDF

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Publication number
CN104103768A
CN104103768A CN201310121394.1A CN201310121394A CN104103768A CN 104103768 A CN104103768 A CN 104103768A CN 201310121394 A CN201310121394 A CN 201310121394A CN 104103768 A CN104103768 A CN 104103768A
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barrier layer
organic
layer
organic barrier
phenyl
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周明杰
钟铁涛
王平
张娟娟
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Priority to CN201310121394.1A priority Critical patent/CN104103768A/en
Publication of CN104103768A publication Critical patent/CN104103768A/en
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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
    • 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
    • H10K50/841—Self-supporting sealing arrangements

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention relates to an organic light-emitting display which includes a substrate, an anode layer, an organic light-emitting function layer, a cathode layer and a package cover, which are arranged to be sequentially laminated. The package cover includes 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. The organic light-emitting display adopts alternative arrangement of the organic barrier layers and the inorganic barrier layers so that the package cover with a waterproof and anti-oxygen function is formed on the cathode layer, wherein the organic barrier layers include the first organic barrier layer, the second organic barrier layer, the third organic barrier layer and the forth organic barrier layer and the inorganic barrier layers include the first inorganic barrier layer and the second inorganic barrier layer and the plurality of layers are arranged alternatively so that compactness is high, waterproof and anti-oxygen capabilities are high, vapor permeability is low and service life of the whole device is prolonged significantly. Moreover, the invention also relates to a manufacturing method of the organic light-emitting display.

Description

Organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to electroluminescent technology field, especially relate 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 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.While 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, by insider, thought to be most likely at 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.Yet traditional OLED ubiquity sealing property is bad, the anti-oxygen effect of waterproof is poor, thereby shorter problem of life-span has limited its extensive use.
Summary of the invention
Based on this, be necessary to provide organic electroluminescence device that the anti-oxygen effect of a kind of waterproof is good and preparation method thereof.
A kind of organic electroluminescence device, comprise the substrate being cascading, anode layer, organic luminescence function layer and cathode layer, described organic electroluminescence device also comprises cap, described cap is by described anode layer, described organic luminescence function layer and described cathode layer are encapsulated on described substrate, described cap comprises first organic barrier layer, be formed at second organic barrier layer of described first organic barrier layer surface, be formed at the first inorganic barrier layer of described second organic barrier layer surface, be formed at the 3rd organic barrier layer on described the first inorganic barrier layer surface, be formed at the 4th organic barrier layer of described the 3rd organic barrier layer surface and the second inorganic barrier layer that is formed at described the 4th organic barrier layer surface,
Wherein, the material on described first organic barrier layer and 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 second organic barrier layer and 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 first inorganic barrier layer is aluminium boride (AlB 2), lanthanum boride (LaB 6), vanadium boride (VB 2), niobium (Nb) boride (NbB), titanium boride (TiB 2) or molybdenum boride (MoB);
The material of described the second inorganic barrier layer is antimony selenide (Sb 2se 3), selenizing molybdenum (MoSe 2), bismuth selenide (Bi 2se 3), selenizing niobium (NbSe 2), selenizing tantalum (TaSe 2) or Berzeline (Cu 2se).
In an embodiment, the quantity of described cap is 2～4 therein, the stacked setting of a plurality of caps.
Therein in an embodiment, described first organic barrier layer is different from the material on described second organic barrier layer, described first organic barrier layer is identical with the material on described the 3rd organic barrier layer, and the material on described second organic barrier layer is identical with the material on described the 4th organic barrier layer.
In an embodiment, the thickness on described first organic barrier layer and described the 3rd organic barrier layer is identical therein, is 200～300nm.
In an embodiment, the thickness on described second organic barrier layer and described the 4th organic barrier layer is identical therein, is 200～300nm.
In an embodiment, the thickness of described the first inorganic barrier layer is 50～100nm therein.
In an embodiment, the thickness of described the second inorganic barrier layer is 50～100nm therein.
In an embodiment, described organic luminescence function layer is included in hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer being cascading on described anode layer therein.
Therein in an embodiment, to be molybdenum trioxide be entrained in N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, the composite material forming in 4'-diamines according to 30% doping mass percent to the material of described hole injection layer; The material of described hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine; The material of described luminescent layer is that three (2-phenylpyridines) close iridium and are entrained according to 5% doping mass percent the composite material forming in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene; The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline; To be nitrogenize caesium be entrained in 4,7-diphenyl-1, the composite material forming in 10-phenanthroline according to 30% doping mass percent to the material of described electron injecting layer.
Above-mentioned organic electroluminescence device adopts organic barrier layer and inorganic barrier layer to be arranged alternately and is formed on the cap on cathode layer with the anti-oxygen function of waterproof, wherein, organic barrier layer comprises first organic barrier layer, second organic barrier layer, the 3rd organic barrier layer and the 4th organic barrier layer, inorganic barrier layer comprises the first inorganic barrier layer and the second inorganic barrier layer, multilayer barrier layer is arranged alternately, compactness is high, and waterproof oxygen ability is strong, and moisture-vapor transmission (WVTR) reaches 10 -4g/ (m 2* day), the life-span of whole device extends greatly.
A manufacture method for organic electroluminescence device, comprises the steps:
In clean electrically-conductive backing plate surface etch, be prepared with the anode pattern of organic electroluminescence devices;
Adopt the mode of vacuum evaporation to evaporate successively and be coated with organic luminescence function layer and cathode layer on the anode pattern surface of described electrically-conductive backing plate;
The mode of employing vacuum evaporation is evaporated and is coated with first organic barrier layer and makes described first organic barrier layer by described anode pattern, described organic luminescence function layer and the encapsulation of described cathode layer and described electrically-conductive backing plate, then adopts the mode of vacuum evaporation to be coated with second organic barrier layer at described first organic barrier layer surface;
Adopt the mode of magnetron sputtering to prepare the first inorganic barrier layer in described second organic barrier layer surface sputter;
Adopt the mode of vacuum evaporation to be coated with the 3rd organic barrier layer in described the first inorganic barrier layer surface evaporation, and be coated with the 4th organic barrier layer at described the 3rd organic barrier layer surface;
Adopt the mode of magnetron sputtering to prepare the second inorganic barrier layer in described the 4th organic barrier layer surface sputter;
Wherein, the material on described first organic barrier layer and 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 second organic barrier layer and 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 first inorganic barrier layer is AlB 2, LaB 6, VB 2, NbB, TiB 2or MoB;
The material of described the second inorganic barrier layer is Sb 2se 3, MoSe 2, Bi 2se 3, NbSe 2, TaSe 2or Cu 2se.
The manufacture method of above-mentioned organic electroluminescence device, technique is simple, and easily large area preparation, can wide popularization and application.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments organic electroluminescence device and preparation method thereof is described in further detail below.
As shown in Figure 1, the organic electroluminescence device 100 of an execution mode comprises substrate 110, anode layer 120, organic luminescence function layer 130, the cathode layer 140 being cascading and anode layer 120, organic luminescence function layer 130 and cathode layer 140 is packaged in to the cap 150 on substrate 110.
Substrate 110 is glass substrate or organic thin film.The material of anode layer 120 is indium tin oxide (ITO), and thickness is 100nm.In the present embodiment, substrate 110 and anode layer 120 are structure as a whole ito glass substrate or conductive organic matter film.
Organic luminescence function layer 130 is included in hole injection layer 131, hole transmission layer 132, luminescent layer 133, electron transfer layer 134 and the electron injecting layer 135 being cascading on anode layer 120.Wherein, the material of hole injection layer 131 is molybdenum trioxide (MoO 3) according to 30% doping mass percent, be entrained in N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, the composite material forming in 4'-diamines (NPB) (i.e. MoO wherein 3with the mass ratio of NPB be 30:100), thickness is 10nm.The material of hole transmission layer 132 is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), and thickness is 30nm.The material of luminescent layer 133 is that three (2-phenylpyridines) close iridium (Ir (ppy) 3) doping mass percent according to 5% is entrained in the composite material that forms in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi) (i.e. Ir (ppy) wherein 3with the mass ratio of TPBi be 5:100), thickness is 20nm.The material of electron transfer layer 134 is 4,7-diphenyl-1,10-phenanthroline (Bphen), and thickness is 10nm.The material of electron injecting layer 135 is nitrogenize caesium (CsN 3) according to 30% doping mass percent, be entrained in 4,7-diphenyl-1, the composite material forming in 10-phenanthroline (wherein, CsN 3with the mass ratio of Bphen be 30:100), thickness is 20nm.
Be appreciated that, in other embodiments, the structure of organic luminescence function layer is not limited to described in present embodiment, as organic light emitting functional layer can also be for comprising at least one in luminescent layer and the hole injection layer arranging in luminescent layer both sides, hole transmission layer, electron transfer layer, electron injecting layer, or organic luminescence function layer has only included luminescent layer.
The material of cathode layer 140 is good metal or the metal alloys of conductivity such as aluminium, silver, platinum.The thickness of cathode layer 140 is 100nm.
Cap 150 comprises first organic barrier layer 151, be formed at second organic barrier layer 152 on 151 surfaces, first organic barrier layer, be formed at 152 surfaces, second organic barrier layer the first inorganic barrier layer 153, be formed at the first inorganic barrier layer 153 surfaces the 3rd organic barrier layer 154, be formed at the 4th organic barrier layer 155 on 154 surfaces, the 3rd organic barrier layer and be formed at second inorganic barrier layer 156 on 155 surfaces, the 4th organic barrier layer.
In the present embodiment, the number of cap 150 is 1～4, preferably 2～4, and the stacked setting of a plurality of caps 150.
The material on first organic barrier layer 151 and the 3rd organic barrier layer 154 is 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 (Alq 3), 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), 4,7-diphenyl-1,10-Phen (BCP) or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).The thickness on first organic barrier layer 151 and the 3rd organic barrier layer 154 is 200～300nm.Preferably, the material on first organic barrier layer 151 and the 3rd organic barrier layer 154 is identical with thickness.
The material on second organic barrier layer 152 and the 4th organic barrier layer 155 is 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, two (2-methyl-8-quinoline)-(4-phenylphenol) aluminium (BAlq) or 3-(4-xenyl)-4 phenyl-5-tert-butyl benzene-1,2,4-triazole (TAZ).The thickness on second organic barrier layer 152 and the 4th organic barrier layer 155 is 200～300nm.Preferably, material and the thickness on second organic barrier layer 152 and the 4th organic barrier layer 155 are identical.
Further, first organic barrier layer 151 is different from the material on second organic barrier layer 152 in the present embodiment, if the material on first organic barrier layer 151 and second organic barrier layer 152 can not be BCP etc. simultaneously.
The material of the first inorganic barrier layer 153 is AlB 2, LaB 6, VB 2, NbB, TiB 2or MoB.The thickness of the first inorganic barrier layer 153 is 50～100nm.
The material of the second inorganic barrier layer 156 is Sb 2se 3, MoSe 2, Bi 2se 3, NbSe 2, TaSe 2or Cu 2se.The thickness of the second inorganic barrier layer 156 is 50～100nm.
100 of above-mentioned organic electroluminescent devices adopt organic barrier layer and inorganic barrier layer to be arranged alternately and are formed on the cap 150 on cathode layer with the anti-oxygen function of waterproof, wherein, organic barrier layer comprises the first the 152, the 3rd organic barrier layer 154, organic barrier layer, organic barrier layer 151, second and the 4th organic barrier layer 155, inorganic barrier layer comprises the first inorganic barrier layer 153 and the second inorganic barrier layer 156, multilayer is arranged alternately, compactness is high, waterproof oxygen ability is strong, and moisture-vapor transmission (WVTR) reaches 10 -4g/ (m 2* day), the life-span of whole device extends greatly.
Present embodiment also provides a kind of manufacture method of organic electroluminescence device, comprises the steps:
Step 1: the anode pattern that is prepared with organic electroluminescence devices in clean electrically-conductive backing plate surface etch.
In the present embodiment, before etching is prepared anode pattern, also comprise clean electrically-conductive backing plate is carried out to surface activation process, to increase the oxygen content of surperficial ITO layer, improve the step of the work function of ITO layer.
Step 2: adopt the mode of vacuum evaporation to evaporate successively and be coated with organic luminescence function layer and cathode layer on the anode pattern surface of electrically-conductive backing plate.
Organic luminescence function layer prepared by present embodiment and cathode layer are as mentioned above.
Step 3: the mode of employing vacuum evaporation is evaporated and is coated with first organic barrier layer and makes described first organic barrier layer by described anode pattern, described organic luminescence function layer and the encapsulation of described cathode layer and described electrically-conductive backing plate, then adopts the mode of vacuum evaporation to be coated with second organic barrier layer at described first organic barrier layer surface.
Step 4: adopt the mode of magnetron sputtering to prepare the first inorganic barrier layer in second organic barrier layer surface sputter.
Step 5: adopt the mode of vacuum evaporation to be coated with the 3rd organic barrier layer in described the first inorganic barrier layer surface evaporation, and be coated with the 4th organic barrier layer at described the 3rd organic barrier layer surface.
Step 6: adopt the mode of magnetron sputtering to prepare the second inorganic barrier layer in described the 4th organic barrier layer surface sputter.
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 form the cap of encapsulation anode pattern, organic luminescence function layer and cathode layer.
When needs are prepared a plurality of cap, only need to repeat above step 3 to step 6.
The manufacture method of above-mentioned organic electroluminescence device, technique is simple, and easily large area preparation, can wide popularization and application.
Be below specific embodiment part:
Embodiment 1
The organic electroluminescence device structure of the present embodiment is: ito glass substrate/MoO 3: NPB(30wt%)/TCTA/Ir (ppy) 3: TPBi(5wt%)/Bphen/CsN 3: Bphen(30wt%)/Al/(TAPC/Bphen/AlB 2/ TAPC/Bphen/Sb 2se 3) 4, wherein, that "/" represents is stacked, ": " represents doping, parenthetic mass percent data representation for the quality of the bi-material that adulterates than numerical value, " (TAPC/Bphen/AlB 2/ TAPC/Bphen/Sb 2se 3) 4" indicate that the structure of 4 stacked settings is TAPC/Bphen/AlB 2/ TAPC/Bphen/Sb 2se 3cap.
The manufacturing process of this organic electroluminescence device is as follows:
A) ito glass substrate pre-treatment: have the ito glass substrate of anode pattern to clean through acetone cleaning, ethanol cleaning, washed with de-ionized water and ethanol successively surface etch, cleaning process is all carried out with supersonic wave cleaning machine, individual event scavenging period is 5 minutes, then with nitrogen, dries up stove-drying; Ito glass after cleaning is carried out to surface activation process, to increase the oxygen content of ITO layer, improve the work function on ITO layer surface; On ito glass substrate, ITO layer thickness is 100nm.
B) preparation of organic luminescence function layer:
Hole injection layer: adopt the mode of vacuum evaporation, by MoO 3be doped in NPB, on ito glass substrate surface, prepare the hole injection layer of thickness 10nm, wherein, vacuum degree 1 * 10 -5pa, evaporation rate moO 3with the mass ratio of NPB be 30:100;
Hole transmission layer: adopt the mode of vacuum evaporation, at hole injection layer surface evaporation TCTA as hole transmission layer, wherein, vacuum degree 1 * 10 -5pa, evaporation rate evaporation thickness 30nm;
Luminescent layer: material of main part adopts TPBi, guest materials adopts Ir (ppy) 3, the mode of employing vacuum evaporation, is doped into guest materials in material of main part, and doping content 5wt%, prepares the luminescent layer that thickness is 20nm on hole transmission layer surface, wherein, vacuum degree 1 * 10 -5pa, evaporation rate
Electron transfer layer: adopt the mode of vacuum evaporation, at surperficial evaporation one deck Bphen of luminescent layer as electron transfer layer, wherein, vacuum degree 1 * 10 -5pa, evaporation rate evaporation thickness 10nm;
Electron injecting layer: adopt the mode of vacuum evaporation, by CsN 3be doped in Bphen, doping content 30wt% prepares the electron injecting layer that a layer thickness is 20nm on electron transfer layer, wherein, and vacuum degree 1 * 10 -5pa, evaporation rate
C) cathode layer: adopt the mode of vacuum evaporation, electron injecting layer surface evaporation prepare a layer thickness be the Al layer of 100nm as cathode layer, wherein, vacuum degree 1 * 10 -5pa, evaporation rate
D) first organic barrier layer: the mode that adopts vacuum evaporation, the TAPC layer that is 200nm in cathode layer surface preparation a layer thickness is as first organic barrier layer, and first organic barrier layer is packaged in anode pattern, organic luminescence function layer and cathode layer on glass substrate, wherein, vacuum degree 1 * 10 -5pa, evaporation rate
E) second organic barrier layer: adopt the mode of vacuum evaporation, first organic barrier layer surface prepare a layer thickness be the Bphen layer of 200nm as second organic barrier layer, wherein, vacuum degree 1 * 10 -5pa, evaporation rate
F) the first inorganic barrier layer: adopt the mode of magnetron sputtering, prepare in first organic barrier layer surface sputter the AlB that a layer thickness is 80nm 2as the first inorganic barrier layer, base vacuum degree 1 * 10 in magnetron sputtering process -5pa.
G) the 3rd organic barrier layer: adopt the mode of vacuum evaporation, on the first inorganic barrier layer surface, prepare again a layer thickness and be the TAPC layer of 200nm as first organic barrier layer, wherein, vacuum degree 1 * 10 -5pa, evaporation rate
H) the 4th organic barrier layer: adopt the mode of vacuum evaporation, first organic barrier layer surface of preparing in step g) prepare a layer thickness be the Bphen layer of 200nm as second organic barrier layer, wherein, vacuum degree 1 * 10 -5pa, evaporation rate
I) second organic barrier layer surface of the second inorganic barrier layer: adopt the mode of magnetron sputtering, at step h) preparing is prepared the Sb that a layer thickness is 70nm 2se 3as the second inorganic barrier layer, in magnetron sputtering process, base vacuum degree is 1 * 10 -5pa.
Repeating step d again)～i) 3 times.
Embodiment 2
The organic electroluminescence device structure of the present embodiment is: ito glass substrate/MoO 3: NPB(30wt%)/TCTA/Ir (ppy) 3: TPBi(5wt%)/Bphen/CsN 3: Bphen(30wt%)/Al/(NPB/BCP/LaB 6/ NPB/BCP/MoSe 2) 3, wherein, that "/" represents is stacked, ": " represents doping, parenthetic mass percent data representation for the quality of the bi-material that adulterates than numerical value, " (NPB/BCP/LaB 6/ NPB/BCP/MoSe 2) 3" structure that represents to have three layers is NPB/BCP/LaB 6/ NPB/BCP/MoSe 2cap.
The manufacturing process of this organic electroluminescence device is as follows:
Step a), b), c) with embodiment 1.
D) first organic barrier layer: the mode that adopts vacuum evaporation, the NPB layer that is 300nm in cathode layer surface preparation a layer thickness is as first organic barrier layer, and first organic barrier layer is packaged in anode pattern, organic luminescence function layer and cathode layer on glass substrate, wherein, vacuum degree 1 * 10 -4pa, evaporation rate
E) second organic barrier layer: adopt the mode of vacuum evaporation, first organic barrier layer surface prepare a layer thickness be the BCP layer of 300nm as second organic barrier layer, wherein, vacuum degree 1 * 10 -4pa, evaporation rate
F) the first inorganic barrier layer: adopt the mode of magnetron sputtering, prepare in first organic barrier layer surface sputter the LaB that a layer thickness is 100nm 6as the first inorganic barrier layer, base vacuum degree 1 * 10 in magnetron sputtering process -4pa.
G) the 3rd organic barrier layer: adopt the mode of vacuum evaporation, on the first inorganic barrier layer surface, prepare again a layer thickness and be the NPB layer of 300nm as first organic barrier layer, wherein, vacuum degree 1 * 10 -4pa, evaporation rate
H) the 4th organic barrier layer: adopt the mode of vacuum evaporation, first organic barrier layer surface of preparing in step g) prepare a layer thickness be the BCP layer of 300nm as second organic barrier layer, wherein, vacuum degree 1 * 10 -4pa, evaporation rate
I) second organic barrier layer surface of the second inorganic barrier layer: adopt the mode of magnetron sputtering, at step h) preparing is prepared the MoSe that a layer thickness is 60nm 2as the second inorganic barrier layer, in magnetron sputtering process, base vacuum degree is 1 * 10 -4pa.
Repeating step d again)～i) 2 times.
Embodiment 3
The organic electroluminescence device structure of the present embodiment is: ito glass substrate/MoO 3: NPB(30wt%)/TCTA/Ir (ppy) 3: TPBi(5wt%)/Bphen/CsN 3: Bphen(30wt%)/Al/(Alq 3/ TPBi/VB 2/ Alq 3/ TPBi/Bi 2se 3) 3, wherein, that "/" represents is stacked, ": " represents doping, parenthetic mass percent data representation for the quality of the bi-material that adulterates than numerical value, " (Alq 3/ TPBi/VB 2/ Alq 3/ TPBi/Bi 2se 3) 3" structure that represents to have three layers is Alq 3/ TPBi/VB 2/ Alq 3/ TPBi/Bi 2se 3cap.
The manufacturing process of this organic electroluminescence device is as follows:
Step a), b), c) with embodiment 1.
D) first organic barrier layer: adopt the mode of vacuum evaporation, the Alq that is 250nm in cathode layer surface preparation a layer thickness 3layer, as first organic barrier layer, and makes first organic barrier layer that anode pattern, organic luminescence function layer and cathode layer are packaged on glass substrate, wherein, and vacuum degree 1 * 10 -4pa, evaporation rate
E) second organic barrier layer: adopt the mode of vacuum evaporation, first organic barrier layer surface prepare a layer thickness be the TPBi layer of 250nm as second organic barrier layer, wherein, vacuum degree 1 * 10 -4pa, evaporation rate
F) the first inorganic barrier layer: adopt the mode of magnetron sputtering, prepare in first organic barrier layer surface sputter the VB that a layer thickness is 50nm 2as the first inorganic barrier layer, base vacuum degree 1 * 10 in magnetron sputtering process -4pa.
G) the 3rd organic barrier layer: adopt the mode of vacuum evaporation, prepare again on the first inorganic barrier layer surface the Alq that a layer thickness is 250nm 3layer as first organic barrier layer, wherein, vacuum degree 1 * 10 -4pa, evaporation rate
H) the 4th organic barrier layer: adopt the mode of vacuum evaporation, first organic barrier layer surface of preparing in step g) prepare a layer thickness be the TPBi layer of 250nm as second organic barrier layer, wherein, vacuum degree 1 * 10 -4pa, evaporation rate
I) second organic barrier layer surface of the second inorganic barrier layer: adopt the mode of magnetron sputtering, at step h) preparing is prepared the Bi that a layer thickness is 100nm 2se 3as the second inorganic barrier layer, in magnetron sputtering process, base vacuum degree is 1 * 10 -4pa.
Repeating step d again)～i) 2 times.
Embodiment 4
The organic electroluminescence device structure of the present embodiment is: ito glass substrate/MoO 3: NPB(30wt%)/TCTA/Ir (ppy) 3: TPBi(5wt%)/Bphen/CsN 3: Bphen(30wt%)/Al/(m-MTDATA/Alq 3/ NbB/m-MTDATA/Alq 3/ NbSe 2) 2, wherein, that "/" represents is stacked, ": " represents doping, parenthetic mass percent data representation for the quality of the bi-material that adulterates than numerical value, " (m-MTDATA/Alq 3/ NbB/m-MTDATA/Alq 3/ NbSe 2) 2" indicate that 2 layers of structure are m-MTDATA/Alq 3/ NbB/m-MTDATA/Alq 3/ NbSe 2cap.
The manufacturing process of this organic electroluminescence device is as follows:
Step a), b), c) with embodiment 1.
D) first organic barrier layer: the mode that adopts vacuum evaporation, the m-MTDATA layer that is 220nm in cathode layer surface preparation a layer thickness is as first organic barrier layer, and first organic barrier layer is packaged in anode pattern, organic luminescence function layer and cathode layer on glass substrate, wherein, vacuum degree 1 * 10 -4pa, evaporation rate
E) second organic barrier layer: adopt the mode of vacuum evaporation, first organic barrier layer surface prepare a layer thickness be the Alq3 layer of 240nm as second organic barrier layer, wherein, vacuum degree 1 * 10 -4pa, evaporation rate
F) the first inorganic barrier layer: adopt the mode of magnetron sputtering, first organic barrier layer surface sputter prepare a layer thickness be the NbB of 60nm as the first inorganic barrier layer, base vacuum degree 1 * 10 in magnetron sputtering process -4pa.
G) the 3rd organic barrier layer: adopt the mode of vacuum evaporation, on the first inorganic barrier layer surface, prepare again a layer thickness and be the m-MTDATA layer of 220nm as first organic barrier layer, wherein, vacuum degree 1 * 10 -4pa, evaporation rate
H) the 4th organic barrier layer: adopt the mode of vacuum evaporation, first organic barrier layer surface of preparing in step g) is prepared the Alq that a layer thickness is 240nm 3layer as second organic barrier layer, wherein, vacuum degree 1 * 10 -4pa, evaporation rate
I) second organic barrier layer surface of the second inorganic barrier layer: adopt the mode of magnetron sputtering, at step h) preparing is prepared the NbSe that a layer thickness is 50nm 2as the second inorganic barrier layer, in magnetron sputtering process, base vacuum degree is 1 * 10 -4pa.
Repeating step d again)～i) 1 time.
Embodiment 5
The organic electroluminescence device structure of the present embodiment is: ito glass substrate/MoO 3: NPB(30wt%)/TCTA/Ir (ppy) 3: TPBi(5wt%)/Bphen/CsN 3: Bphen(30wt%)/Al/(BCP/BAlq/TiB 2/ BCP/BAlq/TaSe 2) 2, wherein, that "/" represents is stacked, ": " represents doping, parenthetic mass percent data representation for the quality of the bi-material that adulterates than numerical value, " (BCP/BAlq/TiB 2/ BCP/BAlq/TaSe 2) 2" indicate that 2 layers of structure are BCP/BAlq/TiB 2/ BCP/BAlq/TaSe 2cap.
The manufacturing process of this organic electroluminescence device is as follows:
Step a), b), c) with embodiment 1.
D) first organic barrier layer: the mode that adopts vacuum evaporation, the BCP layer that is 260nm in cathode layer surface preparation a layer thickness is as first organic barrier layer, and first organic barrier layer is packaged in anode pattern, organic luminescence function layer and cathode layer on glass substrate, wherein, vacuum degree 1 * 10 -4pa, evaporation rate
E) second organic barrier layer: adopt the mode of vacuum evaporation, first organic barrier layer surface prepare a layer thickness be the BAlq layer of 200nm as second organic barrier layer, wherein, vacuum degree 1 * 10 -4pa, evaporation rate
F) the first inorganic barrier layer: adopt the mode of magnetron sputtering, prepare in first organic barrier layer surface sputter the TiB that a layer thickness is 70nm 2as the first inorganic barrier layer, base vacuum degree 1 * 10 in magnetron sputtering process -4pa.
G) the 3rd organic barrier layer: adopt the mode of vacuum evaporation, on the first inorganic barrier layer surface, prepare again a layer thickness and be the BCP layer of 260nm as first organic barrier layer, wherein, vacuum degree 1 * 10 -4pa, evaporation rate
H) the 4th organic barrier layer: adopt the mode of vacuum evaporation, first organic barrier layer surface of preparing in step g) prepare a layer thickness be the BAlq layer of 200nm as second organic barrier layer, wherein, vacuum degree 1 * 10 -4pa, evaporation rate
I) second organic barrier layer surface of the second inorganic barrier layer: adopt the mode of magnetron sputtering, at step h) preparing is prepared the TaSe that a layer thickness is 80nm 2as the second inorganic barrier layer, in magnetron sputtering process, base vacuum degree is 1 * 10 -4pa.
Repeating step d again)～i) 1 time.
Embodiment 6
The organic electroluminescence device structure of the present embodiment is: ito glass substrate/MoO 3: NPB(30wt%)/TCTA/Ir (ppy) 3: TPBi(5wt%)/Bphen/CsN 3: Bphen(30wt%)/Al/(TPBi/TAZ/MoB/TPBi/TAZ/Cu 2se) 2, wherein, that "/" represents is stacked, ": " represents doping, parenthetic mass percent data representation for the quality of the bi-material that adulterates than numerical value, " (TPBi/TAZ/MoB/TPBi/TAZ/Cu 2se) 2" indicate that 2 layers of structure are TPBi/TAZ/MoB/TPBi/TAZ/Cu 2the cap of Se.
The manufacturing process of this organic electroluminescence device is as follows:
Step a), b), c) with embodiment 1.
D) first organic barrier layer: the mode that adopts vacuum evaporation, the TPBi layer that is 200nm in cathode layer surface preparation a layer thickness is as first organic barrier layer, and first organic barrier layer is packaged in anode pattern, organic luminescence function layer and cathode layer on glass substrate, wherein, vacuum degree 1 * 10 -3pa, evaporation rate
E) second organic barrier layer: adopt the mode of vacuum evaporation, first organic barrier layer surface prepare a layer thickness be the TAZ layer of 220nm as second organic barrier layer, wherein, vacuum degree 1 * 10 -3pa, evaporation rate
F) the first inorganic barrier layer: adopt the mode of magnetron sputtering, first organic barrier layer surface sputter prepare a layer thickness be the MoB of 65nm as the first inorganic barrier layer, base vacuum degree 1 * 10 in magnetron sputtering process -3pa.
G) the 3rd organic barrier layer: adopt the mode of vacuum evaporation, on the first inorganic barrier layer surface, prepare again a layer thickness and be the TPBi layer of 200nm as first organic barrier layer, wherein, vacuum degree 1 * 10 -3pa, evaporation rate
H) the 4th organic barrier layer: adopt the mode of vacuum evaporation, first organic barrier layer surface of preparing in step g) prepare a layer thickness be the TAZ layer of 220nm as second organic barrier layer, wherein, vacuum degree 1 * 10 -3pa, evaporation rate
I) second organic barrier layer surface of the second inorganic barrier layer: adopt the mode of magnetron sputtering, at step h) preparing is prepared the Cu that a layer thickness is 50nm 2se is as the second inorganic barrier layer, and in magnetron sputtering process, base vacuum degree is 1 * 10 -3pa.
Repeating step d again)～i) 1 time.
Table 1 is that waterproof oxygen performance and the luminescent lifetime of the various embodiments described above detects data:
Table 1
The ability that can be found out the organic electroluminescence device waterproof that adopts present embodiment structure by table 1 data is strong, and device lifetime 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 substrate being cascading, anode layer, organic luminescence function layer and cathode layer, it is characterized in that, described organic electroluminescence device also comprises cap, described cap is by described anode layer, described organic luminescence function layer and described cathode layer are encapsulated on described substrate, described cap comprises first organic barrier layer, be formed at second organic barrier layer of described first organic barrier layer surface, be formed at the first inorganic barrier layer of described second organic barrier layer surface, be formed at the 3rd organic barrier layer on described the first inorganic barrier layer surface, be formed at the 4th organic barrier layer of described the 3rd organic barrier layer surface and the second inorganic barrier layer that is formed at described the 4th organic barrier layer surface,
Wherein, the material on described first organic barrier layer and 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 second organic barrier layer and 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 first inorganic barrier layer is AlB 2, LaB 6, VB 2, NbB, TiB 2or MoB;
The material of described the second inorganic barrier layer is Sb 2se 3, MoSe 2, Bi 2se 3, NbSe 2, TaSe 2or Cu 2se.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, the quantity of described cap is 2～4, the stacked setting of a plurality of caps.
3. organic electroluminescence device as claimed in claim 1, it is characterized in that, described first organic barrier layer is different from the material on described second organic barrier layer, described first organic barrier layer is identical with the material on described the 3rd organic barrier layer, and the material on described second organic barrier layer is identical with the material on described the 4th organic barrier layer.
4. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness on described first organic barrier layer and described the 3rd organic barrier layer is identical, is 200～300nm.
5. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness on described second organic barrier layer and described the 4th organic barrier layer is identical, is 200～300nm.
6. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described the first inorganic barrier layer is 50～100nm.
7. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described the second inorganic barrier layer is 50～100nm.
8. organic electroluminescence device as claimed in claim 1, is characterized in that, described organic luminescence function layer is included in hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer being cascading on described anode layer.
9. organic electroluminescence device as claimed in claim 8, is characterized in that, to be molybdenum trioxide be entrained in N according to 30% doping mass percent to the material of described hole injection layer, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, the composite material forming in 4'-diamines; The material of described hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine; The material of described luminescent layer is that three (2-phenylpyridines) close iridium and are entrained according to 5% doping mass percent the composite material forming in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene; The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline; To be nitrogenize caesium be entrained in 4,7-diphenyl-1, the composite material forming in 10-phenanthroline according to 30% doping mass percent to the material of described electron injecting layer.
10. a manufacture method for organic electroluminescence device, is characterized in that, comprises the steps:
In clean electrically-conductive backing plate surface etch, be prepared with the anode pattern of organic electroluminescence devices;
Adopt the mode of vacuum evaporation to evaporate successively and be coated with organic luminescence function layer and cathode layer on the anode pattern surface of described electrically-conductive backing plate;
The mode of employing vacuum evaporation is evaporated and is coated with first organic barrier layer and makes described first organic barrier layer by described anode pattern, described organic luminescence function layer and the encapsulation of described cathode layer and described electrically-conductive backing plate, then adopts the mode of vacuum evaporation to be coated with second organic barrier layer at described first organic barrier layer surface;
Adopt the mode of magnetron sputtering to prepare the first inorganic barrier layer in described second organic barrier layer surface sputter;
Adopt the mode of vacuum evaporation to be coated with the 3rd organic barrier layer in described the first inorganic barrier layer surface evaporation, and be coated with the 4th organic barrier layer at described the 3rd organic barrier layer surface;
Adopt the mode of magnetron sputtering to prepare the second inorganic barrier layer in described the 4th organic barrier layer surface sputter;
Wherein, the material on described first organic barrier layer and 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 second organic barrier layer and 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 first inorganic barrier layer is AlB 2, LaB 6, VB 2, NbB, TiB 2or MoB;
The material of described the second inorganic barrier layer is Sb 2se 3, MoSe 2, Bi 2se 3, NbSe 2, TaSe 2or Cu 2se.
CN201310121394.1A 2013-04-09 2013-04-09 Organic light-emitting display and manufacturing method thereof Pending CN104103768A (en)

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Application publication date: 20141015