CN103594644A - Organic electroluminescent device and preparation method thereof - Google Patents

Organic electroluminescent device and preparation method thereof Download PDF

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Publication number
CN103594644A
CN103594644A CN201210290410.5A CN201210290410A CN103594644A CN 103594644 A CN103594644 A CN 103594644A CN 201210290410 A CN201210290410 A CN 201210290410A CN 103594644 A CN103594644 A CN 103594644A
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layer
thickness
negative electrode
coating
electroluminescence device
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周明杰
王平
钟铁涛
张振华
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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
    • H10K50/842—Containers
    • H10K50/8423—Metallic sealing arrangements
    • 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
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/846—Passivation; Containers; Encapsulations comprising getter material or desiccants
    • 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

Abstract

The invention relates to an organic electroluminescent device, comprising an anode conductive substrate, a luminescent layer, a cathode, a protective layer, an oxide layer, an organic barrier layer, a moisture absorption layer and a heat dissipation layer which are sequentially laminated , wherein the oxide layer is made of at least one of SiO2, Al2O3, TiO2, ZrO2, HfO2 and Ta2O5; and the organic barrier layer is made of at least one of polytetrafluoroethylene, methacrylic resin and cycloaliphatic epoxy resin. The organic electroluminescent device further comprises a package cover, wherein the package cover packages the luminescent layer, the cathode, the protective layer, the oxide layer, the organic barrier layer, the moisture absorption layer and the heat dissipation 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, oxide skin(coating), organic barrier layer, moisture absorbed layer and the heat dissipating layer that stack gradually; Wherein,
The material of described oxide skin(coating) is SiO 2, Al 2o 3, TiO 2, ZrO 2, HfO 2and Ta 2o 5in at least one;
The material on described organic barrier layer is at least one in polytetrafluoroethylene, methacrylic resin and cycloaliphatic epoxy resin;
Described organic electroluminescence device also comprises cap, and described cap is packaged in described luminescent layer, negative electrode, protective layer, oxide skin(coating), organic barrier layer, moisture absorbed layer and heat dissipating 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 moisture absorbed layer is at least one in CaO, BaO, SrO and MgO.
In a preferred embodiment, the material of described heat dissipating layer is at least one in aluminium, silver and copper.
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 ald to form oxide skin(coating) on described protective layer, the material of wherein said oxide skin(coating) is SiO 2, Al 2o 3, TiO 2, ZrO 2, HfO 2and Ta 2o 5in at least one, adopt organic substance predecessor as metal or nonmetal source, deionized water is as oxygen source, growth rate is
Figure BDA00002016746100021
thickness is 5nm ~ 20nm;
On described oxide skin(coating), form organic barrier layer, comprise: under inert atmosphere, first at least one in polytetrafluoroethylene, methacrylic resin and cycloaliphatic epoxy resin is spin-coated on described oxide skin(coating), thickness is 1 μ m ~ 1.5 μ m, then adopting wavelength is that the ultraviolet light of 200nm ~ 400nm is cured, and light intensity is 10 ~ 15mW/cm 2, time for exposure 200 ~ 300s;
On described organic barrier layer, form moisture absorbed layer;
On described moisture absorbed layer, form heat dissipating layer; And
Use cap that described luminescent layer, negative electrode, protective layer, oxide skin(coating), organic barrier layer, moisture absorbed layer and heat dissipating 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 BDA00002016746100031
thickness is 200nm ~ 300nm.
In a preferred embodiment, the method that forms described moisture absorbed layer comprises: take in CaO, BaO, SrO, MgO that any one is target, adopt the preparation of vacuum sputtering method to form, base vacuum degree is 2 * 10 -4pa, sputter thickness is 100nm ~ 200nm.
In a preferred embodiment, the method that forms described heat dissipating layer comprises: adopt the method for vacuum evaporation, by least one evaporation in aluminium, silver and copper, to described moisture absorbed layer, vacuum degree is 8 * 10 -5pa ~ 3 * 10 -5pa, evaporation rate is
Figure BDA00002016746100032
thickness is 200nm ~ 500nm
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; Organic barrier layer can cooperatively interact with oxide skin(coating), effectively the corrosion of block water oxygen; Moisture absorbed layer can absorbing moisture, reduces the destruction of moisture to device; 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, oxide skin(coating) 50, organic barrier layer 60, moisture absorbed layer 70 and the heat dissipating layer 80 stacking gradually.Organic electroluminescence device 100 also comprises cap 90, and cap 90 is packaged in functional layer 20, negative electrode 30, protective layer 40, oxide skin(coating) 50, organic barrier layer 60, moisture absorbed layer 70 and heat dissipating layer 80 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.
Oxide skin(coating) 50 is formed at the surface of protective layer 40.The material of oxide skin(coating) 50 is SiO 2, Al 2o 3, TiO 2, ZrO 2, HfO 2and Ta 2o 5in at least one.The thickness of oxide skin(coating) 50 is 5 ~ 20nm.Oxide skin(coating) 50 is as inorganic barrier layer, and compactness is high.
Organic barrier layer 60 is formed at the surface of oxide skin(coating) 50.The material on organic barrier layer 60 is at least one in polytetrafluoroethylene, methacrylic resin and cycloaliphatic epoxy resin.The thickness on organic barrier layer 60 is 1 μ m ~ 1.5 μ m.Organic barrier layer 60 can cooperatively interact with oxide skin(coating) 50, effectively the corrosion of block water oxygen.
Preferably, the number of plies on oxide skin(coating) 50 and organic barrier layer 60 is multilayer, for example, be more than or equal to 3 layers, and these two layers of alternative arrangements, with the 60/ organic barrier layer 60 of oxide skin(coating) 50/, the organic barrier layer of oxide skin(coating) 50/ ... this structural arrangement.
Moisture absorbed layer 70 is formed at the surface on organic barrier layer 60.The material of moisture absorbed layer 70 is at least one in CaO, BaO, SrO and MgO.The thickness of moisture absorbed layer 70 is 100nm ~ 200nm.Moisture absorbed layer 70 can absorbing moisture, reduces the destruction of moisture to device.
Heat dissipating layer 80 is formed at the surface of moisture absorbed layer 70.The material of heat dissipating layer 80 is at least one in aluminium, silver and copper.Adopt metal level to be used as heat dissipating layer, can improve the heat-sinking capability of device, extend device lifetime.
Cap 90 is covered on heat dissipating layer 80.The material of cap 90 is tinsel.The lower surface of cap 90 has been recessed to form host cavity.Functional layer 20, negative electrode 30, protective layer 40, oxide skin(coating) 50, organic barrier layer 60, moisture absorbed layer 70 and heat dissipating layer 80 are all contained in this host cavity.The edge of cap 90 is tightly connected by packaging plastic (not shown) and anode conducting substrate 10, thereby functional layer 20, negative electrode 30, protective layer 40, oxide skin(coating) 50, organic barrier layer 60, moisture absorbed layer 70 and heat dissipating layer 80 are encapsulated in anode conducting substrate 10.Adopt tinsel as cap, can improve the heat-sinking capability 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 organic barrier layer 60 to match with oxide skin(coating) 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 BDA00002016746100061
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 BDA00002016746100063
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 BDA00002016746100071
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 BDA00002016746100072
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
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
Figure BDA00002016746100074
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 BDA00002016746100075
thickness is 200nm ~ 300nm.
The method of step S140, employing ald forms oxide skin(coating) 50 on protective layer 40.
The material of oxide skin(coating) 50 is SiO 2, Al 2o 3, TiO 2, ZrO 2, HfO 2and Ta 2o 5in at least one.While using the method making of ald (ALD), adopt organic substance precursor, for example Si (OC 2h 5) 4, Al (CH 3) 3, TiCl 4, ZrCl 4, HfCl 4, Ta (OC 2h 5) 5deng, as source metal, take deionized water as oxygen source.Growth rate is
Figure BDA00002016746100076
thickness is 5nm ~ 20nm.
Step S150, on oxide skin(coating) 50, form organic barrier layer 60.
The concrete formation step on organic barrier layer 60 is as follows: under inert atmosphere, first at least one in polytetrafluoroethylene, methacrylic resin and cycloaliphatic epoxy resin is spin-coated on described oxide skin(coating), thickness is 1 μ m ~ 1.5 μ m, then adopting wavelength is that the ultraviolet light of 200nm ~ 400nm is cured, and light intensity is 10 ~ 15mW/cm 2, time for exposure 200 ~ 300s.
Preferably, replace repeating step S140, S150 at least three times.
Step S160, on organic barrier layer 60, form moisture absorbed layer 70.
Concrete, take in CaO, BaO, SrO, MgO that any one is target, adopt the preparation of vacuum sputtering method to form moisture absorbed layer 70.Base vacuum degree is 2 * 10 -4pa, sputter thickness is 100nm ~ 200nm.
Step S170, on moisture absorbed layer 70, form heat dissipating layer 80.
Concrete, the method for employing vacuum evaporation forms heat dissipating layer 80 by least one evaporation in aluminium, silver and copper to moisture absorbed layer 70, and vacuum degree is 8 * 10 -5pa ~ 3 * 10 -5pa, evaporation rate is thickness is 200nm ~ 500nm.
Step S180, use cap 90 are encapsulated in functional layer 20, negative electrode 30, protective layer 40, oxide skin(coating) 50, organic barrier layer 60, moisture absorbed layer 70 and heat dissipating layer 80 in anode conducting substrate 10.
The material of cap 90 is tinsel.In cap 90, be formed with host cavity.Thereby cap 90 is covered on heat dissipating layer, 80 surfaces are contained in host cavity by functional layer 20, negative electrode 30, protective layer 40, oxide skin(coating) 50, organic barrier layer 60, moisture absorbed layer 70 and heat dissipating layer 80.
The edge of cap 90 is fixed on anode conducting substrate 10.Edge-coating packaging plastic at cap 90 is tightly connected cap 90 and anode conducting substrate 10, thereby functional layer 20, negative electrode 30, protective layer 40, oxide skin(coating) 50, organic barrier layer 60, moisture absorbed layer 70 and heat dissipating layer 80 are encapsulated in anode conducting substrate 10.In present embodiment, packaging plastic is epoxy encapsulation glue, and the thickness of packaging plastic is 15 μ m ~ 20 μ m, with UV light (λ=365nm), is cured, and light intensity is 10 ~ 15mW/cm 2, the time for exposure is 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 oxide skin(coating) 50 improves with the stacked compactness that makes in organic barrier layer 60, and the two cooperation is the corrosion of block water oxygen effectively; Cap 90 adopts tinsel 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/ (SiO 2/ polytetrafluoroethylene) 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 10 is glass conductive substrates.Conductive substrates 10 has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Preliminary treatment was first carried out to remove the pollutant on substrate 10 surfaces in conductive substrates 10 surfaces before forming functional layer 20, and the oxygen content of carrying out surface active increase conductive substrates 10 surfaces is to improve the work function on conductive substrates 10 surfaces.Be specially, conductive substrates 10 is adopted successively and removes each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB 3).MoO 3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016746100091
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 BDA00002016746100092
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 BDA00002016746100093
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 BDA00002016746100094
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 BDA00002016746100095
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 BDA00002016746100101
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 BDA00002016746100102
thickness 200nm.
4, adopt the method for ald to form oxide skin(coating) on described protective layer.
The material of oxide skin(coating) is SiO 2.Employing ALD(ald) method is made, and organic substance predecessor is Si (OC 2h 5) 4, deionized water is as oxygen source, growth rate
Figure BDA00002016746100103
thickness 5nm.
5, on oxide skin(coating), form organic barrier layer.
The material on organic barrier layer is polytetrafluoroethylene, adopts the technique of first spin coating post-exposure to make, and under inert atmosphere, makes, and gluing thickness 1 μ m, is then cured light intensity 10mW/cm with UV light (λ=365nm) 2, time for exposure 200s.
Replace repeating step 4,5 three three layers of oxide skin(coating) and organic barrier layers with formation alternative arrangement.
6, on organic barrier layer, form moisture absorbed layer.
The material of moisture absorbed layer adopts CaO, uses sputtering method to make, base vacuum degree 2 * 10 -4pa, sputter thickness 100nm.
7, on moisture absorbed layer, form heat dissipating layer.
The material of heat dissipating layer is metallic aluminium.Adopt the method for vacuum evaporation to make, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002016746100104
thickness 200nm.
8, use cap that luminescent layer, negative electrode, protective layer, oxide skin(coating), organic barrier layer, moisture absorbed layer and heat dissipating layer are packaged in described anode conducting substrate.
Edge-coating epoxy encapsulation glue (thickness 15 μ m) at tinsel, is cured light intensity 11mW/cm with UV light (λ=365nm) 2, time for exposure 350s.
Embodiment 2
Preparation structure is: ITO/NPB:MoO 3/ TCTA/TPBI:Ir (ppy) 3/ Bphen/Bphen:CsN 3/ Al/NPB/ (Al 2o 3/ methacrylic resin) 3the organic electroluminescence device of/BaO/Ag/ cap.
1, in conductive substrates, form functional layer.
Conductive substrates 10 is glass conductive substrates.Conductive substrates 10 has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Preliminary treatment was first carried out to remove the pollutant on substrate 10 surfaces in conductive substrates 10 surfaces before forming functional layer 20, and the oxygen content of carrying out surface active increase conductive substrates 10 surfaces is to improve the work function on conductive substrates 10 surfaces.Be specially, conductive substrates 10 is adopted successively and removes each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB 3).MoO 3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016746100111
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 BDA00002016746100112
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 BDA00002016746100113
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 BDA00002016746100114
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 BDA00002016746100115
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 BDA00002016746100116
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 thickness 300nm.
4, adopt the method for ald to form oxide skin(coating) on described protective layer.
The material of oxide skin(coating) is Al 2o 3.Employing ALD(ald) method is made, and organic substance predecessor is Al (CH 3) 3, deionized water is as oxygen source, growth rate
Figure BDA00002016746100122
thickness 20nm.
5, on oxide skin(coating), form organic barrier layer.
The material on organic barrier layer is methacrylic resin, adopts the technique of first spin coating post-exposure to make, and under inert atmosphere, makes, and gluing thickness 1.5 μ m, are then cured light intensity 15mW/cm with UV light (λ=365nm) 2, time for exposure 200s.
Replace repeating step 4,5 three three layers of oxide skin(coating) and organic barrier layers with formation alternative arrangement.
6, on organic barrier layer, form moisture absorbed layer.
The material of moisture absorbed layer adopts BaO, uses sputtering method to make, base vacuum degree 2 * 10 -4pa, sputter thickness 200nm.
7, on moisture absorbed layer, form heat dissipating layer.
The material of heat dissipating layer is argent.Adopt the method for vacuum evaporation to make, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002016746100123
thickness 500nm.
8, use cap that luminescent layer, negative electrode, protective layer, oxide skin(coating), organic barrier layer, moisture absorbed layer and heat dissipating layer are packaged in described anode conducting substrate.
Edge-coating epoxy encapsulation glue (thickness 15 μ m) at tinsel, is cured light intensity 10mW/cm with UV light (λ=365nm) 2, time for exposure 400s.
Embodiment 3
Preparation structure is: ITO/NPB:MoO3/TCTA/TPBI:Ir (ppy) 3/Bphen/Bphen:CsN3/Al/Alq3/ (TiO 2/ cycloaliphatic epoxy resin) 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 10 is glass conductive substrates.Conductive substrates 10 has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Preliminary treatment was first carried out to remove the pollutant on substrate 10 surfaces in conductive substrates 10 surfaces before forming functional layer 20, and the oxygen content of carrying out surface active increase conductive substrates 10 surfaces is to improve the work function on conductive substrates 10 surfaces.Be specially, conductive substrates 10 is adopted successively and removes each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB 3).MoO 3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016746100131
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 BDA00002016746100133
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 BDA00002016746100134
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 BDA00002016746100135
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 BDA00002016746100136
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 BDA00002016746100137
thickness 250nm.
4, adopt the method for ald to form oxide skin(coating) on described protective layer.
The material of oxide skin(coating) is TiO 2.Employing ALD(ald) method is made, and organic substance predecessor is TiCl 4, deionized water is as oxygen source, growth rate
Figure BDA00002016746100138
thickness 10nm.
5, on oxide skin(coating), form organic barrier layer.
The material on organic barrier layer is cycloaliphatic epoxy resin, adopts the technique of first spin coating post-exposure to make, and under inert atmosphere, makes, and gluing thickness 1.2 μ m, are then cured light intensity 11mW/cm with UV light (λ=365nm) 2, time for exposure 230s.
Replace repeating step 4,5 three three layers of oxide skin(coating) and organic barrier layers with formation alternative arrangement.
6, on organic barrier layer, form moisture absorbed layer.
The material of moisture absorbed layer adopts SrO, uses sputtering method to make, base vacuum degree 2 * 10 -4pa, sputter thickness 150nm.
7, on moisture absorbed layer, form heat dissipating layer.
The material of heat dissipating layer is metallic copper.Adopt the method for vacuum evaporation to make, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002016746100141
thickness 300nm.
8, use cap that luminescent layer, negative electrode, protective layer, oxide skin(coating), organic barrier layer, moisture absorbed layer and heat dissipating layer are packaged in described anode conducting substrate.
Edge-coating epoxy encapsulation glue (thickness 15 μ m) at tinsel, is cured light intensity 15mW/cm with UV light (λ=365nm) 2, time for exposure 300s.
Embodiment 4
Preparation structure is: ITO/NPB:MoO 3/ TCTA/TPBI:Ir (ppy) 3/ Bphen/Bphen:CsN 3/ Al/SiO/ (ZrO 2/ polytetrafluoroethylene) 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 10 is glass conductive substrates.Conductive substrates 10 has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Preliminary treatment was first carried out to remove the pollutant on substrate 10 surfaces in conductive substrates 10 surfaces before forming functional layer 20, and the oxygen content of carrying out surface active increase conductive substrates 10 surfaces is to improve the work function on conductive substrates 10 surfaces.Be specially, conductive substrates 10 is adopted successively and removes each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB 3).MoO 3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016746100151
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 BDA00002016746100152
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 BDA00002016746100153
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen 3), CsN 3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
2, on functional layer surface, form negative electrode.
The material of negative electrode is 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 BDA00002016746100156
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 BDA00002016746100157
thickness 200nm.
4, adopt the method for ald to form oxide skin(coating) on described protective layer.
The material of oxide skin(coating) is ZrO 2.Employing ALD(ald) method is made, and organic substance predecessor is ZrCl 4, deionized water is as oxygen source, growth rate
Figure BDA00002016746100158
thickness 10nm.
5, on oxide skin(coating), form organic barrier layer.
The material on organic barrier layer is polytetrafluoroethylene, adopts the technique of first spin coating post-exposure to make, and under inert atmosphere, makes, and gluing thickness 1 μ m, is then cured light intensity 10mW/cm with UV light (λ=365nm) 2, time for exposure 200s.
Replace repeating step 4,5 three three layers of oxide skin(coating) and organic barrier layers with formation alternative arrangement.
6, on organic barrier layer, form moisture absorbed layer.
The material of moisture absorbed layer adopts MgO, uses sputtering method to make, base vacuum degree 2 * 10 -4pa, sputter thickness 100nm.
7, on moisture absorbed layer, form heat dissipating layer.
The material of heat dissipating layer is albronze, and copper aluminium mass ratio is 3:1.Adopt the method for vacuum evaporation to make, vacuum degree 5 * 10 -5pa, evaporation rate thickness 500nm.
8, use cap that luminescent layer, negative electrode, protective layer, oxide skin(coating), organic barrier layer, moisture absorbed layer and heat dissipating layer are packaged in described anode conducting substrate.
Edge-coating epoxy encapsulation glue (thickness 15 μ m) at tinsel, is cured light intensity 11mW/cm with UV light (λ=365nm) 2, time for exposure 350s.
Embodiment 5
Preparation structure is: ITO/NPB:MoO 3/ TCTA/TPBI:Ir (ppy) 3/ Bphen/Bphen:CsN 3/ Al/MgF 2/ (HfO 2/ methacrylic resin) 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 10 is glass conductive substrates.Conductive substrates 10 has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Preliminary treatment was first carried out to remove the pollutant on substrate 10 surfaces in conductive substrates 10 surfaces before forming functional layer 20, and the oxygen content of carrying out surface active increase conductive substrates 10 surfaces is to improve the work function on conductive substrates 10 surfaces.Be specially, conductive substrates 10 is adopted successively and removes each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB 3).MoO 3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
The material of hole transmission layer is 4,4', 4 " tri-(carbazole-9-yl) 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 BDA00002016746100171
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 BDA00002016746100172
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 BDA00002016746100174
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 BDA00002016746100175
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 BDA00002016746100176
thickness 300nm.
4, adopt the method for ald to form oxide skin(coating) on described protective layer.
The material of oxide skin(coating) is HfO 2.Employing ALD(ald) method is made, and organic substance predecessor is HfCl 4, deionized water is as oxygen source, growth rate
Figure BDA00002016746100177
thickness 10nm.
5, on oxide skin(coating), form organic barrier layer.
The material on organic barrier layer is methacrylic resin, adopts the technique of first spin coating post-exposure to make, and under inert atmosphere, makes, and gluing thickness 1.5 μ m, are then cured light intensity 15mW/cm with UV light (λ=365nm) 2, time for exposure 200s.
Replace repeating step 4,5 three three layers of oxide skin(coating) and organic barrier layers with formation alternative arrangement.
6, on organic barrier layer, form moisture absorbed layer.
The material of moisture absorbed layer adopts CaO, uses sputtering method to make, base vacuum degree 2 * 10 -4pa, sputter thickness 200nm.
7, on moisture absorbed layer, form heat dissipating layer.
The material of heat dissipating layer is metallic aluminium.Adopt the method for vacuum evaporation to make, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002016746100181
thickness 300nm.
8, use cap that luminescent layer, negative electrode, protective layer, oxide skin(coating), organic barrier layer, moisture absorbed layer and heat dissipating layer are packaged in described anode conducting substrate.
Edge-coating epoxy encapsulation glue (thickness 15 μ m) at tinsel, is cured light intensity 15mW/cm with UV light (λ=365nm) 2, time for exposure 400s.
Embodiment 6
Preparation structure is: ITO/NPB:MoO 3/ TCTA/TPBI:Ir (ppy) 3/ Bphen/Bphen:CsN 3/ Al/ZnS/ (Ta 2o 5/ cycloaliphatic epoxy resin) 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 10 is glass conductive substrates.Conductive substrates 10 has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Preliminary treatment was first carried out to remove the pollutant on substrate 10 surfaces in conductive substrates 10 surfaces before forming functional layer 20, and the oxygen content of carrying out surface active increase conductive substrates 10 surfaces is to improve the work function on conductive substrates 10 surfaces.Be specially, conductive substrates 10 is adopted successively and removes each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB 3).MoO 3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016746100182
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 BDA00002016746100183
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 BDA00002016746100191
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 BDA00002016746100193
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 BDA00002016746100194
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 BDA00002016746100195
thickness 250nm.
4, adopt the method for ald to form oxide skin(coating) on described protective layer.
The material of oxide skin(coating) is Ta 2o 5.Employing ALD(ald) method is made, and organic substance predecessor is Ta (OC 2h 5) 5, deionized water is as oxygen source, growth rate
Figure BDA00002016746100196
thickness 10nm.
5, on oxide skin(coating), form organic barrier layer.
The material on organic barrier layer is cycloaliphatic epoxy resin, adopts the technique of first spin coating post-exposure to make, and under inert atmosphere, makes, and gluing thickness 1.2 μ m, are then cured light intensity 11mW/cm with UV light (λ=365nm) 2, time for exposure 230s.
Replace repeating step 4,5 three three layers of oxide skin(coating) and organic barrier layers with formation alternative arrangement.
6, on organic barrier layer, form moisture absorbed layer.
The material of moisture absorbed layer adopts BaO, uses sputtering method to make, base vacuum degree 2 * 10 -4pa, sputter thickness 150nm.
7, on moisture absorbed layer, form heat dissipating layer.
The material of heat dissipating layer is argent.Adopt the method for vacuum evaporation to make, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002016746100197
thickness 300nm.
8, use cap that luminescent layer, negative electrode, protective layer, oxide skin(coating), organic barrier layer, moisture absorbed layer and heat dissipating layer are packaged in described anode conducting substrate.
Edge-coating epoxy encapsulation glue (thickness 15 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/NPB/ (Al 2o 3) 3the organic electroluminescence device of/BaO/Ag/ cap.
1, in conductive substrates, form functional layer.
Conductive substrates 10 is glass conductive substrates.Conductive substrates 10 has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Preliminary treatment was first carried out to remove the pollutant on substrate 10 surfaces in conductive substrates 10 surfaces before forming functional layer 20, and the oxygen content of carrying out surface active increase conductive substrates 10 surfaces is to improve the work function on conductive substrates 10 surfaces.Be specially, conductive substrates 10 is adopted successively and removes each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB 3).MoO 3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016746100201
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 BDA00002016746100202
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 BDA00002016746100203
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 BDA00002016746100204
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 BDA00002016746100211
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 BDA00002016746100212
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 BDA00002016746100213
thickness 300nm.
4, adopt the method for ald to form oxide skin(coating) on described protective layer.
The material of oxide skin(coating) is Al 2o 3.Employing ALD(ald) method is made, and organic substance predecessor is Al (CH 3) 3, deionized water is as oxygen source, growth rate
Figure BDA00002016746100214
thickness 20nm.
Repeat this step 3 inferior to form three layers of oxide skin(coating).
5, on 4, form moisture absorbed layer.
The material of moisture absorbed layer adopts BaO, uses sputtering method to make, base vacuum degree 2 * 10 -4pa, sputter thickness 200nm.
6, on moisture absorbed layer, form heat dissipating layer.
The material of heat dissipating layer is argent.Adopt the method for vacuum evaporation to make, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002016746100215
thickness 500nm.
7, use cap that luminescent layer, negative electrode, protective layer, oxide skin(coating), organic barrier layer, moisture absorbed layer and heat dissipating layer are packaged in described anode conducting substrate.
Edge-coating epoxy encapsulation glue (thickness 15 μ m) at tinsel, 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/ (methacrylic resin) 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 10 is glass conductive substrates.Conductive substrates 10 has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Preliminary treatment was first carried out to remove the pollutant on substrate 10 surfaces in conductive substrates 10 surfaces before forming functional layer 20, and the oxygen content of carrying out surface active increase conductive substrates 10 surfaces is to improve the work function on conductive substrates 10 surfaces.Be specially, conductive substrates 10 is adopted successively and removes each Ultrasonic Cleaning of acetone, ethanol, ionized water and ethanol 5min, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB 3).MoO 3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 * 10 -5pa, evaporation rate is
Figure BDA00002016746100221
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 BDA00002016746100223
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 BDA00002016746100224
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 BDA00002016746100225
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 BDA00002016746100226
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 BDA00002016746100227
thickness 300nm.
4, on 3 layers, form organic barrier layer.
The material on organic barrier layer is methacrylic resin, adopts the technique of first spin coating post-exposure to make, and under inert atmosphere, makes, and gluing thickness 1.5 μ m, are then cured light intensity 15mW/cm with UV light (λ=365nm) 2, time for exposure 200s.
Repeat this step 3 inferior to form three layers of organic barrier layer.
5, on organic barrier layer, form moisture absorbed layer.
The material of moisture absorbed layer adopts CaO, uses sputtering method to make, base vacuum degree 2 * 10 -4pa, sputter thickness 200nm.
6, on moisture absorbed layer, form heat dissipating layer.
The material of heat dissipating layer is metallic aluminium.Adopt the method for vacuum evaporation to make, vacuum degree 5 * 10 -5pa, evaporation rate
Figure BDA00002016746100231
thickness 300nm.
7, use cap that luminescent layer, negative electrode, protective layer, oxide skin(coating), organic barrier layer, moisture absorbed layer and heat dissipating layer are packaged in described anode conducting substrate.
Edge-coating epoxy encapsulation glue (thickness 15 μ m) at tinsel, is cured light intensity 15mW/cm with UV light (λ=365nm) 2, time for exposure 400s.
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 9.3 * 10 as can be seen from Table 1 -5g/m 2/ day, the aqueous vapor penetrance (6.4 * 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 8.4×10 -5
Embodiment 2 7.1×10 -5
Embodiment 3 9.3×10 -5
Embodiment 4 8.0×10 -5
Embodiment 5 5.1×10 -5
Embodiment 6 7.7×10 -5
Comparative example 1 3.2×10 -4
Comparative example 2 6.4×10 -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 BDA00002016746100241
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 7512 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, oxide skin(coating), organic barrier layer, moisture absorbed layer and the heat dissipating layer that stack gradually; Wherein,
The material of described oxide skin(coating) is SiO 2, Al 2o 3, TiO 2, ZrO 2, HfO 2and Ta 2o 5in at least one;
The material on described organic barrier layer is at least one in polytetrafluoroethylene, methacrylic resin and cycloaliphatic epoxy resin;
Described organic electroluminescence device also comprises cap, and described cap is packaged in described luminescent layer, negative electrode, protective layer, oxide skin(coating), organic barrier layer, moisture absorbed layer and heat dissipating 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 moisture absorbed layer is at least one in CaO, BaO, SrO and MgO.
4. organic electroluminescence device according to claim 1, is characterized in that, the material of described heat dissipating layer is at least one in aluminium, silver and copper.
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 ald to form oxide skin(coating) on described protective layer, the material of wherein said oxide skin(coating) is SiO 2, Al 2o 3, TiO 2, ZrO 2, HfO 2and Ta 2o 5in at least one, adopt organic substance predecessor as metal or nonmetal source, deionized water is as oxygen source, growth rate is thickness is 5nm ~ 20nm;
On described oxide skin(coating), form organic barrier layer, comprise: under inert atmosphere, first at least one in polytetrafluoroethylene, methacrylic resin and cycloaliphatic epoxy resin is spin-coated on described oxide skin(coating), thickness is 1 μ m ~ 1.5 μ m, then adopting wavelength is that the ultraviolet light of 200nm ~ 400nm is cured, and light intensity is 10 ~ 15mW/cm 2, time for exposure 200 ~ 300s;
On described organic barrier layer, form moisture absorbed layer;
On described moisture absorbed layer, form heat dissipating layer; And
Use cap that described luminescent layer, negative electrode, protective layer, oxide skin(coating), organic barrier layer, moisture absorbed layer and heat dissipating 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 FDA00002016746000021
thickness is 200nm ~ 300nm.
8. the preparation method of organic electroluminescence device according to claim 1, it is characterized in that: the method that forms described moisture absorbed layer comprises: take in CaO, BaO, SrO, MgO that any one is target, adopt the preparation of vacuum sputtering method to form, base vacuum degree is 2 * 10 -4pa, sputter thickness is 100nm ~ 200nm.
9. the preparation method of organic electroluminescence device according to claim 1, it is characterized in that: the method that forms described heat dissipating layer comprises: the method that adopts vacuum evaporation, by at least one evaporation in aluminium, silver and copper, to described moisture absorbed layer, vacuum degree is 8 * 10 -5pa ~ 3 * 10 -5pa, evaporation rate is
Figure FDA00002016746000022
thickness is 200nm ~ 500nm.
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.
CN201210290410.5A 2012-08-15 2012-08-15 Organic electroluminescent device and preparation method thereof Pending CN103594644A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108376747A (en) * 2018-01-31 2018-08-07 云谷（固安）科技有限公司 Organic light-emitting display device and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108376747A (en) * 2018-01-31 2018-08-07 云谷（固安）科技有限公司 Organic light-emitting display device and preparation method thereof

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