CN104051646A - Organic electroluminescent device and packaging method thereof - Google Patents
Organic electroluminescent device and packaging method thereof Download PDFInfo
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- CN104051646A CN104051646A CN201310084228.9A CN201310084228A CN104051646A CN 104051646 A CN104051646 A CN 104051646A CN 201310084228 A CN201310084228 A CN 201310084228A CN 104051646 A CN104051646 A CN 104051646A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
- H10K50/8445—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
Abstract
The invention discloses an organic electroluminescent device and a packaging method thereof. The device comprises an anode, a cavity injection layer, a cavity transmission layer, a luminescent layer, an electron transmission layer, an electron injection layer and a cathode which are successively stacked, and five to seven protection layers stacked on the cathode. Each protection layer comprises an organic barrier layer and an inorganic barrier layer which are stacked. Each organic barrier layer is formed by copper phthalocyanine, N,N'-diphenyl-N,N'-di(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, (8-hydroxyquinoline)aluminum, 4,4',4''-tris(N-3-methylphenyl-N-phenylamino)triphenylamine or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline. Each inorganic barrier layer is formed by mixing one from dirhenium oxide, rhenium oxide, rhenium sesquioxide, rhenium dioxide, dirhenium pentoxide and rhenium trioxide with one from cadmium sulfide, lead sulfide, iron disulfide, copper sulfide, zinc sulfide and nickel sulfide. The service life of the organic electroluminescent device is enabled to be longer.
Description
Technical field
The present invention relates to electroluminescent technology field, particularly relate to a kind of organic electroluminescence device and method for packing 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.In the time being added with voltage on electrode, luminescent layer just produces light radiation.
OLED device 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.
But, luminescent layer in OLED is very responsive for the pollutant in atmosphere, oxygen, steam etc., effect at pollutant, oxygen and steam etc. issues the reduction that biochemical reaction can cause luminous quantum efficiency, and negative electrode is generally formed by more active metal, in air or oxygen, easily weather, thereby the less stable that causes OLED, useful life is shorter.
Summary of the invention
Based on this, be necessary to provide organic electroluminescence device and the method for packing thereof grown a kind of useful life.
A kind of organic electroluminescence device, comprise the anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, also comprise 5～7 protective layers that are laminated on described negative electrode, each protective layer comprises organic barrier layer and is laminated in the inorganic barrier layer on described organic barrier layer; Wherein, described organic barrier layer is by CuPc, 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 or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene forms, and described inorganic barrier layer is mixed to form by the one in a kind of and cadmium sulfide, vulcanized lead, ferrous disulfide, copper sulfide, zinc sulphide and the nickel sulfide that are oxidized in two rheniums, rheium oxide, rhenium sesquioxide, rhenium dioxide, five oxidation two rheniums and rhenium trioxide.
In an embodiment, a kind of mass fraction that accounts for described inorganic barrier layer in described oxidation two rheniums, rheium oxide, rhenium sesquioxide, rhenium dioxide, five oxidation two rheniums and rhenium trioxide is 10～30% therein.
In an embodiment, the thickness on described organic barrier layer is 200 nanometer～300 nanometers therein.
In an embodiment, the thickness of described inorganic barrier layer is 100 nanometer～200 nanometers therein.
A method for packing for organic electroluminescence device, comprises the steps:
Step 1: anode is provided, adopts vacuum evaporation to form hole injection layer on described anode;
Step 2: adopt vacuum evaporation to form hole transmission layer on described hole injection layer;
Step 3: adopt vacuum evaporation to form luminescent layer on described hole transmission layer;
Step 4: adopt vacuum evaporation to form electron transfer layer on described luminescent layer;
Step 5: adopt vacuum evaporation to form electron injecting layer on described electron transfer layer;
Step 6: adopt vacuum evaporation negative electrode on described electron injecting layer;
Step 7: adopt vacuum evaporation to form organic barrier layer on described negative electrode, described organic barrier layer is by CuPc, 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 or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene forms;
Step 8: adopt vacuum evaporation to form inorganic barrier layer on described organic barrier layer, described inorganic barrier layer is mixed to form by the one in a kind of and cadmium sulfide, vulcanized lead, ferrous disulfide, copper sulfide, zinc sulphide and the nickel sulfide that are oxidized in two rheniums, rheium oxide, rhenium sesquioxide, rhenium dioxide, five oxidation two rheniums and rhenium trioxide, and described organic barrier layer and inorganic barrier layer form a protective layer;
Step 9: alternately repeating said steps seven and described step 84 to 6 times, on described negative electrode, form 5～7 protective layers, obtain organic electroluminescence device.
In an embodiment, in described step 7～step 9, the vacuum degree of vacuum evaporation is 1 × 10 therein
-5pa～1 × 10
-3pa.
In an embodiment, in described step 7～step 9, evaporation rate is therein
Therein in an embodiment, before described employing vacuum evaporation forms the step of hole injection layer on described anode, also comprise the cleaning step of antianode, described cleaning step is: described anode is put into acetone, ethanol, deionized water and ethanol successively and carry out ultrasonic cleaning, each ultrasonic cleaning 5 minutes, then dry up with nitrogen, then use oven for drying.
Therein in an embodiment, after described cleaning step completes, described employing vacuum evaporation also comprised the step of described anode being carried out to surface activation process form the step of hole injection layer on described anode before, and the step of described activation processing is: the anode after adopting ultraviolet-ozone to cleaning-drying is processed 30～50 minutes.
Stacked 5～7 protective layers on the negative electrode of above-mentioned organic electroluminescence device; active organic layer and negative electrode are packaged between protective layer and anode; the fine and close protective layer being formed by above-mentioned organic material and inorganic material can reduce outside water, the erosion of oxygen isoreactivity material to organic layer and negative electrode effectively; and 5～7 protective layers can meet the sealing requirements of encapsulation; organic layer to organic electroluminescence device and negative electrode form effective protection, thereby make the useful life of organic electroluminescence device higher.
Brief description of the drawings
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is the method for packing flow chart of the organic electroluminescence device of an execution mode.
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.
Refer to Fig. 1, the organic electroluminescence device 100 of an execution mode, comprises the anode 10, hole injection layer 20, hole transmission layer 30, luminescent layer 40, electron transfer layer 50, electron injecting layer 60, negative electrode 70 and the protective layer 80 that stack gradually.
Anode 10 can be indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), is preferably indium tin oxide glass (ITO).
In other embodiments, anode 10 also can comprise the flexible base, board that the permeabilities such as Merlon base board are higher and be laminated in indium and tin oxide film, aluminium zinc oxide film or the indium-zinc oxide film on flexible base, board.
Preferably, the thickness of anode 10 is 100 nanometers.
Hole injection layer 20 is by molybdenum trioxide (MoO
3) be doped in N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, form in 4'-diamines (NPB).Wherein, molybdenum trioxide (MoO
3) mass fraction that accounts for hole injection layer 20 is 30%.
Preferably, the thickness of hole injection layer 20 is 10 nanometers.
Hole transmission layer 30 is by 4,4', and 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) forms.
Preferably, the thickness of hole transmission layer 30 is 30 nanometers.
Luminescent layer 40 closes iridium (Ir (ppy) by three (2-phenylpyridines)
3) be doped in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI) and form.Wherein, three (2-phenylpyridines) close iridium (Ir (ppy)
3) mass fraction that accounts for luminescent layer 40 is 5%.
Preferably, the thickness of luminescent layer 40 is 20 nanometers.
Electron transfer layer 50 is by 4,7-diphenyl-1, and 10-phenanthroline (Bphen) forms.
Preferably, the thickness of electron transfer layer 50 is 10 nanometers.
Electron injecting layer 60 is by cesium azide (CsN
3) mix 4,7-diphenyl-1, in 10-phenanthroline (Bphen), form.Wherein, cesium azide (CsN
3) mass fraction that accounts for electron injecting layer 60 is 30%.
Preferably, the thickness of electron injecting layer 60 is 20 nanometers.
Negative electrode 70 is formed by metallic aluminium (Al).Preferably, the thickness of negative electrode 70 is 150 nanometers.
In present embodiment, the quantity of protective layer 80 is 5, and 5 protective layers are laminated on negative electrode 70.In other embodiments, the quantity of protective layer 80 can be 6 or 7.5～7 protective layers 80 make the waterproof oxygen performance of organic electroluminescence device 100 higher.
Each protective layer 80 comprises organic barrier layer 81 and is laminated in the inorganic barrier layer 82 on organic barrier layer 81.
Organic barrier layer 81 is by phthalocyanine (H
2pc), 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) or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene (BCP) form.The evenness on the organic barrier layer being formed by these several materials is high, and light transmittance is high, and internal stress is little, is conducive to form fine and close, smooth inorganic barrier layer 82 on organic barrier layer 81.
Preferably, the thickness on organic barrier layer 81 is 200 nanometer～300 nanometers.
Inorganic barrier layer 82 is by oxidation two rhenium (Re
2o), rheium oxide (ReO), rhenium sesquioxide (Re
2o
3), rhenium dioxide (ReO
2), five oxidation two rhenium (Re
2o
5) and rhenium trioxide (ReO
3) in one and cadmium sulfide (CdS), vulcanized lead (PbS), ferrous disulfide (FeS
2), one in copper sulfide (CuS), zinc sulphide (ZnS) and nickel sulfide (NiS) is mixed to form.Barrier properties and the light transmittance of oxide are higher; sulfide plays stress buffer effect; make inorganic barrier layer 82 have higher barrier properties and light transmittance, and stability is higher, inorganic barrier layer 82 is laminated in the comparatively stable protective layer 80 of formation on organic barrier layer 81.
Inorganic barrier layer 82 is steamed and forms altogether by the oxide of sulfide and rhenium, and the common steaming compactness of the oxide of sulfide and rhenium is better, can on the surface on organic barrier layer 81, form fine and close film, thereby improves waterproof oxygen performance.
Preferably, the thickness of inorganic barrier layer 82 is 100 nanometer～200 nanometers.
In present embodiment, can be good at exclusion of water, oxygen isoreactivity material by multiple organic barrier layers 81 and alternately laminated 5 protective layers 80 that form of inorganic barrier layer 82, make life-span (the T70@1000cd/m of organic electroluminescence device 100
2) reach more than 2000 hours.
The evenness on the organic barrier layer 81 being formed by above-mentioned material is good; be conducive to inorganic matter film forming on 81 surfaces, organic barrier layer; be conducive to form fine and close inorganic barrier layer 82; thereby form the higher protective layer 80 of compactness; make protective layer 80 oxygen, the steam etc. in blocks air effectively, water vapor permeable rate reaches 10
-3g/m
2day; and 5～7 protective layers can further meet the sealing requirements of encapsulation; can effectively protect hole injection layer 20, hole transmission layer 30, luminescent layer 40, electron transfer layer 50, electron injecting layer 60 and negative electrode 70, make the useful life of organic electroluminescence device 100 longer.
Refer to Fig. 2, the method for packing of the organic electroluminescence device in an execution mode, comprises the steps:
Step S110: anode is provided, adopts vacuum evaporation to form hole injection layer on anode.
Anode can be indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), is preferably indium tin oxide glass (ITO).
In other embodiments, anode also can be formed by the higher flexible base, board of the permeabilities such as Merlon base board and indium and tin oxide film, aluminium zinc oxide film or the indium-zinc oxide film being laminated on flexible base, board.
Adopt vacuum evaporation on the dry glass substrate of cleaning or Merlon base board evaporation indium tin oxide, aluminium zinc oxide or indium-zinc oxide, form anode pattern at glass substrate or Merlon base board, obtain anode.
Preferably, the thickness of anode is 100 nanometers.
Before employing vacuum evaporation forms hole injection layer on anode, first anode is put into acetone, ethanol, deionized water and ethanol successively and carry out ultrasonic cleaning, each ultrasonic cleaning 5 minutes, then dries up with nitrogen, use again oven for drying, obtain cleaning, dry anode.Further anode is carried out to surface-active-treatment, to increase the oxygen content of anode surface, improve the work function of anode.Carry out the step of surface-active-treatment for adopting ultraviolet-ozone (UV-ozone) to process 30～50 minutes the anode after cleaning-drying.
Hole injection layer is by molybdenum trioxide (MoO
3) be doped in N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, form in 4'-diamines (NPB).Wherein, molybdenum trioxide (MoO
3) mass fraction that accounts for hole injection layer is 30%.
Preferably, the thickness of hole injection layer is 10 nanometers.
The vacuum degree of vacuum evaporation is 1 × 10
-5pa.Evaporation rate is
Step S120: adopt vacuum evaporation to form hole transmission layer on hole injection layer.
Hole transmission layer is by 4,4', and 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) forms.
Preferably, the thickness of hole transmission layer is 30 nanometers.
The vacuum degree of vacuum evaporation is 3 × 10
-5pa.Evaporation rate is
Step S130: adopt vacuum evaporation to form luminescent layer on hole transmission layer.
Luminescent layer closes iridium (Ir (ppy) by three (2-phenylpyridines)
3) be doped in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI) and form.Wherein, three (2-phenylpyridines) close iridium (Ir (ppy)
3) mass fraction that accounts for luminescent layer is 5%.
Preferably, the thickness of luminescent layer is 20 nanometers.
The vacuum degree of vacuum evaporation is 3 × 10
-5pa.Evaporation rate is
Step S140: adopt vacuum evaporation to form electron transfer layer on luminescent layer.
Electron transfer layer is by 4,7-diphenyl-1, and 10-phenanthroline (Bphen) forms.
Preferably, the thickness of electron transfer layer is 10 nanometers.
The vacuum degree of vacuum evaporation is 3 × 10
-5pa.Evaporation rate is
Step S150: adopt vacuum evaporation to form electron injecting layer on electron transfer layer.
Electron injecting layer is by cesium azide (CsN
3) mix 4,7-diphenyl-1, in 10-phenanthroline (Bphen), form.Wherein, cesium azide (CsN
3) mass fraction that accounts for electron injecting layer is 30%.
Preferably, the thickness of electron injecting layer is 20 nanometers.
The vacuum degree of vacuum evaporation is 3 × 10
-5pa.Evaporation rate is
Step S160: adopt vacuum evaporation negative electrode on electron injecting layer.
Negative electrode is formed by metallic aluminium (Al).Preferably, the thickness of negative electrode is 150 nanometers.
The vacuum degree of vacuum evaporation is 3 × 10
-5pa.Evaporation rate is
Step S170: adopt vacuum evaporation to form organic barrier layer on negative electrode, organic barrier layer is by CuPc, 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 or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene forms.
Preferably, the thickness on organic barrier layer is 200 nanometer～300 nanometers.
The vacuum degree of vacuum evaporation is 1 × 10
-5pa～1 × 10
-3pa.Evaporation rate is
Step S180: adopt vacuum evaporation to form inorganic barrier layer on organic barrier layer; inorganic barrier layer is mixed to form by the one in a kind of and cadmium sulfide, vulcanized lead, ferrous disulfide, copper sulfide, zinc sulphide and the nickel sulfide that are oxidized in two rheniums, rheium oxide, rhenium sesquioxide, rhenium dioxide, five oxidation two rheniums and rhenium trioxide;, organic barrier layer and inorganic barrier layer form a protective layer.
The oxide of sulfide and rhenium steams formation inorganic barrier layer altogether.Inorganic barrier layer is laminated in and on organic barrier layer, forms a protective layer.
Preferably, the thickness of inorganic barrier layer is 100 nanometer～200 nanometers.
The vacuum degree of vacuum evaporation is 1 × 10
-5pa～1 × 10
-3pa.Evaporation rate is
Inorganic barrier layer is laminated in organic barrier layer and forms a protective layer.
Step S190: alternately repeating step S170 and step S1804 to 6 time, on negative electrode, form 5～7 protective layers, obtain organic electroluminescence device.
Alternately repeating step S170 and step S1804 to 6 time, forms 4～6 protective layers, thereby on negative electrode, forms 5～7 protective layers, obtains organic electroluminescence device.
The method for packing of above-mentioned organic electroluminescence device adopts the method for vacuum evaporation on negative electrode, to form 5～7 protective layers, thereby by hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode are packaged between anode and 5～7 protective layers, can be good at protecting hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode are packaged in protective layer and anode, it is higher that encapsulation obtains stability, the organic electroluminescence device of growing useful life, and packaging technology is simple, be easy to extensive encapsulation.
It is below specific embodiment.
Embodiment 1
Structure is ITO/MoO
3: NPB/TCTA/Ir (ppy)
3: TPBI/Bphen/CsN
3: Bphen/ZnS/Ag/ZnS/ (CuPc/Re
2o:NiS)
7the encapsulation of organic electroluminescence device
(1) provide anode, anode is indium tin oxide glass, is expressed as ITO.First anode is put into acetone, ethanol, deionized water and ethanol successively and carry out ultrasonic cleaning, each ultrasonic cleaning 5 minutes, then dries up with nitrogen, then uses oven for drying, obtains cleaning, dry anode.Further adopt ultraviolet-ozone (UV-ozone) to process and carry out surface-active-treatment 30 minutes the anode after cleaning-drying, to increase the oxygen content of anode surface, improve the work function of anode;
(2) hole injection layer that adopts vacuum evaporation to form on the surface of anode, the vacuum degree of vacuum evaporation is 3 × 10
-5pa, evaporation rate is
hole injection layer is by molybdenum trioxide (MoO
3) be doped in N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, form in 4'-diamines (NPB), are expressed as MoO
3: NPB, wherein molybdenum trioxide (MoO
3) mass fraction that accounts for hole injection layer is 30%; The thickness of hole injection layer is 10 nanometers;
(3) hole transmission layer that adopts vacuum evaporation to form on the surface of hole injection layer, the vacuum degree of vacuum evaporation is 3 × 10
-5pa, evaporation rate is
hole transmission layer is by 4,4', and 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) forms; The thickness of hole transmission layer is 30 nanometers;
(4) adopt vacuum evaporation on hole transmission layer, to form luminescent layer, the vacuum degree of vacuum evaporation is 3 × 10
-5pa, evaporation rate is
luminescent layer closes iridium (Ir (ppy) by three (2-phenylpyridines)
3) be doped in formation in 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), be expressed as Ir (ppy)
3: TPBI, wherein three (2-phenylpyridines) close iridium (Ir (ppy)
3) mass fraction that accounts for luminescent layer is 5%; The thickness of luminescent layer is 20 nanometers;
(5) adopt vacuum evaporation on luminescent layer, to form electron transfer layer, the vacuum degree of vacuum evaporation is 3 × 10
-5pa, evaporation rate is
electron transfer layer is by 4,7-diphenyl-1, and 10-phenanthroline (Bphen) forms, and the thickness of electron transfer layer is 10 nanometers;
(6) adopt vacuum evaporation on electron transfer layer, to form electron injecting layer, the vacuum degree of vacuum evaporation is 3 × 10
-5pa, evaporation rate is
electron injecting layer is by cesium azide (CsN
3) mix 4,7-diphenyl-1, in 10-phenanthroline (Bphen), form, be expressed as CsN
3: Bphen, wherein cesium azide (CsN
3) mass fraction that accounts for electron injecting layer is 30%; The thickness of electron injecting layer is 20 nanometers;
(7) adopt vacuum evaporation on electron injecting layer, to form negative electrode, the vacuum degree of vacuum evaporation is 3 × 10
-5pa, evaporation rate is
negative electrode comprises the first zinc sulfide layer, silver layer and the second zinc sulfide layer that stack gradually on electron injecting layer, is expressed as ZnS/Ag/ZnS, and the thickness of the first zinc sulfide layer and the second zinc sulfide layer is 30 nanometers, and the thickness of silver layer is 10 nanometers;
(8) adopt vacuum evaporation on negative electrode, to form organic barrier layer, the vacuum degree of vacuum evaporation is 1 × 10
-5pa, evaporation rate is
organic barrier layer is formed by CuPc (CuPc), and the thickness on organic barrier layer is 300 nanometers;
(9) adopt vacuum evaporation to steam altogether oxidation two rheniums and nickel sulfide, on organic barrier layer, form inorganic barrier layer, vacuum degree is 1 × 10
-5pa, evaporation rate is
inorganic barrier layer is mixed to form by being oxidized two rheniums and nickel sulfide, is expressed as Re
2o:NiS, being wherein oxidized the mass fraction that two rheniums account for inorganic barrier layer is 20%, the thickness of inorganic barrier layer is 150 nanometers; Organic barrier layer and inorganic barrier layer form a protective layer, are expressed as CuPc/Re
2o:NiS;
(10) replace repeating step (8) and step (9) 6 times, finally on negative electrode, form 7 stacked protective layers, be expressed as (CuPc/Re
2o:NiS)
7, obtaining structure is ITO/MoO
3: NPB/TCTA/Ir (ppy)
3: TPBI/Bphen/CsN
3: Bphen/ZnS/Ag/ZnS/ (CuPc/Re
2o:NiS)
7organic electroluminescence device.
Embodiment 2
Structure is ITO/MoO
3: NPB/TCTA/Ir (ppy)
3: TPBI/Bphen/CsN
3: Bphen/ZnS/Ag/ZnS/ (NBP/ReO:ZnS)
6the encapsulation of organic electroluminescence device
In step (1)～(7), the time of carrying out surface activation process except antianode is 50 minutes, and all the other are with embodiment 1.
(8) adopt vacuum evaporation on negative electrode, to form organic barrier layer, the vacuum degree of vacuum evaporation is 5 × 10
-5pa, evaporation rate is
organic barrier layer is by N, N'-diphenyl-N, and N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB) forms, and the thickness on organic barrier layer is 300 nanometers;
(9) adopt vacuum evaporation to steam altogether rheium oxide and zinc sulphide, on organic barrier layer, form inorganic barrier layer, vacuum degree is 5 × 10
-5pa, evaporation rate is
inorganic barrier layer is mixed to form by rheium oxide and zinc sulphide, is expressed as ReO:ZnS, and wherein to account for the mass fraction of inorganic barrier layer be 10% to rheium oxide, and the thickness of inorganic barrier layer is 100 nanometers; Organic barrier layer and inorganic barrier layer form a protective layer, are expressed as NBP/ReO:ZnS;
(10) replace repeating step (8) and step (9) 5 times, finally on negative electrode, form 6 stacked protective layers, be expressed as (NBP/ReO:ZnS)
6, obtaining structure is ITO/MoO
3: NPB/TCTA/Ir (ppy)
3: TPBI/Bphen/CsN
3: Bphen/ZnS/Ag/ZnS/ (NBP/ReO:ZnS)
6organic electroluminescence device.
Embodiment 3
Structure is ITO/MoO
3: NPB/TCTA/Ir (ppy)
3: TPBI/Bphen/CsN
3: Bphen/ZnS/Ag/ZnS/ (Alq
3/ Re
2o
3: CuS)
6the encapsulation of organic electroluminescence device
In step (1)～(7), the time of carrying out surface activation process except antianode is 40 minutes, and all the other are with embodiment 1.
(8) adopt vacuum evaporation on negative electrode, to form organic barrier layer, the vacuum degree of vacuum evaporation is 5 × 10
-5pa, evaporation rate is
organic barrier layer is by (oxine)-aluminium (Alq
3) form, the thickness on organic barrier layer is 200 nanometers;
(9) adopt vacuum evaporation to steam altogether rhenium sesquioxide and copper sulfide, on organic barrier layer, form inorganic barrier layer, vacuum degree is 5 × 10
-5pa, evaporation rate is
inorganic barrier layer is mixed to form by rhenium sesquioxide and copper sulfide, is expressed as Re
2o
3: CuS, wherein to account for the mass fraction of inorganic barrier layer be 30% to rhenium sesquioxide, the thickness of inorganic barrier layer is 200 nanometers; Organic barrier layer and inorganic barrier layer form a protective layer, are expressed as Alq
3/ Re
2o
3: CuS;
(10) replace repeating step (8) and step (9) 5 times, finally on negative electrode, form 6 stacked protective layers, be expressed as (Alq
3/ Re
2o
3: CuS)
6, obtaining structure is ITO/MoO
3: NPB/TCTA/Ir (ppy)
3: TPBI/Bphen/CsN
3: Bphen/ZnS/Ag/ZnS/ (Alq
3/ Re
2o
3: CuS)
6organic electroluminescence device.
Embodiment 4
Structure is ITO/MoO
3: NPB/TCTA/Ir (ppy)
3: TPBI/Bphen/CsN
3: Bphen/ZnS/Ag/ZnS/ (m-MTDATA/ReO
2: FeS
2)
6the encapsulation of organic electroluminescence device
In step (1)～(7), the time of carrying out surface activation process except antianode is 45 minutes, and all the other are with embodiment 1.
(8) adopt vacuum evaporation on negative electrode, to form organic barrier layer, the vacuum degree of vacuum evaporation is 5 × 10
-5pa, evaporation rate is
organic barrier layer is by 4,4', and 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA) forms, and the thickness on organic barrier layer is 240 nanometers;
(9) adopt vacuum evaporation to steam altogether rhenium dioxide and ferrous disulfide, on organic barrier layer, form inorganic barrier layer, vacuum degree is 5 × 10
-5pa, evaporation rate is
inorganic barrier layer is mixed to form by rhenium dioxide and ferrous disulfide, is expressed as ReO
2: FeS
2, wherein to account for the mass fraction of inorganic barrier layer be 15% to rhenium dioxide, the thickness of inorganic barrier layer is 180 nanometers; Organic barrier layer and inorganic barrier layer form a protective layer, are expressed as m-MTDATA/ReO
2: FeS
2;
(10) replace repeating step (8) and step (9) 5 times, finally on negative electrode, form 6 stacked protective layers, be expressed as (m-MTDATA/ReO
2: FeS
2)
6, obtaining structure is ITO/MoO
3: NPB/TCTA/Ir (ppy)
3: TPBI/Bphen/CsN
3: Bphen/ZnS/Ag/ZnS/ (m-MTDATA/ReO
2: FeS
2)
6organic electroluminescence device.
Embodiment 5
Structure is ITO/MoO
3: NPB/TCTA/Ir (ppy)
3: TPBI/Bphen/CsN
3: Bphen/ZnS/Ag/ZnS/ (BCP/Re
2o
5: PbS)
6the encapsulation of organic electroluminescence device
Step (1)～(7) are with embodiment 1.
(8) adopt vacuum evaporation on negative electrode, to form organic barrier layer, the vacuum degree of vacuum evaporation is 5 × 10
-5pa, evaporation rate is
organic barrier layer is by 2,9-dimethyl-4,7-biphenyl-1, and 10-phenanthrolene (BCP) forms, and the thickness on organic barrier layer is 260 nanometers;
(9) adopt vacuum evaporation to steam altogether five oxidation two rheniums and vulcanized lead, on organic barrier layer, form inorganic barrier layer, vacuum degree is 5 × 10
-5pa, evaporation rate is
inorganic barrier layer is mixed to form by five oxidation two rheniums and vulcanized lead, is expressed as Re
2o
5: PbS, the mass fraction that wherein five oxidation two rheniums account for inorganic barrier layer is 20%, the thickness of inorganic barrier layer is 140 nanometers; Organic barrier layer and inorganic barrier layer form a protective layer, are expressed as BCP/Re
2o
5: PbS;
(10) replace repeating step (8) and step (9) 5 times, finally on negative electrode, form 6 stacked protective layers, be expressed as (BCP/Re
2o
5: PbS)
6, obtaining structure is ITO/MoO
3: NPB/TCTA/Ir (ppy)
3: TPBI/Bphen/CsN
3: Bphen/ZnS/Ag/ZnS/ (BCP/Re
2o
5: PbS)
6organic electroluminescence device.
Embodiment 6
Structure is ITO/MoO
3: NPB/TCTA/Ir (ppy)
3: TPBI/Bphen/CsN
3: Bphen/ZnS/Ag/ZnS/ (CuPc/ReO
3: CdS)
5the encapsulation of organic electroluminescence device
Step (1)～(7) are with embodiment 1.
(8) adopt vacuum evaporation on negative electrode, to form organic barrier layer, the vacuum degree of vacuum evaporation is 1 × 10
-3pa, evaporation rate is
organic barrier layer is formed by CuPc (CuPc), and the thickness on organic barrier layer is 220 nanometers;
(9) adopt vacuum evaporation to steam altogether rhenium trioxide and cadmium sulfide, on organic barrier layer, form inorganic barrier layer, vacuum degree is 1 × 10
-3pa, evaporation rate is
inorganic barrier layer is mixed to form by rhenium trioxide and cadmium sulfide, is expressed as ReO
3: CdS, wherein to account for the mass fraction of inorganic barrier layer be 19% to rhenium trioxide, the thickness of inorganic barrier layer is 150 nanometers; Organic barrier layer and inorganic barrier layer form a protective layer, are expressed as CuPc/ReO
3: CdS;
(10) replace repeating step (8) and step (9) 4 times, finally on negative electrode, form 5 stacked protective layers, be expressed as (CuPc/ReO
3: CdS)
5, obtaining structure is ITO/MoO
3: NPB/TCTA/Ir (ppy)
3: TPBI/Bphen/CsN
3: Bphen/ZnS/Ag/ZnS/ (CuPc/ReO
3: CdS)
5organic electroluminescence device.
Comparative example 1
Structure is ITO/MoO
3: NPB/TCTA/Ir (ppy)
3: TPBI/Bphen/CsN
3: the encapsulation of the organic electroluminescence device of Bphen/ZnS/Ag/ZnS
The structure of this organic electroluminescence device is not except there is no protective layer, and all the other are with embodiment 1.
Method is with step (1)～(7) of embodiment 1.
Table 1 is water vapor permeable rate and the useful life of the organic electroluminescence device of embodiment 1～6 and comparative example 1.
Water vapor permeable rate and the useful life of the organic electroluminescence device of table 1 embodiment 1～6 and comparative example 1
As seen from Table 1; with respect to comparative example 1, the water vapor permeable rate of the organic electroluminescence device of embodiment 1～6 is higher, illustrates that the organic electroluminescence device waterproof of embodiment 1～6, oxygen ability are strong; can effectively protect organic layer and negative electrode, thereby useful life is longer.And, because the light transmission of protective layer is better, make the light transmittance of encapsulating face of the organic electroluminescence device of embodiment 1～6 higher, bright dipping is effective.
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 (9)
1. an organic electroluminescence device, comprise the anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the negative electrode that stack gradually, it is characterized in that, also comprise 5～7 protective layers that are laminated on described negative electrode, each protective layer comprises organic barrier layer and is laminated in the inorganic barrier layer on described organic barrier layer; Wherein, described organic barrier layer is by CuPc, 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 or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene forms, and described inorganic barrier layer is mixed to form by the one in a kind of and cadmium sulfide, vulcanized lead, ferrous disulfide, copper sulfide, zinc sulphide and the nickel sulfide that are oxidized in two rheniums, rheium oxide, rhenium sesquioxide, rhenium dioxide, five oxidation two rheniums and rhenium trioxide.
2. organic electroluminescence device according to claim 1, is characterized in that, a kind of mass fraction that accounts for described inorganic barrier layer in described oxidation two rheniums, rheium oxide, rhenium sesquioxide, rhenium dioxide, five oxidation two rheniums and rhenium trioxide is 10～30%.
3. organic electroluminescence device according to claim 1, is characterized in that, the thickness on described organic barrier layer is 200 nanometer～300 nanometers.
4. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described inorganic barrier layer is 100 nanometer～200 nanometers.
5. a method for packing for organic electroluminescence device, is characterized in that, comprises the steps:
Step 1: anode is provided, adopts vacuum evaporation to form hole injection layer on described anode;
Step 2: adopt vacuum evaporation to form hole transmission layer on described hole injection layer;
Step 3: adopt vacuum evaporation to form luminescent layer on described hole transmission layer;
Step 4: adopt vacuum evaporation to form electron transfer layer on described luminescent layer;
Step 5: adopt vacuum evaporation to form electron injecting layer on described electron transfer layer;
Step 6: adopt vacuum evaporation negative electrode on described electron injecting layer;
Step 7: adopt vacuum evaporation to form organic barrier layer on described negative electrode, described organic barrier layer is by CuPc, 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 or 2,9-dimethyl-4,7-biphenyl-1,10-phenanthrolene forms;
Step 8: adopt vacuum evaporation to form inorganic barrier layer on described organic barrier layer, described inorganic barrier layer is mixed to form by the one in a kind of and cadmium sulfide, vulcanized lead, ferrous disulfide, copper sulfide, zinc sulphide and the nickel sulfide that are oxidized in two rheniums, rheium oxide, rhenium sesquioxide, rhenium dioxide, five oxidation two rheniums and rhenium trioxide, and described organic barrier layer and inorganic barrier layer form a protective layer;
Step 9: alternately repeating said steps seven and described step 84 to 6 times, on described negative electrode, form 5～7 protective layers, obtain organic electroluminescence device.
6. the method for packing of organic electroluminescence device according to claim 5, is characterized in that, in described step 7～step 9, the vacuum degree of vacuum evaporation is 1 × 10
-5pa～1 × 10
-3pa.
7. the method for packing of organic electroluminescence device according to claim 5, is characterized in that, in described step 7～step 9, evaporation rate is
8. the method for packing of organic electroluminescence device according to claim 5, it is characterized in that, before described employing vacuum evaporation forms the step of hole injection layer on described anode, also comprise the cleaning step of antianode, described cleaning step is: described anode is put into acetone, ethanol, deionized water and ethanol successively and carry out ultrasonic cleaning, each ultrasonic cleaning 5 minutes, then dries up with nitrogen, then uses oven for drying.
9. the method for packing of organic electroluminescence device according to claim 8, it is characterized in that, after described cleaning step completes, described employing vacuum evaporation also comprised the step of described anode being carried out to surface activation process form the step of hole injection layer on described anode before, and the step of described activation processing is: the anode after adopting ultraviolet-ozone to cleaning-drying is processed 30～50 minutes.
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| WO2021042570A1 (en) * | 2019-09-03 | 2021-03-11 | 武汉华星光电半导体显示技术有限公司 | Thin film encapsulation layer, organic light-emitting diode device and manufacturing method therefor |
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