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CN103594647A - Organic electroluminescent device and preparation method thereof - Google Patents

Organic electroluminescent device and preparation method thereof Download PDF

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Publication number
CN103594647A
CN103594647A CN201210290574.8A CN201210290574A CN103594647A CN 103594647 A CN103594647 A CN 103594647A CN 201210290574 A CN201210290574 A CN 201210290574A CN 103594647 A CN103594647 A CN 103594647A
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layer
protective layer
thickness
negative electrode
organic electroluminescence
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周明杰
王平
钟铁涛
梁禄生
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract

The invention relates to an organic electroluminescent device, comprising an anode conductive substrate, a luminescent layer, a cathode, a protective layer, a metal barrier layer, a carbon-fluorine-oxygen compound and an external protective layer which are sequentially laminated, wherein the metal barrier layer is made of at least one of Ag, Al, Au, Cu, Ni and Mg. The organic electroluminescent device further comprises a package cover, wherein the package cover packages the luminescent layer, the cathode, the protective layer, the metal barrier layer, the carbon-fluorine-oxygen compound and the external protective layer on the anode conductive substrate. The organic electroluminescent device is long in service life. The invention further provides a preparation method of the organic electroluminescent device.

Description

Organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) is a kind of current mode light emitting semiconductor device based on organic material.Its typical structure is that the luminous organic material of 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 device 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.Because the whole world is increasing, throw light on 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.
Yet organic electroluminescence device is subject to after moisture and moisture erosion, can cause that the material of organic electroluminescence device inner member occurs aging and then lost efficacy, thereby the life-span of described organic electroluminescence device is shorter.
Summary of the invention
Based on this, be necessary to provide longer organic electroluminescence device of a kind of life-span and preparation method thereof.
, comprise the anode conducting substrate, luminescent layer, negative electrode, protective layer, metal barrier, carbon fluorine oxide layer and the outer protective layer that stack gradually; Wherein,
The material of described metal barrier is at least one in Ag, Al, Au, Cu, Ni and Mg;
The material of described carbon fluorine oxide layer is
Figure BDA00002016948400011
wherein, x=1 or 2; Y=1 or 2; Z=1 or 2; N=50 ~ 100;
Described organic electroluminescence device also comprises cap, and described cap is packaged in described luminescent layer, negative electrode, protective layer, metal barrier, carbon fluorine oxide layer and outer protective layer in described anode conducting substrate.
In a preferred embodiment, the material of described protective layer is CuPc, NPB, Alq3, SiO, MgF 2and at least one in ZnS.
In a preferred embodiment, the material of described outer protective layer is SiO.
In a preferred embodiment, the material of described cap is PET.
In a preferred embodiment, described negative electrode comprises two layer medium layer and is located at the metal level between described two layer medium layer, and the material of described dielectric layer is zinc sulphide, tin indium oxide or zinc oxide aluminum, and the material of described metal level is at least one in aluminium, silver and gold.
A preparation method for organic electroluminescence device, comprises the steps:
In anode conducting substrate, form luminescent layer;
On described luminescent layer, form negative electrode;
On described negative electrode, form protective layer;
Adopt the method for vacuum evaporation to form metal barrier on described protective layer, the material of wherein said metal barrier is at least one in Ag, Al, Au, Cu, Ni and Mg, and vacuum degree is 8 * 10 -5pa ~ 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400021
thickness is 100nm ~ 200nm;
On described metal barrier, form carbon fluorine oxide layer, comprising: carbon fluorine oxide is spin-coated on described metal barrier, and thickness is 1 μ m ~ 1.5 μ m, then adopts ultraviolet light to be cured, and the molecular formula of described carbon fluorine oxide is
Figure BDA00002016948400022
wherein, x=1 or 2; Y=1 or 2; Z=1 or 2; N=50 ~ 100;
On described carbon fluorine oxide layer, form outer protective layer; And
Use cap that described luminescent layer, negative electrode, protective layer, metal barrier, carbon fluorine oxide layer and outer protective layer are packaged in described anode conducting substrate.
In a preferred embodiment, adopt the method for vacuum evaporation to form protective layer, the material of wherein said protective layer is CuPc, NPB, Alq3, SiO, MgF 2and at least one in ZnS, vacuum degree is 8 * 10 -5pa ~ 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400031
thickness is 200nm ~ 300nm.
In a preferred embodiment, the method that forms described moisture absorbed layer comprises: adopt the mode of vacuum evaporation to prepare described outer protective layer, the material of described outer protective layer is SiO, and vacuum degree is 8 * 10 -5pa ~ 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400032
thickness is 100nm ~ 150nm.
In a preferred embodiment; using cap that described luminescent layer, negative electrode, protective layer, metal barrier, carbon fluorine oxide layer and outer protective layer are packaged in to the suprabasil method of described anode conducting comprises: at PET film edge coating thickness, be the epoxy encapsulation glue of 1 ~ 1.5 μ m; then the UV light that is 200 ~ 400nm with wavelength by described epoxy encapsulation adhesive curing to described anode conducting substrate, light intensity 10 ~ 15mW/cm 2, time for exposure 300 ~ 400s.
In a preferred embodiment, adopt vapour deposition method to form described negative electrode, described negative electrode comprises two layer medium layer and is located at the metal level between described two layer medium layer, the material of described dielectric layer is zinc sulphide, tin indium oxide or zinc oxide aluminum, and the material of described metal level is at least one in aluminium, silver and gold.
Above-mentioned organic electroluminescence device adopts the method for evaporation to prepare protective layer, avoids negative electrode to be damaged; Carbon fluorine oxide layer can cooperatively interact with metal barrier, effectively the corrosion of block water oxygen; Cap can further improve waterproof oxygen ability, thereby makes the life-span of organic electroluminescence device longer.
Accompanying drawing explanation
By the more specifically explanation of the preferred embodiments of the present invention shown in accompanying drawing, above-mentioned and other object of the present invention, that Characteristics and advantages will become will be more clear.In whole accompanying drawings, identical Reference numeral is indicated identical part, and deliberately by actual size equal proportion convergent-divergent, draws accompanying drawing, focuses on illustrating purport of the present invention.
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is preparation method's the flow chart of the organic electroluminescent 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 have been 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, so 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 anode conducting substrate 10, functional layer 20, negative electrode 30, protective layer 40, metal barrier 50, carbon fluorine oxide layer 60 and the outer protective layer 70 stacking gradually.Organic electroluminescence device 100 also comprises cap 80, and cap 80 is packaged in functional layer 20, negative electrode 30, protective layer 40, metal barrier 50, carbon fluorine oxide layer 60 and outer protective layer 70 in anode conducting substrate 10.
Anode conducting substrate 10 is glass conductive substrates or organic PETG (PET) film substrate that conducts electricity.The ITO layer in anode conducting substrate 10 with the anode pattern of being prepared with.The thickness of ITO layer is 100nm ~ 150nm.
Functional layer 20 is formed at anode conducting substrate 10 surfaces.Functional layer 20 comprises hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, the electron injecting layer stacking gradually.Be appreciated that hole injection layer, hole transmission layer, electron transfer layer, electron injecting layer can omit, now functional layer 20 only comprises luminescent layer.
In present embodiment, the material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB 3).MoO 3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.
The material of hole transmission layer is 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamines (TCTA).The thickness of hole transmission layer is 30nm.
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy) 3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen 3).CsN 3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.
It should be noted that, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer also can adopt other materials as required.
Negative electrode 30 is formed at the surface of functional layer 20.Negative electrode 30 can be single layer structure or sandwich construction.When negative electrode 30 is single layer structure, the thickness of negative electrode is 100nm, and the material of negative electrode 30 is aluminium (Al), silver (Ag) or gold (Au); When negative electrode 30 is sandwich construction, negative electrode 30 comprises two layer medium layer and is located at the metal level between two layer medium layer, the thickness of dielectric layer is 30nm, the thickness of metal level is 10nm, the material of dielectric layer is zinc sulphide (ZnS), tin indium oxide (ITO) or zinc oxide aluminum (AZO), and the material of metal level is silver (Ag).
Protective layer 40 is formed at the surface of negative electrode 30.The material of protective layer 40 is CuPc(CuPc), NPB, Alq3(tri--(oxine) aluminium), SiO, MgF 2and at least one in ZnS.The thickness of protective layer 40 is 200nm ~ 300nm.The effect of protective layer 40 is for preventing that negative electrode 30 is subject to the destruction of subsequent technique in preparation process.
Metal barrier 50 is formed at the surface of protective layer 40.The material of metal barrier 50 is at least one in Ag, Al, Au, Cu, Ni and Mg.The thickness of metal barrier 50 is 100 ~ 200nm.Metal barrier 50 can improve the waterproof oxygen ability of device.
Carbon fluorine oxide layer 60 is formed at the surface of metal barrier 50.The material of carbon fluorine oxide layer 60 is
Figure BDA00002016948400051
wherein, x=1 or 2; Y=1 or 2; Z=1 or 2; N=50 ~ 100.
The thickness of carbon fluorine oxide layer 60 is 1 μ m ~ 1.5 μ m.Carbon fluorine oxide layer 60 rete evenness are high, have lower Young's modulus, can significantly reduce the stress of rete.
Preferably, metal barrier 50 forms barrier layer with carbon fluorine oxide layer 60, and the number of plies on barrier layer is three layers, for example, be more than or equal to 3 layers.Form block water, the erosion of oxygen isoreactivity material to organic electroluminescence device better of acting as of multilayer barrier layer, the life-span of improving organic electroluminescence device.
Outer protective layer 70 is formed at the surface of carbon fluorine oxide layer 60.The material of outer protective layer 70 is SiO.Acting as of outer protective layer forms fine and close diaphragm, can further improve the packaging effect of organic electroluminescence device.
Cap 80 is covered on outer protective layer 70.The material of cap 80 can be PET(PETG).The lower surface of cap 80 has been recessed to form host cavity.Functional layer 20, negative electrode 30, protective layer 40, metal barrier 50, carbon fluorine oxide layer 60 and outer protective layer 70 are all contained in this host cavity.The edge of cap 80 is tightly connected by packaging plastic (not shown) and anode conducting substrate 10, thereby functional layer 20, negative electrode 30, protective layer 40, metal barrier 50, carbon fluorine oxide layer 60 and outer protective layer 70 are encapsulated in anode conducting substrate 10.When I PET of material of anode conducting substrate 10, adopt PET as cap, can improve the sealability of device, and can encapsulation be dropped to minimum on the impact of light efficiency.
The mode that above-mentioned organic electroluminescence device 100 adopts carbon fluorine oxide layer 60 to match with metal barrier 50, the corrosion of block water oxygen effectively.
Refer to Fig. 2, the preparation method of above-mentioned organic electroluminescence device 100 comprises the steps:
Step S110, in anode conducting substrate 10, form functional layer 20.
Anode conducting substrate 10 can be glass conductive substrates or organic PETG (PET) film substrate that conducts electricity.Anode conducting substrate 10 has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm ~ 150nm.
Preliminary treatment was first carried out to remove the pollutant on anode conducting substrate 10 surfaces in anode conducting substrate 10 surfaces before forming functional layer 20, and the oxygen content of carrying out surface active increase anode conducting substrate 10 surfaces is to improve the work function on anode conducting substrate 10 surfaces.Be specially, anode conducting substrate 10 is adopted successively and removes each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min, dry up afterwards with nitrogen, baking box is dried.
Functional layer 20 comprises hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, the electron injecting layer stacking gradually.
In present embodiment, the material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB 3).MoO 3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400061
The material of hole transmission layer is 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamines (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400071
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy) 3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400073
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen 3), CsN 3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
It should be noted that, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer also can adopt other materials as required.Hole injection layer, hole transmission layer, electron transfer layer, electron injecting layer can omit, and now functional layer 20 only comprises luminescent layer.
Step S120, on functional layer 20 surface, form negative electrodes 30.
Negative electrode 30 can be single layer structure or sandwich construction.
When negative electrode 30 is single layer structure, the thickness of negative electrode 30 is 100nm, and the material of negative electrode 30 is aluminium (Al), silver (Ag) or gold (Au), and negative electrode 30 is formed by vacuum evaporation, and vacuum degree is 5 * 10 -5pa, evaporation rate is
Figure BDA00002016948400075
When negative electrode 30 is sandwich construction, negative electrode 30 comprises two layer medium layer and is located at the metal level between two layer medium layer.The thickness of dielectric layer is 30nm, and the thickness of metal level is 10nm.The material of dielectric layer is zinc sulphide (ZnS), tin indium oxide (ITO) or zinc oxide aluminum (AZO), and the material of metal level is silver (Ag).Wherein, tin indium oxide (ITO) or zinc oxide aluminum (AZO) are made by sputter, base vacuum degree 2 * 10 -4pa; ZnS or Ag are formed by vacuum evaporation, and vacuum degree is 5 * 10 -5pa, evaporation rate is
The method of step S130, employing vacuum evaporation forms protective layer 40 on negative electrode 30.
The material of protective layer 40 is CuPc, NPB, Alq3, SiO, MgF 2and at least one in ZnS.During vacuum evaporation, vacuum degree is 8 * 10 -5pa ~ 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400077
thickness is 200nm ~ 300nm.
The method of step S140, employing vacuum evaporation forms metal barrier 50 on protective layer 40.
The material of metal barrier 50 is at least one in Ag, Al, Au, Cu, Ni and Mg.While using the method making of vacuum evaporation, vacuum degree is 8 * 10 -5pa ~ 3 * 10 -5pa, evaporation rate
Figure BDA00002016948400081
thickness 100nm ~ 200nm.
Step S150, on metal barrier 50, form carbon fluorine oxide layer 60.
The concrete formation step of carbon fluorine oxide layer 60 is as follows: carbon fluorine oxide is spin-coated on described metal barrier, and thickness is 1 μ m ~ 1.5 μ m, then adopts ultraviolet light to be cured, and the molecular formula of described carbon fluorine oxide is
Figure BDA00002016948400082
wherein, x=1 or 2; Y=1 or 2; Z=1 or 2; N=50 ~ 100.
Preferably, repeating step S140, S150 at least three times successively.
Step S160, on carbon fluorine oxide layer 60, form outer protective layer 70.
Concrete, adopt the mode of vacuum evaporation to prepare outer protective layer 70.The material of outer protective layer 70 is SiO.During preparation, vacuum degree is 8 * 10 -5pa ~ 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400083
thickness is 100nm ~ 150nm.
Step S170, use cap 80 are encapsulated in functional layer 20, negative electrode 30, protective layer 40, metal barrier 50, carbon fluorine oxide layer 60 and outer protective layer 70 in anode conducting substrate 10.
The material of cap 80 is PET.In cap 80, be formed with host cavity.Thereby cap 80 is covered on heat dissipating layer, 80 surfaces are contained in host cavity by functional layer 20, negative electrode 30, protective layer 40, metal barrier 50, carbon fluorine oxide layer 60 and outer protective layer 70.
Concrete grammar is: at PET film edge coating thickness, be the epoxy encapsulation glue of 1 ~ 1.5 μ m, the UV light that is then 200 ~ 400nm with wavelength by described epoxy encapsulation adhesive curing to anode conducting substrate 10, light intensity 10 ~ 15mW/cm 2, time for exposure 300 ~ 400s.
The preparation method of above-mentioned organic electroluminescence device, preparation technology is simple, easily preparation in enormous quantities; Adopt the method for evaporation to prepare protective layer 40, avoid negative electrode to be damaged; Thereby metal barrier 50 improves with the stacked compactness that makes of carbon fluorine oxide layer 60, and the two cooperation is the corrosion of block water oxygen effectively; Cap 80 adopts PET can effectively improve waterproof oxygen ability, extends the useful life of organic electroluminescence device 100.
Below in conjunction with specific embodiment, organic electroluminescence device provided by the invention and preparation method thereof is elaborated.
Embodiment 1
Preparation structure is: ITO/NPB:MoO 3/ TCTA/TPBI:Ir (ppy) 3/ Bphen/Bphen:CsN 3/ Al/CuPc/ (Ag/ carbon fluorine oxide) 3the organic electroluminescence device of/CaO/Cu/ cap.
The preparation method of above-mentioned organic electroluminescence device, comprises the following steps:
1, in conductive substrates, form functional layer.
Conductive substrates is glass conductive substrates.Conductive substrates has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Preliminary treatment was first carried out to remove the pollutant of substrate surface in conductive substrates surface before forming functional layer, and the oxygen content of carrying out surface active increase conductive substrates surface is to improve the work function on conductive substrates surface.Be specially, conductive substrates is adopted to each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min successively, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB 3).MoO 3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400091
The material of hole transmission layer is 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamines (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy) 3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400094
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen 3), CsN 3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400101
2, on functional layer surface, form negative electrode.
The material of negative electrode is aluminium.The thickness of negative electrode is 100nm.Negative electrode is formed by vacuum evaporation, and vacuum degree is 5 * 10 -5pa, evaporation rate is
Figure BDA00002016948400102
3, at cathode surface, form protective layer.
Adopt the mode of vacuum evaporation on negative electrode, to prepare one deck CuPc, vacuum degree 3 * 10 -5pa, evaporation rate
Figure BDA00002016948400103
thickness 200nm.
4, adopt the method for vacuum evaporation to form metal barrier on described protective layer.
The material of metal barrier is Ag.Adopt the method for vacuum evaporation to make, vacuum degree is 5 * 10 -5pa, evaporation rate is thickness is 100nm.
5, on metal barrier, form carbon fluorine oxide layer.
The material of carbon fluorine oxide layer is
Figure BDA00002016948400105
adopt the technique of first spin coating post-exposure to make, gluing thickness 1 μ m, is then cured light intensity 10mW/cm with UV light (λ=365nm) 2, time for exposure 200s.
Repeating step 4,5 three three-layer metal barrier layer and carbon fluorine oxide layers with formation alternative arrangement.
6, on carbon fluorine oxide layer, form outer protective layer.
The material of outer protective layer adopts SiO, adopts the method for vacuum evaporation to make, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002016948400106
thickness 100nm.
7, use cap that luminescent layer, negative electrode, protective layer, metal barrier, carbon fluorine oxide layer and outer protective layer are packaged in described anode conducting substrate.
Edge-coating epoxy encapsulation glue (thickness 1 μ m) at PET film, is cured light intensity 10mW/cm with UV light (λ=365nm) 2, time for exposure 400s.
Embodiment 2
Preparation structure is: ITO/NPB:MoO 3/ TCTA/TPBI:Ir (ppy) 3/ Bphen/Bphen:CsN 3/ Al/NPB/ (Al/ carbon fluorine oxide) 3the organic electroluminescence device of/BaO/Ag/ cap.
1, in conductive substrates, form functional layer.
Conductive substrates is glass conductive substrates.Conductive substrates has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Preliminary treatment was first carried out to remove the pollutant of substrate surface in conductive substrates surface before forming functional layer, and the oxygen content of carrying out surface active increase conductive substrates surface is to improve the work function on conductive substrates surface.Be specially, conductive substrates is adopted to each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min successively, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB 3).MoO 3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400111
The material of hole transmission layer is 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamines (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400112
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy) 3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400113
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400114
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen 3), CsN 3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
2, on functional layer surface, form negative electrode.
The material of negative electrode is ZnS/Al/ZnS.The thickness of negative electrode is 110nm.Negative electrode is formed by vacuum evaporation, and vacuum degree is 5 * 10 -5pa, evaporation rate is
Figure BDA00002016948400116
3, at cathode surface, form protective layer.
Adopt the mode of vacuum evaporation on negative electrode, to prepare one deck NPB, vacuum degree 3 * 10 -5pa, evaporation rate
Figure BDA00002016948400121
thickness 300nm.
4, adopt the method for vacuum evaporation to form metal barrier on described protective layer.
The material of metal barrier is Al.Adopt the method for vacuum evaporation to make, vacuum degree is 5 * 10 -5pa, evaporation rate thickness is 200nm.
5, on metal barrier, form carbon fluorine oxide layer.
The material of carbon fluorine oxide layer is
Figure BDA00002016948400123
adopt the technique of first spin coating post-exposure to make, gluing thickness 1.5 μ m, are then cured light intensity 15mW/cm with UV light (λ=365nm) 2, time for exposure 200s.
Repeating step 4,5 three three-layer metal barrier layer and carbon fluorine oxide layers with formation alternative arrangement.
6, on carbon fluorine oxide layer, form outer protective layer.
The material of outer protective layer adopts SiO, adopts the method for vacuum evaporation to make, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002016948400124
thickness 150nm.
7, use cap that luminescent layer, negative electrode, protective layer, metal barrier, carbon fluorine oxide layer and outer protective layer are packaged in described anode conducting substrate.
Edge-coating epoxy encapsulation glue (thickness 1.5 μ m) at tinsel, is cured light intensity 15mW/cm with UV light (λ=365nm) 2, time for exposure 300s.
Embodiment 3
Preparation structure is: ITO/NPB:MoO3/TCTA/TPBI:Ir (ppy) 3/Bphen/Bphen:CsN3/Al/Alq3/ (Au/ carbon fluorine oxide) 3the organic electroluminescence device of/SrO/Cu/ cap.
The preparation method of above-mentioned organic electroluminescence device, comprises the following steps:
1, in conductive substrates, form functional layer.
Conductive substrates is glass conductive substrates.Conductive substrates has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Preliminary treatment was first carried out to remove the pollutant of substrate surface in conductive substrates surface before forming functional layer, and the oxygen content of carrying out surface active increase conductive substrates surface is to improve the work function on conductive substrates surface.Be specially, conductive substrates is adopted to each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min successively, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB 3).MoO 3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400131
The material of hole transmission layer is 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamines (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy) 3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400133
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400134
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen 3), CsN 3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
2, on functional layer surface, form negative electrode.
The material of negative electrode is ITO/Ag/ITO.The thickness of negative electrode is 120nm.Negative electrode is formed by vacuum evaporation, and vacuum degree is 5 * 10 -5pa, evaporation rate is
Figure BDA00002016948400136
3, at cathode surface, form protective layer.
Adopt the mode of vacuum evaporation on negative electrode, to prepare one deck Alq3, vacuum degree 3 * 10 -5pa, evaporation rate
Figure BDA00002016948400137
thickness 250nm.
4, adopt the method for vacuum evaporation to form metal barrier on described protective layer.
The material of metal barrier is Au.Adopt the method for vacuum evaporation to make, vacuum degree is 5 * 10 -5pa, evaporation rate
Figure BDA00002016948400141
thickness is 150nm.
5, on metal barrier, form carbon fluorine oxide layer.
The material of carbon fluorine oxide layer is
Figure BDA00002016948400142
adopt the technique of first spin coating post-exposure to make, gluing thickness 1.2 μ m, are then cured light intensity 11mW/cm with UV light (λ=365nm) 2, time for exposure 230s.
Repeating step 4,5 three three-layer metal barrier layer and carbon fluorine oxide layers with formation alternative arrangement.
6, on carbon fluorine oxide layer, form outer protective layer.
The material of outer protective layer adopts SiO, adopts the method for vacuum evaporation to make, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002016948400143
thickness 120nm.
7, use cap that luminescent layer, negative electrode, protective layer, metal barrier, carbon fluorine oxide layer and outer protective layer are packaged in described anode conducting substrate.
Edge-coating epoxy encapsulation glue (thickness 1.2 μ m) at tinsel, is cured light intensity 11mW/cm with UV light (λ=365nm) 2, time for exposure 350s.
Embodiment 4
Preparation structure is: ITO/NPB:MoO 3/ TCTA/TPBI:Ir (ppy) 3/ Bphen/Bphen:CsN 3/ Al/SiO/ (Cu/ carbon fluorine oxide) 3the organic electroluminescence device of/MgO/Cu-Al/ cap.
The preparation method of above-mentioned organic electroluminescence device, comprises the following steps:
1, in conductive substrates, form functional layer.
Conductive substrates is glass conductive substrates.Conductive substrates has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Preliminary treatment was first carried out to remove the pollutant of substrate surface in conductive substrates surface before forming functional layer, and the oxygen content of carrying out surface active increase conductive substrates surface is to improve the work function on conductive substrates surface.Be specially, conductive substrates is adopted to each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min successively, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB 3).MoO 3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400151
The material of hole transmission layer is 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamines (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400152
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy) 3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400153
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400154
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen 3), CsN 3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400155
2, on functional layer surface, form negative electrode.
The material of negative electrode is AZO/Au/AZO.The thickness of negative electrode is 110nm.Negative electrode is formed by vacuum evaporation, and vacuum degree is 5 * 10 -5pa, evaporation rate is
Figure BDA00002016948400156
3, at cathode surface, form protective layer.
Adopt the mode of vacuum evaporation on negative electrode, to prepare one deck SiO, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002016948400157
thickness 200nm.
4, adopt the method for vacuum evaporation to form metal barrier on described protective layer.
The material of metal barrier is Cu.Adopt the method for vacuum evaporation to make, vacuum degree is 7 * 10 -5pa, evaporation rate thickness is 100nm.
5, on metal barrier, form carbon fluorine oxide layer.
The material of carbon fluorine oxide layer is
Figure BDA00002016948400161
adopt the technique of first spin coating post-exposure to make, under inert atmosphere, make, gluing thickness 1 μ m, is then cured light intensity 10mW/cm with UV light (λ=365nm) 2, time for exposure 200s.
Repeating step 4,5 three three-layer metal barrier layer and carbon fluorine oxide layers with formation alternative arrangement.
6, on carbon fluorine oxide layer, form outer protective layer.
The material of outer protective layer adopts SiO, adopts the method for vacuum evaporation to make, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002016948400162
thickness 100nm.
7, use cap that luminescent layer, negative electrode, protective layer, metal barrier, carbon fluorine oxide layer and outer protective layer are packaged in described anode conducting substrate.
Edge-coating epoxy encapsulation glue (thickness 1 μ m) at tinsel, is cured light intensity 10mW/cm with UV light (λ=365nm) 2, time for exposure 400s.
Embodiment 5
Preparation structure is: ITO/NPB:MoO 3/ TCTA/TPBI:Ir (ppy) 3/ Bphen/Bphen:CsN 3/ Al/MgF 2/ (Ni/ carbon fluorine oxide) 3the organic electroluminescence device of/CaO/Al/ cap.
The preparation method of above-mentioned organic electroluminescence device, comprises the following steps:
1, in conductive substrates, form functional layer.
Conductive substrates is glass conductive substrates.Conductive substrates has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Preliminary treatment was first carried out to remove the pollutant of substrate surface in conductive substrates surface before forming functional layer, and the oxygen content of carrying out surface active increase conductive substrates surface is to improve the work function on conductive substrates surface.Be specially, conductive substrates is adopted to each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min successively, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB 3).MoO 3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400171
The material of hole transmission layer is 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamines (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400172
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy) 3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400174
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen 3), CsN 3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
2, on functional layer surface, form negative electrode.
The material of negative electrode is AZO/Al/AZO.The thickness of negative electrode is 100nm.Negative electrode is formed by vacuum evaporation, and vacuum degree is 5 * 10 -5pa, evaporation rate is
Figure BDA00002016948400176
3, at cathode surface, form protective layer.
Adopt the mode of vacuum evaporation on negative electrode, to prepare one deck MgF 2, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002016948400177
thickness 300nm.
4, adopt the method for vacuum evaporation to form metal barrier on described protective layer.
The material of metal barrier is Ni.Adopt the method for vacuum evaporation to make, vacuum degree is 5 * 10 -5pa, evaporation rate
Figure BDA00002016948400178
thickness is 200nm.
5, on metal barrier, form carbon fluorine oxide layer.
The material of carbon fluorine oxide layer is adopt the technique of first spin coating post-exposure to make, under inert atmosphere, make, gluing thickness 1.5 μ m, are then cured light intensity 15mW/cm with UV light (λ=365nm) 2, time for exposure 200s.
Repeating step 4,5 three three-layer metal barrier layer and carbon fluorine oxide layers with formation alternative arrangement.
6, on carbon fluorine oxide layer, form outer protective layer.
The material of outer protective layer adopts SiO, adopts the method for vacuum evaporation to make, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002016948400181
thickness 150nm.
7, use cap that luminescent layer, negative electrode, protective layer, metal barrier, carbon fluorine oxide layer and outer protective layer are packaged in described anode conducting substrate.
Edge-coating epoxy encapsulation glue (thickness 1.5 μ m) at tinsel, is cured light intensity 15mW/cm with UV light (λ=365nm) 2, time for exposure 300s.
Embodiment 6
Preparation structure is: ITO/NPB:MoO 3/ TCTA/TPBI:Ir (ppy) 3/ Bphen/Bphen:CsN 3/ Al/ZnS/ (Mg/ carbon fluorine oxide) 3the organic electroluminescence device of/BaO/Ag/ cap.
The preparation method of above-mentioned organic electroluminescence device, comprises the following steps:
1, in conductive substrates, form functional layer.
Conductive substrates is glass conductive substrates.Conductive substrates has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Preliminary treatment was first carried out to remove the pollutant of substrate surface in conductive substrates surface before forming functional layer, and the oxygen content of carrying out surface active increase conductive substrates surface is to improve the work function on conductive substrates surface.Be specially, conductive substrates is adopted to each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min successively, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB 3).MoO 3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400182
The material of hole transmission layer is 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamines (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400191
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy) 3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400192
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400193
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen 3), CsN 3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400194
2, on functional layer surface, form negative electrode.
The material of negative electrode is ZnS/Au/ZnS.The thickness of negative electrode is 100nm.Negative electrode is formed by vacuum evaporation, and vacuum degree is 5 * 10 -5pa, evaporation rate is
Figure BDA00002016948400195
3, at cathode surface, form protective layer.
Adopt the mode of vacuum evaporation on negative electrode, to prepare one deck ZnS, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002016948400196
thickness 250nm.
4, adopt the method for vacuum evaporation to form metal barrier on described protective layer.
The material of metal barrier is Mg.Adopt the method for vacuum evaporation to make, vacuum degree is 5 * 10 -5pa, evaporation rate
Figure BDA00002016948400197
thickness is 150nm.
5, on metal barrier, form carbon fluorine oxide layer.
The material of carbon fluorine oxide layer is adopt the technique of first spin coating post-exposure to make, under inert atmosphere, make, gluing thickness 1.2 μ m, are then cured light intensity 11mW/cm with UV light (λ=365nm) 2, time for exposure 230s.
Repeating step 4,5 three three-layer metal barrier layer and carbon fluorine oxide layers with formation alternative arrangement.
6, on carbon fluorine oxide layer, form outer protective layer.
The material of outer protective layer adopts SiO, adopts the method for vacuum evaporation to make, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002016948400201
thickness 130nm.
7, use cap that luminescent layer, negative electrode, protective layer, metal barrier, carbon fluorine oxide layer and outer protective layer are packaged in described anode conducting substrate.
Edge-coating epoxy encapsulation glue (thickness 1.2 μ m) at tinsel, is cured light intensity 11mW/cm with UV light (λ=365nm) 2, time for exposure 350s.
Comparative example 1
Preparation structure is: ITO/NPB:MoO 3/ TCTA/TPBI:Ir (ppy) 3/ Bphen/Bphen:CsN 3/ Al/CuPc/ (Ag) 3the organic electroluminescence device of/CaO/Cu/ cap.
The preparation method of above-mentioned organic electroluminescence device, comprises the following steps:
1, in conductive substrates, form functional layer.
Conductive substrates is glass conductive substrates.Conductive substrates has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Preliminary treatment was first carried out to remove the pollutant of substrate surface in conductive substrates surface before forming functional layer, and the oxygen content of carrying out surface active increase conductive substrates surface is to improve the work function on conductive substrates surface.Be specially, conductive substrates is adopted to each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min successively, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB 3).MoO 3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400202
The material of hole transmission layer is 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamines (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400203
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy) 3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400211
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400212
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen 3), CsN 3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400213
2, on functional layer surface, form negative electrode.
The material of negative electrode is aluminium.The thickness of negative electrode is 100nm.Negative electrode is formed by vacuum evaporation, and vacuum degree is 5 * 10 -5pa, evaporation rate is
Figure BDA00002016948400214
3, at cathode surface, form protective layer.
Adopt the mode of vacuum evaporation on negative electrode, to prepare one deck CuPc, vacuum degree 3 * 10 -5pa, evaporation rate
Figure BDA00002016948400215
thickness 200nm.
4, adopt the method for vacuum evaporation to form metal barrier on described protective layer.
The material of metal barrier is Ag.Adopt the method for vacuum evaporation to make, vacuum degree is 5 * 10 -5pa, evaporation rate is
Figure BDA00002016948400216
thickness is 100nm.
Repeating step 4 three times.
5, on 4, form outer protective layer.
The material of outer protective layer adopts SiO, adopts the method for vacuum evaporation to make, vacuum degree 5 * 10 -5pa, evaporation rate thickness 100nm.
6, use cap that luminescent layer, negative electrode, protective layer, metal barrier, carbon fluorine oxide layer and outer protective layer are packaged in described anode conducting substrate.
Edge-coating epoxy encapsulation glue (thickness 1 μ m) at PET film, is cured light intensity 10mW/cm with UV light (λ=365nm) 2, time for exposure 400s.
Comparative example 2
Preparation structure is: ITO/NPB:MoO 3/ TCTA/TPBI:Ir (ppy) 3/ Bphen/Bphen:CsN 3/ Al/MgF 2/ (carbon fluorine oxide) 3the organic electroluminescence device of/CaO/Al/ cap.
The preparation method of above-mentioned organic electroluminescence device, comprises the following steps:
1, in conductive substrates, form functional layer.
Conductive substrates is glass conductive substrates.Conductive substrates has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Preliminary treatment was first carried out to remove the pollutant of substrate surface in conductive substrates surface before forming functional layer, and the oxygen content of carrying out surface active increase conductive substrates surface is to improve the work function on conductive substrates surface.Be specially, conductive substrates is adopted to each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min successively, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB 3).MoO 3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400221
The material of hole transmission layer is 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamines (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400222
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy) 3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400223
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen 3), CsN 3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016948400225
2, on functional layer surface, form negative electrode.
The material of negative electrode is AZO/Al/AZO.The thickness of negative electrode is 100nm.Negative electrode is formed by vacuum evaporation, and vacuum degree is 5 * 10 -5pa, evaporation rate is
Figure BDA00002016948400226
3, at cathode surface, form protective layer.
Adopt the mode of vacuum evaporation on negative electrode, to prepare one deck MgF 2, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002016948400231
thickness 300nm.
4, on 3, form carbon fluorine oxide layer.
The material of carbon fluorine oxide layer is
Figure BDA00002016948400232
adopt the technique of first spin coating post-exposure to make, under inert atmosphere, make, gluing thickness 1.5 μ m, are then cured light intensity 15mW/cm with UV light (λ=365nm) 2, time for exposure 200s.
Repeating step 4 three times.
5, on 4, form outer protective layer.
The material of outer protective layer adopts SiO, adopts the method for vacuum evaporation to make, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002016948400233
thickness 150nm.
6, use cap that luminescent layer, negative electrode, protective layer, metal barrier, carbon fluorine oxide layer and outer protective layer are packaged in described anode conducting substrate.
Edge-coating epoxy encapsulation glue (thickness 1.5 μ m) at tinsel, is cured light intensity 15mW/cm with UV light (λ=365nm) 2, time for exposure 300s.
The preparation used of the embodiment of the present invention and comparative example and tester are: high vacuum coating equipment (scientific instrument development center, Shenyang Co., Ltd, pressure <1 * 10 -32400), chroma-luminance meter (Konica Minolta, model: CS-100A), IEI point gum machine system, DYMAX photocuring system Pa), current-voltage tester (U.S. Keithly company, model:.
Refer to table 1, table 1 is depicted as the test result of aqueous vapor penetrance (Water Vapor Transmission Rate) of the organic electroluminescence device of embodiment 1 ~ embodiment 6 and comparative example 1 ~ 2 preparation.The aqueous vapor penetrance of the organic electroluminescence device of embodiment 1 ~ embodiment 6 preparations is all less than 7.5 * 10 as can be seen from Table 1 -4g/m 2/ day, the aqueous vapor penetrance (6.6 * 10 of the organic electroluminescence device of preparing much smaller than comparative example -2) waterproof effect is better, can effectively reduce the erosion of outside aqueous vapor to organic electroluminescence device, thereby improve the life-span of organic electroluminescence device.
Table 1
WVTR(g/m 2/day)
Embodiment 1 7.5×10 -4
Embodiment 2 7.0×10 -4
Embodiment 3 4.7×10 -4
Embodiment 4 3.2×10 -4
Embodiment 5 6.9×10 -4
Embodiment 6 6.4×10 -4
Comparative example 1 1.3×10 -3
Comparative example 2 6.6×10 -2
Refer to table 2, it is 1000cd/m at original intensity that table 2 is depicted as organic electroluminescence device prepared by embodiment 1 ~ embodiment 6 and comparative example 2condition under life-span.
Table 2
Figure BDA00002016948400241
As can be seen from Table 2, the initial brightness of the organic electroluminescence device of embodiment 1 ~ embodiment 6 preparations is 1000cd/m 2time, the life-span reaches more than 8000 hours, and the life-span is longer.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.

Claims (10)

1. an organic electroluminescence device, is characterized in that, comprises the anode conducting substrate, luminescent layer, negative electrode, protective layer, metal barrier, carbon fluorine oxide layer and the outer protective layer that stack gradually; Wherein,
The material of described metal barrier is at least one in Ag, Al, Au, Cu, Ni and Mg;
The material of described carbon fluorine oxide layer is
Figure FDA00002016948300011
wherein, x=1 or 2; Y=1 or 2; Z=1 or 2; N=50 ~ 100;
Described organic electroluminescence device also comprises cap, and described cap is packaged in described luminescent layer, negative electrode, protective layer, metal barrier, carbon fluorine oxide layer and outer protective layer in described anode conducting substrate.
2. organic electroluminescence device according to claim 1, is characterized in that: the material of described protective layer is CuPc, NPB, Alq3, SiO, MgF 2and at least one in ZnS.
3. organic electroluminescence device according to claim 1, is characterized in that: the material of described outer protective layer is SiO.
4. organic electroluminescence device according to claim 1, is characterized in that, described metal barrier and carbon fluorine oxide layer form barrier layer, and the number of plies on described barrier layer is three layers.
5. organic electroluminescence device according to claim 1, it is characterized in that: described negative electrode comprises two layer medium layer and is located at the metal level between described two layer medium layer, the material of described dielectric layer is zinc sulphide, tin indium oxide or zinc oxide aluminum, and the material of described metal level is at least one in aluminium, silver and gold.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the steps:
In anode conducting substrate, form luminescent layer;
On described luminescent layer, form negative electrode;
On described negative electrode, form protective layer;
Adopt the method for vacuum evaporation to form metal barrier on described protective layer, the material of wherein said metal barrier is at least one in Ag, Al, Au, Cu, Ni and Mg, and vacuum degree is 8 * 10 -5pa ~ 3 * 10 -5pa, evaporation rate is thickness is 100nm ~ 200nm;
On described metal barrier, form carbon fluorine oxide layer, comprising: carbon fluorine oxide is spin-coated on described metal barrier, and thickness is 1 μ m ~ 1.5 μ m, then adopts ultraviolet light to be cured, and the molecular formula of described carbon fluorine oxide is
Figure FDA00002016948300021
wherein, x=1 or 2; Y=1 or 2; Z=1 or 2; N=50 ~ 100;
On described carbon fluorine oxide layer, form outer protective layer; And
Use cap that described luminescent layer, negative electrode, protective layer, metal barrier, carbon fluorine oxide layer and outer protective layer are packaged in described anode conducting substrate.
7. the preparation method of organic electroluminescence device according to claim 1, is characterized in that: adopt the method for vacuum evaporation to form protective layer, the material of wherein said protective layer is CuPc, NPB, Alq3, SiO, MgF 2and at least one in ZnS, vacuum degree is 8 * 10 -5pa ~ 3 * 10 -5pa, evaporation rate is
Figure FDA00002016948300022
thickness is 200nm ~ 300nm.
8. the preparation method of organic electroluminescence device according to claim 1, is characterized in that: adopt the mode of vacuum evaporation to prepare described outer protective layer, the material of described outer protective layer is SiO, and vacuum degree is 8 * 10 -5pa ~ 3 * 10 -5pa, evaporation rate is
Figure FDA00002016948300023
thickness is 100nm ~ 150nm.
9. the preparation method of organic electroluminescence device according to claim 1; it is characterized in that: use cap that described luminescent layer, negative electrode, protective layer, metal barrier, carbon fluorine oxide layer and outer protective layer are packaged in to the suprabasil method of described anode conducting and comprise: at PET film edge coating thickness, be the epoxy encapsulation glue of 1 ~ 1.5 μ m; then the UV light that is 200 ~ 400nm with wavelength by described epoxy encapsulation adhesive curing to described anode conducting substrate, light intensity 10 ~ 15mW/cm 2, time for exposure 300 ~ 400s.
10. the preparation method of organic electroluminescence device according to claim 1, it is characterized in that: adopt vapour deposition method to form described negative electrode, described negative electrode comprises two layer medium layer and is located at the metal level between described two layer medium layer, the material of described dielectric layer is zinc sulphide, tin indium oxide or zinc oxide aluminum, and the material of described metal level is at least one in aluminium, silver and gold.
CN201210290574.8A 2012-08-15 2012-08-15 Organic electroluminescent device and preparation method thereof Pending CN103594647A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110246981A (en) * 2019-06-06 2019-09-17 福仕保(江苏)新材料有限公司 Organic illuminating electronic device encapsulation structure and its production technology
CN110911586A (en) * 2019-12-03 2020-03-24 江苏集萃有机光电技术研究所有限公司 OLED panel, preparation method of OLED panel and display device

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110246981A (en) * 2019-06-06 2019-09-17 福仕保(江苏)新材料有限公司 Organic illuminating electronic device encapsulation structure and its production technology
CN110911586A (en) * 2019-12-03 2020-03-24 江苏集萃有机光电技术研究所有限公司 OLED panel, preparation method of OLED panel and display device
CN110911586B (en) * 2019-12-03 2022-02-18 江苏集萃有机光电技术研究所有限公司 OLED panel, preparation method of OLED panel and display device

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