[go: up one dir, main page]

CN103594650A - Organic electroluminescent device and preparation method thereof - Google Patents

Organic electroluminescent device and preparation method thereof Download PDF

Info

Publication number
CN103594650A
CN103594650A CN201210290621.9A CN201210290621A CN103594650A CN 103594650 A CN103594650 A CN 103594650A CN 201210290621 A CN201210290621 A CN 201210290621A CN 103594650 A CN103594650 A CN 103594650A
Authority
CN
China
Prior art keywords
layer
thickness
negative electrode
electroluminescence device
organic electroluminescence
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201210290621.9A
Other languages
Chinese (zh)
Inventor
周明杰
王平
钟铁涛
张振华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
Original Assignee
Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Oceans King Lighting Science and Technology Co Ltd, Shenzhen Oceans King Lighting Engineering Co Ltd filed Critical Oceans King Lighting Science and Technology Co Ltd
Priority to CN201210290621.9A priority Critical patent/CN103594650A/en
Publication of CN103594650A publication Critical patent/CN103594650A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/80Constructional details
    • H10K50/84Passivation; Containers; Encapsulations
    • H10K50/842Containers
    • H10K50/8423Metallic sealing arrangements
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/80Constructional details
    • H10K50/84Passivation; Containers; Encapsulations
    • H10K50/844Encapsulations
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/80Constructional details
    • H10K50/84Passivation; Containers; Encapsulations
    • H10K50/846Passivation; Containers; Encapsulations comprising getter material or desiccants
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention relates to an organic electroluminescent device, comprising an anode conductive substrate, a luminescent layer, a cathode, a protective layer, a carbide layer, an organic barrier layer, a moisture absorption layer and a heat dissipation layer which are sequentially laminated, wherein the carbide layer is made of at least one of SiC, WC, TaC, BC, TiC and HfC; 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 carbide 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, carbide lamella, organic barrier layer, moisture absorbed layer and the heat dissipating layer that stack gradually; Wherein,
The material of described carbide lamella is at least one in SiC, WC, TaC, BC, TiC and HfC;
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, carbide lamella, 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 magnetron sputtering to form carbide lamella on described protective layer, the material of wherein said carbide lamella is at least one in SiC, WC, TaC, BC, TiC and HfC, and base vacuum degree is 2 * 10 -4pa, thickness is 80nm ~ 120nm;
On described carbide lamella, 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 carbide lamella, 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, carbide lamella, 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 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 BDA00002016036500031
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 carbide lamella, 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, carbide lamella 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, carbide lamella 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.
Carbide lamella 50 is formed at the surface of protective layer 40.The material of carbide lamella 50 is at least one in SiC, WC, TaC, BC, TiC and HfC.The thickness of carbide lamella 50 is 80 ~ 120nm.Carbide lamella 50 is as inorganic barrier layer, and carbide combines by the higher covalent bond of bond energy, has good corrosion resistance, and its capacity of heat transmission is also stronger.
Organic barrier layer 60 is formed at the surface of carbide lamella 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 carbide lamella 50, effectively the corrosion of block water oxygen.
Preferably, the number of plies on carbide lamella 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 carbide lamella 50/, the organic barrier layer of carbide lamella 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, carbide lamella 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, carbide lamella 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 carbide lamella 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
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 BDA00002016036500062
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 BDA00002016036500063
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 BDA00002016036500071
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 BDA00002016036500072
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 BDA00002016036500073
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 BDA00002016036500075
thickness is 200nm ~ 300nm.
The method of step S140, employing magnetron sputtering forms carbide lamella 50 on protective layer 40.
The material of carbide lamella 50 is at least one in SiC, WC, TaC, BC, TiC and HfC.While using the method making of magnetron sputtering, adopt SiC, WC, TaC, BC, TiC or HfC etc. as target, base vacuum degree is 2 * 10 -4pa, thickness is 80nm ~ 120nm.
Step S150, on carbide lamella 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 carbide lamella, 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
Figure BDA00002016036500081
thickness is 200nm ~ 500nm.
Step S180, use cap 90 are encapsulated in functional layer 20, negative electrode 30, protective layer 40, carbide lamella 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, carbide lamella 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, carbide lamella 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 carbide lamella 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/ (SiC/ 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 BDA00002016036500091
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 BDA00002016036500092
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 BDA00002016036500093
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 BDA00002016036500094
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 BDA00002016036500095
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 BDA00002016036500101
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 BDA00002016036500102
thickness 200nm.
4, adopt the method for magnetron sputtering to form carbide lamella on described protective layer.
The material of carbide lamella is SiC.Adopt the method for magnetron sputtering to make, target is SiC, and base vacuum degree is 2 * 10 -4pa, thickness is 80nm.
5, on carbide lamella, 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 carbide lamella 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 BDA00002016036500103
thickness 200nm.
8, use cap that luminescent layer, negative electrode, protective layer, carbide lamella, 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/ (WC/ 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
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 BDA00002016036500112
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 BDA00002016036500113
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 BDA00002016036500114
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 BDA00002016036500116
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 BDA00002016036500117
thickness 300nm.
4, adopt the method for magnetron sputtering to form carbide lamella on described protective layer.
The material of carbide lamella is WC.Adopt the method for magnetron sputtering to make, target is WC, and base vacuum degree is 2 * 10 -4pa, thickness is 100nm.
5, on carbide lamella, 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 carbide lamella 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 BDA00002016036500121
thickness 500nm.
8, use cap that luminescent layer, negative electrode, protective layer, carbide lamella, 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/ (TaC/ 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 BDA00002016036500131
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 BDA00002016036500132
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 BDA00002016036500133
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 BDA00002016036500134
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 BDA00002016036500135
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 BDA00002016036500136
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 BDA00002016036500137
thickness 250nm.
4, adopt the method for magnetron sputtering to form carbide lamella on described protective layer.
The material of carbide lamella is TaC.Adopt the method for magnetron sputtering to make, target is TaC, and base vacuum degree is 2 * 10 -4pa, thickness is 120nm.
5, on carbide lamella, 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 carbide lamella 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 BDA00002016036500141
thickness 300nm.
8, use cap that luminescent layer, negative electrode, protective layer, carbide lamella, 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/ (BC/ 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 BDA00002016036500151
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 BDA00002016036500152
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 BDA00002016036500153
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 BDA00002016036500154
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 BDA00002016036500155
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 BDA00002016036500156
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 BDA00002016036500157
thickness 200nm.
4, adopt the method for magnetron sputtering to form carbide lamella on described protective layer.
The material of carbide lamella is BC.Adopt the method for magnetron sputtering to make, target is BC, and base vacuum degree is 2 * 10 -4pa, thickness is 80nm.
5, on carbide lamella, 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 carbide lamella 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
Figure BDA00002016036500161
thickness 500nm.
8, use cap that luminescent layer, negative electrode, protective layer, carbide lamella, 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/ (TiC/ 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 BDA00002016036500162
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 BDA00002016036500171
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 BDA00002016036500172
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 BDA00002016036500173
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 BDA00002016036500174
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 BDA00002016036500175
thickness 300nm.
4, adopt the method for magnetron sputtering to form carbide lamella on described protective layer.
The material of carbide lamella is TiC.Adopt the method for magnetron sputtering to make, target is TiC, and base vacuum degree is 2 * 10 -4pa, thickness is 120nm.
5, on carbide lamella, 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 carbide lamella 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 BDA00002016036500181
thickness 300nm.
8, use cap that luminescent layer, negative electrode, protective layer, carbide lamella, 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/ (HfC/ 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 BDA00002016036500182
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 BDA00002016036500183
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 BDA00002016036500184
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 BDA00002016036500192
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 BDA00002016036500193
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 thickness 250nm.
4, adopt the method for magnetron sputtering to form carbide lamella on described protective layer.
The material of carbide lamella is HfC.Adopt the method for magnetron sputtering to make, target is HfC, and base vacuum degree is 2 * 10 -4pa, thickness is 100nm.
5, on carbide lamella, 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 carbide lamella 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 BDA00002016036500195
thickness 300nm.
8, use cap that luminescent layer, negative electrode, protective layer, carbide lamella, 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/MgF 2/ (TiC) 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 BDA00002016036500201
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 BDA00002016036500202
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 BDA00002016036500203
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 BDA00002016036500211
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 BDA00002016036500212
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 BDA00002016036500213
thickness 300nm.
4, adopt the method for magnetron sputtering to form carbide lamella on described protective layer.
The material of carbide lamella is TiC.Adopt the method for magnetron sputtering to make, target is TiC, and base vacuum degree is 2 * 10 -4pa, thickness is 120nm.
Repeat 4 three times.
5, on 4, 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 BDA00002016036500214
thickness 300nm.
7, use cap that luminescent layer, negative electrode, protective layer, carbide lamella, 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.
Comparative example 2
Preparation structure is: ITO/NPB:MoO 3/ TCTA/TPBI:Ir (ppy) 3/ Bphen/Bphen:CsN 3/ Al/ZnS/ (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 BDA00002016036500221
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 BDA00002016036500222
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 BDA00002016036500223
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 BDA00002016036500224
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 BDA00002016036500225
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 BDA00002016036500226
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 BDA00002016036500227
thickness 250nm.
4, on 3, 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.
Repeat 4 three times.
5, 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.
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 BDA00002016036500231
thickness 300nm.
7, use cap that luminescent layer, negative electrode, protective layer, carbide lamella, 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.
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 (3.7 * 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 5.0×10 -5
Embodiment 2 4.4×10 -5
Embodiment 3 5.6×10 -5
Embodiment 4 3.7×10 -5
Embodiment 5 6.5×10 -5
Embodiment 6 5.1×10 -5
Comparative example 1 2.5×10 -4
Comparative example 2 3.7×10 -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 BDA00002016036500241
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 11000 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, carbide lamella, organic barrier layer, moisture absorbed layer and the heat dissipating layer that stack gradually; Wherein,
The material of described carbide lamella is at least one in SiC, WC, TaC, BC, TiC and HfC;
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, carbide lamella, 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 magnetron sputtering to form carbide lamella on described protective layer, the material of wherein said carbide lamella is at least one in SiC, WC, TaC, BC, TiC and HfC, and base vacuum degree is 2 * 10 -4pa, thickness is 80nm ~ 120nm;
On described carbide lamella, 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 carbide lamella, 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, carbide lamella, 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 FDA00002016036400021
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 FDA00002016036400022
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.
CN201210290621.9A 2012-08-15 2012-08-15 Organic electroluminescent device and preparation method thereof Pending CN103594650A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210290621.9A CN103594650A (en) 2012-08-15 2012-08-15 Organic electroluminescent device and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210290621.9A CN103594650A (en) 2012-08-15 2012-08-15 Organic electroluminescent device and preparation method thereof

Publications (1)

Publication Number Publication Date
CN103594650A true CN103594650A (en) 2014-02-19

Family

ID=50084709

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210290621.9A Pending CN103594650A (en) 2012-08-15 2012-08-15 Organic electroluminescent device and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103594650A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104201288A (en) * 2014-09-12 2014-12-10 上海和辉光电有限公司 Organic light-emitting device and displayer comprising same
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 (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104201288A (en) * 2014-09-12 2014-12-10 上海和辉光电有限公司 Organic light-emitting device and displayer comprising same
CN104201288B (en) * 2014-09-12 2017-03-15 上海和辉光电有限公司 Organic electroluminescence device and the display comprising the device
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

Similar Documents

Publication Publication Date Title
CN103855315A (en) Organic light-emitting device and preparation method thereof
CN103594649A (en) Organic electroluminescent device and preparation method thereof
CN103730595A (en) Organic light-emitting device and preparation method thereof
CN103594645A (en) Organic electroluminescent device and preparation method thereof
CN103730594A (en) Organic light-emitting device and preparation method thereof
CN103594650A (en) Organic electroluminescent device and preparation method thereof
CN103594643A (en) Organic electroluminescent device and preparation method thereof
CN103594647A (en) Organic electroluminescent device and preparation method thereof
CN103730593A (en) Organic light-emitting device and preparation method thereof
CN104078595A (en) Organic light-emitting diode and preparation method thereof
CN103855321A (en) Organic light-emitting device and preparation method thereof
CN104103764A (en) Organic light-emitting display and manufacturing method thereof
CN103594644A (en) Organic electroluminescent device and preparation method thereof
CN103855316A (en) Organic light-emitting device and preparation method thereof
CN103855320A (en) Organic light-emitting device and preparation method thereof
CN103855308B (en) A kind of organic electroluminescence device and preparation method thereof
CN104078590A (en) Organic light-emitting diode and preparation method thereof
CN104103768A (en) Organic light-emitting display and manufacturing method thereof
CN104183767A (en) Organic light emitting diode and preparation method thereof
CN103682119A (en) Organic light-emitting device and preparation method thereof
CN103594646A (en) Organic electroluminescent device and preparation method thereof
CN103594638A (en) Organic electroluminescent device and preparation method thereof
CN103427040B (en) Organic electroluminescence device and preparation method thereof
CN103855319B (en) A kind of organic electroluminescence device and preparation method thereof
CN104078587A (en) Organic light-emitting device and fabrication method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20140219