WO2014082300A1 - 一种有机电致发光器件及其制备方法 - Google Patents

一种有机电致发光器件及其制备方法 Download PDF

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WO2014082300A1
WO2014082300A1 PCT/CN2012/085669 CN2012085669W WO2014082300A1 WO 2014082300 A1 WO2014082300 A1 WO 2014082300A1 CN 2012085669 W CN2012085669 W CN 2012085669W WO 2014082300 A1 WO2014082300 A1 WO 2014082300A1
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layer
carbide
nitride
oxide
thickness
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PCT/CN2012/085669
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English (en)
French (fr)
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周明杰
王平
钟铁涛
陈吉星
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海洋王照明科技股份有限公司
深圳市海洋王照明工程有限公司
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Priority to PCT/CN2012/085669 priority Critical patent/WO2014082300A1/zh
Publication of WO2014082300A1 publication Critical patent/WO2014082300A1/zh

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations

Definitions

  • the present invention relates to the field of electronic devices, and in particular, to an organic electroluminescent device and a method for fabricating the same.
  • OLED organic electroluminescent device
  • ITO indium-oxide-semiconductor
  • a metal electrode having a low work function is provided above the light-emitting layer.
  • OLED The device has the advantages of active illumination, high luminous efficiency, low power consumption, lightness, thinness, and no viewing angle limitation. It is considered by the industry to be the next generation device most likely to dominate the future lighting and display device market. As a new lighting and display technology, OLED technology has developed rapidly over the past decade and has achieved great success. As more and more lighting and display manufacturers around the world have invested in research and development, it has greatly promoted the industrialization of OLEDs, making OLEDs The growth rate of the industry is staggering, and it has reached the eve of mass production.
  • a glass cover or a metal cover is used for packaging, and the edges thereof are sealed with an ultraviolet polymer resin, but the glass cover or the metal cover used in this method tends to be bulky, which increases the weight of the device, and the method cannot be applied to flexibility.
  • Packaging of organic electroluminescent devices are used for packaging, and the edges thereof are sealed with an ultraviolet polymer resin, but the glass cover or the metal cover used in this method tends to be bulky, which increases the weight of the device, and the method cannot be applied to flexibility.
  • Packaging of organic electroluminescent devices are used for packaging, and the edges thereof are sealed with an ultraviolet polymer resin, but the glass cover or the metal cover used in this method tends to be bulky, which increases the weight of the device, and the method cannot be applied to flexibility.
  • Packaging of organic electroluminescent devices are used for packaging, and the edges thereof are sealed with an ultraviolet polymer resin, but the glass cover or the metal cover used in this method tends to be bulky, which increases the weight of the device, and the method cannot be applied to flexibility
  • the present invention provides an organic electroluminescent device and a method of fabricating the same.
  • the organic electroluminescent device can effectively reduce the erosion of the organic electroluminescent device by active substances such as water vapor and oxygen, protect the organic functional materials and electrodes of the organic electroluminescent device from damage, and significantly improve the lifetime of the device.
  • the method of the invention is suitable for encapsulating an organic electroluminescent device prepared from a conductive glass substrate.
  • the method of the invention is particularly suitable for packaging flexible organic electroluminescent devices.
  • the present invention provides an organic electroluminescent device
  • the substrate, the anode, the functional layer, the cathode, the encapsulation layer and the encapsulation cover are sequentially stacked, and the substrate and the encapsulation cover form a closed space, and the anode, the functional layer, the cathode and the encapsulation layer are accommodated in the enclosed space, wherein the
  • the encapsulation layer in turn includes a protective layer, an oxynitride film, an organic barrier layer, a moisture absorbing layer, and a heat dissipation layer;
  • the oxynitride film is a nitride film doped with an oxide and a carbide, wherein the oxide material is silicon dioxide, aluminum oxide, zirconium dioxide, hafnium oxide, titanium dioxide or pentoxide ⁇ , the carbide material is silicon carbide, tungsten carbide, tantalum carbide, boron carbide, titanium carbide, tantalum carbide, and the nitride material is silicon nitride, aluminum nitride, boron nitride, silicon nitride, Tantalum nitride or titanium nitride, the mass ratio of the oxide, the carbide to the nitride is 2 to 6 : 1 to 5 : 9 to 17 .
  • the oxynitride film has a thickness of from 100 nm to 150 nm.
  • the material of the protective layer is copper phthalocyanine, N, N'-(1-naphthyl)-N, N'-diphenyl -4,4'-biphenyldiamine, octahydroxyquinoline aluminum, silicon oxide, magnesium fluoride or zinc sulfide, the thickness of the protective layer is 200 nm to 300 nm;
  • the material of the organic barrier layer is polytetrafluoroethylene, methacrylic resin or cycloaliphatic epoxy resin, and the thickness of the organic barrier layer is 1 ⁇ 1.5 ⁇ m.
  • the material of the moisture absorbing layer is calcium oxide, cerium oxide, cerium oxide or magnesium oxide, and the thickness of the moisture absorbing layer is 100 nm. ⁇ 200nm ;
  • the heat dissipating layer is made of aluminum, silver, copper or a combination thereof, and has a thickness of 200 nm to 500 nm;
  • the package cover is a metal foil, and the material of the metal foil is silver, aluminum or copper.
  • the oxynitride film and the organic barrier layer are alternately laminated, and the number of laminated layers is three or more.
  • Another aspect of the invention provides a method of fabricating an organic electroluminescent device, comprising the steps of:
  • anode of an organic electroluminescent device on a clean glass substrate or an organic film substrate; sequentially preparing a functional layer, a cathode and an encapsulation layer on the anode conductive substrate by vacuum evaporation, and encapsulating the package cover by ultraviolet curing Forming a closed space between the substrate and the package cover;
  • the preparation of the encapsulation layer comprises first preparing the protective layer by vacuum evaporation on the cathode;
  • the oxide material is silicon dioxide, aluminum oxide, zirconium dioxide, hafnium oxide, titanium dioxide or pentoxide
  • the nitride material is silicon nitride, aluminum nitride, boron nitride, silicon nitride, tantalum nitride or titanium nitride
  • the carbide material is silicon carbide, tungsten carbide, tantalum carbide, Boron carbide, titanium carbide or tantalum carbide
  • the magnetron sputtering condition is: using a three-target magnetron sputtering deposition system, setting the background vacuum degree to be 1 ⁇ 10 -5 Pa - 1 ⁇ 10 -3 Pa, film layer The thickness is set to be 10 nm to 150 nm, and the mass ratio of the oxide, the carbide to the nitride is 2 to 6:1 to 5:
  • the organic barrier layer on the oxycarbon compound film by a spin coating and post-exposure process, wherein the spin-on-exposure process is performed by spin coating the organic barrier layer material, and then using a wavelength It is cured by UV light from 200nm to 400nm with a light intensity of 10 mW/cm 2 to 15 mW/cm 2 and an exposure time of 200 s to 300 s.
  • the moisture absorption layer is prepared by sputtering on the organic barrier layer, and the heat sink is vacuum-deposited on the moisture absorption layer. ;
  • the metal foil is packaged by the encapsulant to form a package cover, so that the substrate and the package cover form a sealed space, and the anode, the functional layer, the cathode and the encapsulation layer are accommodated in the closed space.
  • the oxynitride film has a thickness of 100 to 150 nm.
  • the material of the protective layer is copper phthalocyanine, N, N'-(1-naphthyl)-N, N'-diphenyl -4,4'-biphenyldiamine, octahydroxyquinoline aluminum, silicon oxide, magnesium fluoride or zinc sulfide, the thickness of the protective layer is 200-300 nm;
  • the material of the organic barrier layer is polytetrafluoroethylene, methacrylic resin or cycloaliphatic epoxy resin, and the thickness of the organic barrier layer is 1 ⁇ 1.5 ⁇ m.
  • the material of the moisture absorbing layer is calcium oxide, cerium oxide, cerium oxide or magnesium oxide, and the thickness of the moisture absorbing layer is 100 nm. ⁇ 200nm.
  • the material of the heat dissipation layer is aluminum, silver, copper or a combination thereof, and the heat dissipation layer has a thickness of 200 to 500 nm. .
  • the package cover is a metal foil, and the material of the metal foil is silver, aluminum or copper.
  • the preparation process of the oxynitride film and the organic barrier layer is repeated, and the oxynitride film and the organic barrier layer are laminated, and the number of layers alternately stacked is 3 or more. .
  • the organic electroluminescent device of the invention can effectively reduce the erosion of the organic electroluminescent device by the active substances such as external water and oxygen, thereby effectively protecting the organic functional materials and the electrodes of the device, and significantly improving the life of the organic electroluminescent device.
  • the water-repellent property (WVTR) is 5.3E -5 g/m 2 ⁇ day and the lifetime is 13,813 hours or more.
  • the organic electroluminescent device material of the invention is cheap, the packaging method is simple, and the preparation is easy, and it is suitable for industrial large-scale production. use.
  • FIG. 1 is a schematic structural view of an organic electroluminescent device of the present invention
  • FIG. 3 is a flow chart showing the preparation of an encapsulation layer of the organic electroluminescent device of the present invention.
  • the present invention provides an organic electroluminescent device 100 comprising a substrate 10 and an anode 20 which are sequentially stacked.
  • the functional layer 30, the cathode 40, the encapsulation layer 50 and the encapsulation cover 60, the substrate 10 and the encapsulation cover 60 form a closed space, and the anode 20, the functional layer 30, the cathode 40 and the encapsulation layer are formed. 50 is packaged in this space.
  • the substrate 10 is a glass substrate or an organic film, and the organic film is specifically: polyethylene terephthalate;
  • an anode 20 is disposed on the substrate 10, and the anode 20 is indium tin oxide;
  • the functional layer 30 is formed on the surface of the anode 20.
  • Functional layer 30 The hole injection layer, the hole transport layer, the light-emitting layer, the electron transport layer, and the electron injection layer which are sequentially stacked are included. It can be understood that the hole injection layer, the hole transport layer, the electron transport layer, and the electron injection layer may be omitted, and the functional layer 30 at this time. Only the luminescent layer is included;
  • the hole injection layer is N,N'-bis(1-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4-4'-diamine (NPB) and doped in NPB Molybdenum oxide (MoO 3 ).
  • the mass percentage of MoO 3 is 30%.
  • the thickness of the hole injection layer is 10 nm;
  • the hole transport layer is 4,4',4''-tris(carbazol-9-yl)triphenylamine (TCTA).
  • the thickness of the hole transport layer is 30nm.
  • the luminescent layer material includes a host material and a guest material doped in the host material.
  • the host material is 1,3,5-tris(1-phenyl-lH-benzimidazol-2-yl)benzene (TPBI), and the guest material is tris(2-phenylpyridine) ruthenium (Ir(ppy) 3 ).
  • the mass percentage of the guest material is 5%.
  • the thickness of the light-emitting layer was 20 nm.
  • the material of the electron transport layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).
  • the thickness of the electron transport layer is 10nm.
  • the material of the electron injecting layer includes Bphen and azide ruthenium (CsN 3 ) doped in Bphen.
  • the mass percentage of CsN 3 is 30%.
  • the thickness of the electron injecting layer was 20 nm.
  • the hole injection layer, the hole transport layer, the light-emitting layer, the electron transport layer, and the electron injection layer may be other materials as needed.
  • a cathode 40 and a cathode 40 are disposed on the functional layer 30. It may be a single layer of metal, which is aluminum, silver and gold; or a laminated transparent cathode, which is ITO/Ag/ITO or ZnS/Ag/ZnS.
  • an encapsulation layer 50 is disposed on the cathode 40, and the encapsulation layer 50 includes a protective layer 501.
  • the protective layer 501 and the material of the protective layer 501 are copper phthalocyanine, N, N'-(1-naphthyl)-N , N'-diphenyl-4,4'-biphenyldiamine, octahydroxyquinoline aluminum, silicon oxide, magnesium fluoride or zinc sulfide, and the protective layer has a thickness of 200 to 300 nm.
  • an oxycarbon compound film 502, an oxynitride film 502, is provided on the protective layer 501.
  • a nitride film doped with an oxide and a carbide wherein the oxide material is silicon dioxide, aluminum oxide, zirconium dioxide, hafnium oxide, titanium dioxide or tantalum pentoxide, the nitride material
  • the carbide material is silicon carbide, tungsten carbide, tantalum carbide, boron carbide, titanium carbide or tantalum carbide
  • the mass ratio of the oxide, the carbide to the nitride is 2 to 6 : 1 to 5 : 9 to 17;
  • the oxycarbon compound film 502 has a thickness of 100 to 150 nm.
  • an organic barrier layer 503, an organic barrier layer 503, is disposed on the surface of the oxycarbon compound film 502.
  • the material is PTFE, methacrylic resin or cycloaliphatic epoxy resin, and the thickness is 1 ⁇ 1.5 ⁇ m.
  • the alternate arrangement of the oxynitride film and the organic barrier layer can extend the water-oxygen permeation path, and alternately set up to compensate for the pores, so that the organic matter and the inorganic matter combine to relieve the stress.
  • a moisture absorbing layer 504 and a moisture absorbing layer 504 are disposed on the surface of the organic barrier layer 503.
  • the material is calcium oxide, cerium oxide, cerium oxide or magnesium oxide, and the thickness is from 100 nm to 200 nm.
  • a heat dissipation layer 505 is disposed on the surface of the moisture absorption layer 504, and the heat dissipation layer 505
  • the material is aluminum, silver, copper or a combination thereof, and has a thickness of 200 to 500 nm.
  • the package cover 60 is used for encapsulation with the substrate 10 as a boundary, so that the substrate 10 and the package cover 60 A sealed space is formed between the above layers in the sealed space, and the package cover 60 is a metal foil including a silver, aluminum or copper foil.
  • the method for preparing the organic electroluminescent device 100 provided by the present invention is as follows according to FIG. 2, and the specific steps include:
  • S101 prepares the anode 20 on the substrate 10 and forms a functional layer 30 on the anode 20.
  • the functional layer 30 includes a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer which are sequentially stacked.
  • the substrate 10 may be a glass substrate or an organic polyethylene terephthalate (PET) film substrate.
  • substrate 10 The anode 20 is prepared and the anode 20 is an ITO layer. The thickness of the ITO layer is from 100 nm to 150 nm.
  • the surface of the substrate 10 is pretreated to remove the substrate before forming the anode 20 and the functional layer 30. Contaminants on the surface and surface activation increase the oxygen content of the surface of the substrate 10 to increase the work function of the surface of the substrate 10. Specifically, the substrate 10 is sequentially ultrasonically cleaned by removing acetone, ethanol, ionized water, and ethanol. 5 min, then dried with nitrogen and oven dried.
  • the material of the hole injection layer includes N,N'-bis(1-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4-4'-diamine ( NPB) and molybdenum oxide (MoO 3 ) doped in NPB.
  • the mass percentage of MoO 3 is 30%.
  • the thickness of the hole injection layer was 10 nm.
  • the hole injection layer was formed by vacuum evaporation, and the degree of vacuum was 3 ⁇ 10 -5 Pa, and the evaporation rate was 0.1 ⁇ / s.
  • the material of the hole transport layer is 4,4',4''-tris(carbazol-9-yl)triphenylamine (TCTA).
  • the thickness of the hole transport layer was 30 nm.
  • the hole transport layer was formed by vacuum evaporation, and the degree of vacuum was 3 ⁇ 10 -5 Pa, and the evaporation rate was 0.1 ⁇ / s.
  • the material of the luminescent layer includes a host material and a guest material doped in the host material.
  • the host material is 1,3,5-tris(1-phenyl-lH-benzimidazol-2-yl)benzene (TPBI), and the guest material is tris(2-phenylpyridine) ruthenium (Ir(ppy) 3 ).
  • the mass percentage of the guest material is 5%.
  • the thickness of the light-emitting layer was 20 nm.
  • the light-emitting layer was formed by vacuum evaporation, and the degree of vacuum was 3 ⁇ 10 -5 Pa, and the evaporation rate was 0.2 ⁇ / s.
  • the material of the electron transport layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).
  • the electron transport layer has a thickness of 10 nm.
  • the electron transport layer was formed by vacuum evaporation, having a degree of vacuum of 3 ⁇ 10 -5 Pa and an evaporation rate of 0.1 ⁇ / s.
  • the material of the electron injecting layer includes Bphen and azide strontium (CsN3) doped in Bphen, and the mass percentage of CsN3 is 30%.
  • the thickness of the electron injecting layer was 20 nm.
  • the electron injecting layer was formed by vacuum evaporation, and the degree of vacuum was 3 ⁇ 10 -5 Pa, and the evaporation rate was 0.2 ⁇ / s.
  • the hole injection layer, the hole transport layer, the light-emitting layer, the electron transport layer, and the electron injection layer may be other materials as needed.
  • the hole injection layer, the hole transport layer, the electron transport layer, and the electron injection layer may be omitted, and the functional layer at this time 20 Includes only the luminescent layer.
  • Step S120 forming a cathode 40 on the surface of the functional layer 30.
  • the cathode 30 may have a single layer structure.
  • the thickness of the cathode 30 is 100 nm.
  • the material of the cathode 30 is aluminum (Al), silver (Ag) or gold (Au), and the cathode 30 is formed by vacuum evaporation, having a degree of vacuum of 5 ⁇ 10 -5 Pa and an evaporation rate of 5 ⁇ / s. It may also be a laminated transparent cathode which is ITO/Ag/ITO or ZnS/Ag/ZnS.
  • Step S130 vapor deposition on the cathode 40 to form an encapsulation layer.
  • the preparation steps of the encapsulation layer are as follows:
  • the encapsulation layer in turn includes a protective layer 501, an oxycarbon compound film 502, an organic barrier layer 503, and a moisture absorbing layer 504. And heat sink 505.
  • Step S1301 vapor deposition on the cathode 40 to form a protective layer 501
  • the material of the protective layer 501 is copper phthalocyanine, N, N'-(1-naphthyl)-N, N'-diphenyl-4, 4'- Biphenyldiamine, octahydroxyquinoline aluminum, silicon oxide, magnesium fluoride or zinc sulfide
  • the thickness of the protective layer is 200 to 300 nm.
  • the evaporation condition is that the degree of vacuum is 8 ⁇ 10 -5 Pa to 3 ⁇ 10 -5 Pa , and the evaporation rate is 0.5 ⁇ / s to 5 ⁇ / s ;
  • a oxynitride film 502 is formed on the protective layer 502 by magnetron sputtering, and the oxynitride film 502 is a nitride film doped with an oxide and a carbide, wherein the oxide material is two Silica, trialumina, zirconia, ceria, titania or tantalum pentoxide, said nitride material being silicon nitride, aluminum nitride, boron nitride, silicon nitride, tantalum nitride or Titanium nitride, the carbide material is silicon carbide, tungsten carbide, tantalum carbide, boron carbide, titanium carbide or tantalum carbide, and the mass ratio of the oxide, the carbide to the nitride is 2 to 6: 1 to 5 : 9 to 17 .
  • the oxide material is two Silica, trialumina, zirconia, ceria, titania or tantalum pentoxide
  • the magnetron sputtering condition is: using a three-target magnetron sputtering deposition system, setting the background vacuum degree to be 1 ⁇ 10 -5 Pa to 1 ⁇ 10 -3 Pa, and the film layer thickness is set to 80 nm to 150 nm,
  • the mass ratio of the oxide, the carbide to the nitride is 2 to 6:1 to 5:9 to 17 as a target, and the sputtering is performed at a sputtering rate of 5 nm/min to 40 nm/min to obtain oxygen.
  • Step S1303 spin-coating the organic barrier layer 503 on the oxycarbon compound film 502, and then curing by ultraviolet light under an inert atmosphere, the ultraviolet curing condition is a wavelength of 200 nm to 400 nm, and the light intensity is 10 mW/cm 2 to 15 mW/cm. 2 , the exposure time is 200 s to 300 s, and the thickness of the organic barrier layer 503 is 1 ⁇ m to 1.5 ⁇ m;
  • Step S1304 a moisture absorbing layer 504 is prepared on the organic barrier layer 503 by sputtering, and the material of the moisture absorbing layer 504 is calcium oxide, cerium oxide, cerium oxide or magnesium oxide, and has a thickness of 100 nm to 200 nm.
  • the sputtering condition is that the sputtering method is specifically a degree of vacuum of 1 ⁇ 10 -5 Pa to 1 ⁇ 10 -3 Pa and a vapor deposition rate of 1 ⁇ to 5 ⁇ /s;
  • Step S1305 a heat dissipation layer 505 is prepared on the moisture absorption layer 504 by evaporation, and the heat dissipation layer 505 is made of aluminum, silver, copper or a combination thereof, and has a thickness of 200 nm to 500 nm.
  • the evaporation condition is that the degree of vacuum is 8 ⁇ 10 -5 Pa to 3 ⁇ 10 -5 Pa, and the evaporation rate is 1 ⁇ / s to 5 ⁇ / s;
  • the stacked oxynitride film is prepared by alternately repeating steps S1303 and S1304. 502 and an organic barrier layer 503, the number of alternately stacked layers is 3 or more layers;
  • Step S140 forming a package cover 60 on the surface of the encapsulation layer 50.
  • the package encapsulant is applied on the edge of the package cover, and the encapsulant is hardened by ultraviolet curing and drying.
  • the ultraviolet light has a wavelength of 200 nm to 400 nm, the light intensity is 10 mW/cm 2 to 15 mW/cm 2 , and the exposure time is 300 s to 400 s.
  • a sealed space is formed between the package cover 60 and the substrate 10.
  • a method for preparing an organic electroluminescent device comprising the steps of:
  • substrate pretreatment and anode preparation acetone, ethanol, deionized water and ethanol are used for cleaning by ultrasonic cleaning machine.
  • the washing time is 5 for each washing. After a minute, it is blown dry with nitrogen, dried in an oven and used for later use; ITO glass is placed on the substrate, and the substrate loaded with ITO glass is subjected to surface activation treatment to increase the oxygen content of the surface layer and improve the work function of the anode surface. ;
  • the thickness of the ITO glass is 100 nm;
  • the material of the hole injection layer includes N,N'-bis(1-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4-4'-diamine (NPB) and doping Molybdenum oxide (MoO 3 ) in NPB.
  • the mass percentage of MoO 3 is 30%.
  • the thickness of the hole injection layer was 10 nm.
  • the hole injection layer was formed by vacuum evaporation, and the degree of vacuum was 3 ⁇ 10 -5 Pa, and the evaporation rate was 0.1 ⁇ / s. ;
  • the material of the hole transport layer is 4,4',4''-tris(carbazol-9-yl)triphenylamine (TCTA).
  • the thickness of the hole transport layer was 30 nm.
  • the hole transport layer was formed by vacuum evaporation, and the degree of vacuum was 3 ⁇ 10 -5 Pa, and the evaporation rate was 0.1 ⁇ / s.
  • the material of the luminescent layer includes a host material and a guest material doped in the host material.
  • the host material is 1,3,5-tris(1-phenyl-lH-benzimidazol-2-yl)benzene (TPBI), and the guest material is tris(2-phenylpyridine) ruthenium (Ir(ppy) 3 ).
  • the mass percentage of the guest material is 5%.
  • the thickness of the light-emitting layer was 20 nm.
  • the light-emitting layer was formed by vacuum evaporation, and the degree of vacuum was 3 ⁇ 10 -5 Pa, and the evaporation rate was 0.2 ⁇ / s.
  • the material of the electron transport layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).
  • the electron transport layer has a thickness of 10 nm.
  • the electron transport layer was formed by vacuum evaporation, having a degree of vacuum of 3 ⁇ 10 -5 Pa and an evaporation rate of 0.1 ⁇ / s.
  • the material of the electron injecting layer includes Bphen and azide strontium (CsN 3 ) doped in Bphen, and the mass percentage of CsN 3 is 30%.
  • the thickness of the electron injecting layer was 20 nm.
  • the electron injecting layer was formed by vacuum evaporation, and the degree of vacuum was 3 ⁇ 10 -5 Pa, and the evaporation rate was 0.2 ⁇ / s.
  • the metal cathode is made of aluminum (Al), the thickness is 100 nm, the vapor deposition vacuum is 5 ⁇ 10 -5 Pa, and the evaporation rate is 5 ⁇ /s;
  • the encapsulation layer comprising a protective layer, an oxycarbon compound film, an organic barrier layer, a moisture absorption layer and a heat dissipation layer;
  • a protective layer was formed by vapor deposition on the cathode, and the material of the protective layer was copper phthalocyanine, and the thickness of the protective layer was 200 nm.
  • the evaporation condition is that the degree of vacuum is 3 ⁇ 10 -5 Pa and the evaporation rate is 0.5 ⁇ / s;
  • An oxynitride film is formed by magnetron sputtering on the protective layer, and the oxynitride film is a nitride film doped with an oxide and a carbide, wherein the oxide material is silicon dioxide and the nitride material is four. Silicon nitride, the carbide material is silicon carbide, and the mass ratio of oxide, carbide and nitride is 4:3:13.
  • the magnetron sputtering conditions are: using a three-target magnetron sputtering deposition system, setting the background vacuum to 1 ⁇ 10 -5 Pa, the film thickness is set to 120 nm, and the sputtering rate is 5 nm/min for magnetic control.
  • An oxygen-oxygen carbon compound film was obtained by sputtering.
  • the organic barrier layer is spin-coated on the oxycarbon compound film, the organic barrier layer material is polytetrafluoroethylene, and then cured by ultraviolet light under an inert atmosphere, and the ultraviolet curing condition is a wavelength of 365 nm, a light intensity of 10 mW/cm 2 , and an exposure time. 200 s, the thickness of the organic barrier layer is 1 ⁇ m;
  • the oxycarbon compound film and the organic barrier layer are alternately prepared three times;
  • a moisture absorbing layer was prepared by sputtering on the organic barrier layer, and the material of the moisture absorbing layer was calcium oxide having a thickness of 200 nm.
  • the sputtering condition is that the sputtering method is specifically a vacuum degree of 2 ⁇ 10 ⁇ 4 Pa and a vapor deposition rate of 5 ⁇ /s;
  • the heat dissipation layer is prepared by vapor deposition on the moisture absorption layer, and the heat dissipation layer is made of aluminum and has a thickness of 200 nm.
  • the evaporation condition is that the degree of vacuum is 5 ⁇ 10 -5 Pa and the evaporation rate is 1 ⁇ / s;
  • the package encapsulant is coated on the edge of the package cover, and the encapsulant is hardened by ultraviolet curing and drying.
  • the ultraviolet light has a wavelength of 365 nm, the light intensity is 11 mW/cm 2 , and the exposure time is 350 s, so that a sealed space is formed between the package cover and the substrate.
  • a method for preparing an organic electroluminescent device comprising the steps of:
  • the encapsulation layer comprising a protective layer, an oxycarbon compound film, an organic barrier layer, a moisture absorption layer and a heat dissipation layer;
  • a protective layer is formed on the cathode by vapor deposition.
  • the material of the protective layer is N, N'-(1-naphthyl)-N, N'-diphenyl-4,4'-biphenyldiamine, and the thickness of the protective layer is 300nm.
  • the evaporation condition is that the degree of vacuum is 3 ⁇ 10 -5 Pa and the evaporation rate is 5 ⁇ / s;
  • An oxynitride film is formed by magnetron sputtering on the protective layer, and the oxynitride film is a nitride film doped with an oxide and a carbide, wherein the oxide material is trialumina and the nitride material is nitrogen.
  • the carbide material is tungsten carbide, and the mass ratio of oxide, carbide and nitride is 2:1:17.
  • the magnetron sputtering conditions are: using a three-target magnetron sputtering deposition system, setting the background vacuum to 2 ⁇ 10 -4 Pa, the film thickness is set to 100 nm, and the sputtering rate is 1 nm/min. Controlled sputtering to obtain an oxynitride film.
  • the organic barrier layer is spin-coated on the oxycarbon compound film, the organic barrier layer material is methacrylic resin, and then cured by ultraviolet light under an inert atmosphere, and the ultraviolet curing condition is a wavelength of 365 nm, a light intensity of 15 mW/cm 2 , and an exposure time. 200 s, the thickness of the organic barrier layer is 1.5 ⁇ m;
  • the oxycarbon compound film and the organic barrier layer are alternately prepared three times;
  • a moisture absorbing layer was prepared by sputtering on the organic barrier layer, and the material of the moisture absorbing layer was cerium oxide and the thickness was 200 nm.
  • the sputtering condition is that the sputtering method is specifically a vacuum degree of 2 ⁇ 10 ⁇ 4 Pa and a vapor deposition rate of 5 ⁇ /s;
  • the heat dissipation layer is prepared by vapor deposition on the moisture absorption layer, and the heat dissipation layer is made of silver and has a thickness of 500 nm.
  • the evaporation condition is that the degree of vacuum is 5 ⁇ 10 -5 Pa and the evaporation rate is 5 ⁇ / s;
  • the package encapsulant is coated on the edge of the encapsulation cover.
  • the encapsulation cover is made of aluminum foil.
  • the encapsulation adhesive is hardened by ultraviolet curing.
  • the ultraviolet wavelength is 365 nm
  • the light intensity is 10 mW/cm 2
  • the exposure time is 400 s.
  • a sealed space is formed between the substrate and the substrate.
  • a method for preparing an organic electroluminescent device comprising the steps of:
  • the encapsulation layer comprising a protective layer, an oxycarbon compound film, an organic barrier layer, a moisture absorption layer and a heat dissipation layer;
  • a protective layer was formed by vapor deposition on the cathode, and the material of the protective layer was octahydroxyquinoline aluminum, and the thickness of the protective layer was 250 nm.
  • the evaporation condition is that the degree of vacuum is 3 ⁇ 10 -5 Pa and the evaporation rate is 2 ⁇ / s;
  • An oxynitride film is formed by magnetron sputtering on the protective layer, and the oxynitride film is a nitride film doped with an oxide and a carbide, wherein the oxide material is titanium dioxide and the nitride material is boron nitride.
  • the carbide material is niobium carbide, and the mass ratio of oxide, carbide to nitride is 6:5:9.
  • the magnetron sputtering conditions are: using a three-target magnetron sputtering deposition system, setting the background vacuum to 2 ⁇ 10 -4 Pa, the film thickness is set to 150 nm, and the sputtering rate is 40 nm/min. Controlled sputtering to obtain an oxynitride film.
  • the organic barrier layer is spin-coated on the oxynitride film, the organic barrier layer material is a ring-fat epoxy resin, and then cured by ultraviolet light under an inert atmosphere, the ultraviolet curing condition is a wavelength of 365 nm, the light intensity is 11 mW/cm 2 , and the exposure is performed.
  • the time is 230 s, and the thickness of the organic barrier layer is 1.2 ⁇ m;
  • the oxycarbon compound film and the organic barrier layer are alternately prepared four times;
  • a moisture absorbing layer was prepared by sputtering on the organic barrier layer, and the material of the moisture absorbing layer was cerium oxide having a thickness of 150 nm.
  • the sputtering condition is that the sputtering method is specifically a vacuum degree of 2 ⁇ 10 ⁇ 4 Pa and a vapor deposition rate of 5 ⁇ /s;
  • the heat dissipation layer is prepared by vapor deposition on the moisture absorption layer, and the heat dissipation layer is made of copper and has a thickness of 300 nm.
  • the evaporation condition is that the degree of vacuum is 5 ⁇ 10 -5 Pa and the evaporation rate is 2 ⁇ / s;
  • the package encapsulant is coated on the edge of the encapsulation cover.
  • the encapsulation cover is made of copper foil.
  • the encapsulation adhesive is hardened by ultraviolet curing and drying.
  • the ultraviolet light has a wavelength of 365 nm, the light intensity is 15 mW/cm 2 , and the exposure time is 300 s.
  • a sealed space is formed between the substrate and the substrate.
  • a method for preparing an organic electroluminescent device comprising the steps of:
  • the encapsulation layer comprising a protective layer, an oxycarbon compound film, an organic barrier layer, a moisture absorption layer and a heat dissipation layer;
  • a protective layer was formed by vapor deposition on the cathode, and the material of the protective layer was silicon oxide, and the thickness of the protective layer was 200 nm.
  • the evaporation condition is that the degree of vacuum is 5 ⁇ 10 -5 Pa and the evaporation rate is 0.5 ⁇ / s;
  • An oxynitride film is formed by magnetron sputtering on the protective layer, and the oxynitride film is a nitride film doped with an oxide and a carbide, wherein the oxide material is zirconium dioxide and the nitride material is nitrogen. Silicon, the carbide material is boron carbide, and the mass ratio of oxide, carbide and nitride is 2:1:7.
  • the magnetron sputtering conditions are: using a three-target magnetron sputtering deposition system, setting the background vacuum to 2 ⁇ 10 -4 Pa, the film thickness is set to 130 nm, and the sputtering rate is 20 nm/min. Controlled sputtering to obtain an oxynitride film.
  • the organic barrier layer is spin-coated on the oxycarbon compound film, the organic barrier layer material is polytetrafluoroethylene, and then cured by ultraviolet light under an inert atmosphere, and the ultraviolet curing condition is a wavelength of 365 nm, a light intensity of 10 mW/cm 2 , and an exposure time. 200 s, the thickness of the organic barrier layer is 1 ⁇ m;
  • the oxycarbon carbon compound film and the organic barrier layer are alternately prepared five times;
  • a moisture absorbing layer was prepared by sputtering on the organic barrier layer, and the material of the moisture absorbing layer was magnesium oxide having a thickness of 100 nm.
  • the sputtering condition is that the sputtering method is specifically a vacuum degree of 2 ⁇ 10 ⁇ 4 Pa and a vapor deposition rate of 5 ⁇ /s;
  • the heat dissipation layer is prepared by vapor deposition on the moisture absorption layer, and the material of the heat dissipation layer is copper aluminum alloy.
  • the mass ratio of copper to aluminum is 3:1 and the thickness is 500 nm.
  • the evaporation condition is that the degree of vacuum is 5 ⁇ 10 -5 Pa and the evaporation rate is 2 ⁇ / s;
  • the package encapsulant is coated on the edge of the package cover.
  • the encapsulation cover is made of copper foil.
  • the encapsulation adhesive is cured by ultraviolet curing and drying.
  • the ultraviolet light has a wavelength of 365 nm, the light intensity is 11 mW/cm 2 , and the exposure time is 350 s.
  • a sealed space is formed between the substrate and the substrate.
  • a method for preparing an organic electroluminescent device comprising the steps of:
  • the encapsulation layer comprising a protective layer, an oxycarbon compound film, an organic barrier layer, a moisture absorption layer and a heat dissipation layer;
  • a protective layer was formed by vapor deposition on the cathode, and the material of the protective layer was magnesium fluoride, and the thickness of the protective layer was 300 nm.
  • the evaporation condition is that the degree of vacuum is 5 ⁇ 10 -5 Pa and the evaporation rate is 5 ⁇ / s;
  • An oxynitride film is formed by magnetron sputtering on the protective layer, and the oxynitride film is a nitride film doped with an oxide and a carbide, wherein the oxide material is cerium oxide and the nitride material is nitrogen. ⁇ , the carbide material is talking titanium, the mass ratio of oxide, carbide and nitride is 1:1:3.
  • the magnetron sputtering conditions are: using a three-target magnetron sputtering deposition system, setting the background vacuum to 2 ⁇ 10 -4 Pa, the film thickness is set to 140 nm, and the sputtering rate is 1 nm/min. Controlled sputtering to obtain an oxynitride film.
  • the organic barrier layer is spin-coated on the oxycarbon compound film, the organic barrier layer material is methacrylic resin, and then cured by ultraviolet light under an inert atmosphere, and the ultraviolet curing condition is a wavelength of 365 nm, a light intensity of 15 mW/cm 2 , and an exposure time. 200 s, the thickness of the organic barrier layer is 1.5 ⁇ m;
  • a moisture absorbing layer was prepared by sputtering on the organic barrier layer, and the material of the moisture absorbing layer was calcium oxide having a thickness of 200 nm.
  • the sputtering condition is that the sputtering method is specifically a vacuum degree of 2 ⁇ 10 ⁇ 4 Pa and a vapor deposition rate of 5 ⁇ /s;
  • the heat dissipation layer is prepared by vapor deposition on the moisture absorption layer, and the material of the heat dissipation layer is copper aluminum alloy.
  • the mass ratio of copper to aluminum is 3:1 and the thickness is 500 nm.
  • the evaporation condition is that the degree of vacuum is 5 ⁇ 10 -5 Pa and the evaporation rate is 2 ⁇ / s;
  • the package encapsulant is coated on the edge of the encapsulation cover.
  • the encapsulation cover is made of copper foil.
  • the encapsulant is hardened by ultraviolet curing and drying.
  • the ultraviolet light has a wavelength of 365 nm, the light intensity is 15 mW/cm 2 , and the exposure time is 400 s.
  • a sealed space is formed between the substrate and the substrate.
  • a method for preparing an organic electroluminescent device comprising the steps of:
  • the encapsulation layer comprising a protective layer, an oxycarbon compound film, an organic barrier layer, a moisture absorption layer and a heat dissipation layer;
  • a protective layer was formed by vapor deposition on the cathode, and the material of the protective layer was zinc sulfide, and the thickness of the protective layer was 250 nm.
  • the evaporation condition is that the degree of vacuum is 5 ⁇ 10 -5 Pa and the evaporation rate is 2 ⁇ / s;
  • An oxynitride film is formed by magnetron sputtering on the protective layer, and the oxynitride film is a nitride film doped with an oxide and a carbide, wherein the oxide material is tantalum pentoxide, and the nitride material is Titanium nitride, the carbide material is niobium carbide, and the mass ratio of oxide, carbide and nitride is 1:1:3.
  • the magnetron sputtering conditions are: using a three-target magnetron sputtering deposition system, setting the background vacuum to 2 ⁇ 10 -4 Pa, the film thickness is set to 120 nm, and the sputtering rate is 5 nm/min. Controlled sputtering to obtain an oxynitride film.
  • the organic barrier layer is spin-coated on the oxynitride film, the organic barrier layer material is a ring-fat epoxy resin, and then cured by ultraviolet light under an inert atmosphere, the ultraviolet curing condition is a wavelength of 365 nm, the light intensity is 11 mW/cm 2 , and the exposure is performed.
  • the time is 230 s, and the thickness of the organic barrier layer is 1.2 ⁇ m;
  • a moisture absorbing layer was prepared by sputtering on the organic barrier layer, and the material of the moisture absorbing layer was cerium oxide having a thickness of 150 nm.
  • the sputtering condition is that the sputtering method is specifically a vacuum degree of 2 ⁇ 10 ⁇ 4 Pa and a vapor deposition rate of 5 ⁇ /s;
  • the heat dissipation layer is prepared by vapor deposition on the moisture absorption layer, and the heat dissipation layer is made of silver and has a thickness of 300 nm.
  • the evaporation condition is that the degree of vacuum is 5 ⁇ 10 -5 Pa and the evaporation rate is 3 ⁇ / s;
  • the package encapsulant is coated on the edge of the package cover.
  • the encapsulation cover is made of copper foil.
  • the encapsulation adhesive is cured by ultraviolet curing and drying.
  • the ultraviolet light has a wavelength of 365 nm, the light intensity is 11 mW/cm 2 , and the exposure time is 350 s.
  • a sealed space is formed between the substrate and the substrate.
  • test conditions for water oxygen permeability of organic electroluminescent devices are: Equipment: Keithley 2400 of Keithley , sample holder; method: test the change of Ca film resistance; conditions: temperature 20-25 ° C, humidity 40% ⁇ 60%.
  • the results are as follows:
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example 6 WVTR(g/m 2 /day) 4.4 E -5 3.1 E -5 5.3 E -5 4.0 E -5 2.1 E -5 3.7 E -5
  • Table 1 shows the water oxygen permeability of the organic electroluminescent devices of Examples 1 to 6, so that the water resistance (WVTR) reached 5.3E -5 g/m 2 ⁇ day .
  • the organic electroluminescent device life testing conditions Equipment: Keithley Keithley2400, Konica Minolta colorimeter CS-100A; Method: Test luminance from 1000cd / m 2 down to the time used 700cd / m 2 ; Conditions: temperature 20-25 ° C, humidity 40% ⁇ 60%.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example 6 Life (ten thousand hours) ( T70@1000cd/m2 ) 1.3001 1.3411 1.2812 1.3114 1.3813 1.3305
  • Table 2 shows the lifespan of the organic electroluminescent devices of Examples 1 to 6. It can be seen that the lifetime of the organic electroluminescent device of the present invention is more than 130.13 million hours (T70@1000 cd/m 2 ).
  • the organic electroluminescent device provided by the invention can effectively reduce the erosion of the organic electroluminescent device by external water, oxygen and other active substances, thereby forming an effective protection for the organic functional material and the electrode of the device, and satisfying the sealing property of the package. Requirements can be significantly improved The lifetime of OLED devices.

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Abstract

一种有机电致发光器件（100），包括依次层叠的基板（10）、阳极（20）、功能层（30）、阴极（40）、封装层（50）及封装盖（60），基板（10）和封装盖（60）形成封闭空间，阳极（20）、功能层（30）、阴极（40）和封装层（50）容置在该封闭空间内，封装层（50）依次包括保护层（501）、氧氮碳化合物膜（502）、有机阻挡层（503）、湿气吸收层（504）和散热层（505）；氧氮碳化合物膜（502）为掺杂有氧化物和碳化物的氮化物膜。还提供了该有机电致发光器件（100）的制备方法，该方法可有效地减少水汽、氧对有机电致发光器件的侵蚀，从而对有机功能材料及电极形成有效的保护，显著提高有机电致发光器件的寿命。该方法尤其适用于封装柔性有机电致发光器件。

Description

一种有机电致发光器件及其制备方法 技术领域
本发明涉及电子器件相关领域，尤其涉及一种有机电致发光器件及其制备方法。
背景技术
有机电致发光器件（ OLED ）是基于有机材料的一种电流型半导体发光器件。其典型结构是在 ITO 玻璃上制备几十纳米厚的有机发光材料作发光层，发光层上方有低功函数的金属电极。当电极上加有电压时，发光层就产生光辐射。
OLED 器件具有主动发光、发光效率高、功耗低、轻、薄、无视角限制等优点，被业内人士认为是最有可能在未来的照明和显示器件市场上占据霸主地位的新一代器件。作为一项崭新的照明和显示技术， OLED 技术在过去的十多年里发展迅猛，取得了巨大的成就。由于全球越来越多的照明和显示厂家纷纷投入研发，大大的推动了 OLED 的产业化进程，使得 OLED 产业的成长速度惊人，目前已经到达了大规模量产的前夜。
传统技术中采用玻璃盖或金属盖进行封装，其边沿用紫外聚合树脂密封，但这种方法中使用的玻璃盖或金属盖体积往往较大，增加了器件的重量，并且该方法不能应用于柔性有机电致放光器件的封装。
 发明内容
为克服上述现有技术的缺陷，本发明提供了一种有机电致发光器件及其制备方法。该有机电致发光器件可有效地减少水汽、氧等活性物质对有机电致发光器件的侵蚀，保护有机电致发光器件的有机功能材料和电极免遭破坏，对器件的寿命有显著的提高。本发明方法适用于封装以导电玻璃基板制备的有机电致发光器件。本发明方法尤其适用于封装柔性有机电致发光器件。
一方面，本发明提供了一种有机电致发光器件，
包括依次层叠的基板、阳极、功能层、阴极、封装层和封装盖，基板和封装盖形成封闭空间，阳极、功能层、阴极、封装层容置在该封闭空间内，其特征在于，所述封装层依次包括保护层、氧氮碳化合物膜、有机阻挡层、湿气吸收层和散热层；
所述氧氮碳化合物膜为掺杂有氧化物和碳化物的氮化物膜，其中，所述氧化物材料为二氧化硅、三氧化铝、二氧化锆、二氧化铪、二氧化钛或五氧化二钽，所述碳化物材料为碳化硅、碳化钨、碳化钽、碳化硼、碳化钛、碳化铪，所述氮化物材料为四氮化三硅、氮化铝、氮化硼、氮化硅、氮化钽或氮化钛，所述氧化物、所述碳化物与所述氮化物的质量比为 2 ～ 6 ： 1 ～ 5 ： 9 ～ 17 。
优选地，所述氧氮碳化合物膜的厚度为 100 nm ～ 150 nm 。
优选地，所述保护层的材料为酞菁铜、 N ， N'- （ 1- 萘基） - N ， N'- 二苯基 -4,4'- 联苯二胺、八羟基喹啉铝、氧化硅、氟化镁或硫化锌，保护层的厚度为 200 nm ～ 300nm ；
所述有机阻挡层的材料为聚四氟乙烯、甲基丙烯酸树脂或环脂肪环氧树脂，所述有机阻挡层的厚度为 1 ～ 1.5µm 。
优选地，所述湿气吸收层的材料为氧化钙、氧化钡、氧化锶或氧化镁，所述湿气吸收层的厚度为 100nm ～ 200nm ；
所述散热层的材料为铝、银、铜或他们的组合物，厚度为 200nm ～ 500nm ；及
所述封装盖为金属薄片，金属薄片的材料为银、铝或铜。
优选地，所述氧氮碳化合物膜与所述有机阻挡层交替层叠设置，层叠层数大于等于三层。
本发明另一方面提供一种有机电致发光器件的制备方法，包括以下步骤：
在洁净的玻璃基板或有机薄膜基板上制备有机电致发光器件的阳极；采用真空蒸镀的方法在阳极导电基板上依次制备功能层、阴极和封装层，采用紫外光固化方式将封装盖进行封装，使所述基板和所述封装盖形成封闭空间；
所述封装层的制备包括首先在阴极上采用真空蒸镀的方式制备所述保护层；
在所述保护层上采用磁控溅射共溅制备所述氧氮碳化合物膜，其中，所述氧化物材料为二氧化硅、三氧化铝、二氧化锆、二氧化铪、二氧化钛或五氧化二钽，所述氮化物材料为四氮化三硅、氮化铝、氮化硼、氮化硅、氮化钽或氮化钛，所述碳化物材料为碳化硅、碳化钨、碳化钽、碳化硼、碳化钛或碳化铪，所述磁控溅射条件为：采用三靶磁控溅射沉积***，设置本底真空度为 1 × 10-5Pa ～ 1 × 10-3Pa ，膜层厚度设置为 10 0nm ～ 150nm ，将所述氧化物、所述碳化物与所述氮化物的质量比为 2 ～ 6 ： 1 ～ 5 ： 9 ～ 17 作为靶材，在溅射速率为 5nm/mi n ～ 40nm/min 条件下进行磁控溅射得到氧氮碳化合物膜；
然后在所述氧氮碳化合物膜上采用先旋涂后曝光的工艺制备所述有机阻挡层，所述先旋涂后曝光的工艺过程为，将所述有机阻挡层材料旋涂，然后用波长为 200nm ～ 400nm 紫外光固化，光强为 10 mW/cm2 ～ 15 mW/cm2 ， 曝光时间 200 s ～ 300s ；
接着在所述有机阻挡层上采用溅射方式制备所述湿气吸收层，在所述湿气吸收层上真空蒸镀所述散热片 ；
最后采用封装胶将金属薄片封装形成封装盖，使所述基板和所述封装盖形成密闭空间，将所述阳极、功能层、阴极和封装层容置在该封闭空间内。
优选地，所述所述氧氮碳化合物膜的厚度为 100 ～ 150nm 。
优选地，所述保护层的材料为酞菁铜、 N ， N'- （ 1- 萘基） - N ， N'- 二苯基 -4,4'- 联苯二胺、八羟基喹啉铝、氧化硅、氟化镁或硫化锌，保护层的厚度为 200 ～ 300nm ；
所述有机挡层的材料为聚四氟乙烯、甲基丙烯酸树脂或环脂肪环氧树脂，所述有机挡层的厚度为 1 ～ 1.5µm 。
优选地，所述湿气吸收层的材料为氧化钙、氧化钡、氧化锶或氧化镁，所述湿气吸收层的厚度为 100nm ～ 200nm 。
优选地，所述散热层的材料为铝、银、铜或他们的组合物，所述散热层的厚度为 200 ～ 500nm 。
优选地，所述封装盖为金属薄片，金属薄片的材料为银、铝或铜。
优选地，重复制备所述氧氮碳化合物膜和有机阻挡层的制备工艺，使所述氧氮碳化合物膜和有机阻挡层层叠设置，交替层叠层数为大于等于 3 层。。
本发明提供了一种有机电致发光器件及其制备方法具有以下有益效果：
本发明有机电致发光器件可以有效地减少外部水、氧等活性物质对有机电致发光器件的侵蚀，从而对器件有机功能材料及电极形成有效的保护，显著地提高有机电致发光器件的寿命；使防水性能（ WVTR ）达到 5.3E-5g/m2 · day ，寿命达 13,813 小时以上，本发明有机电致发光器件材料廉价，封装方法方式简单，易大面积制备，适于工业化大规模使用。
 附图说明
图 1 是本发明有机电致发光器件的结构示意图；
图 2 是本发明有机电致发光器件的制备流程图；
图 3 是本发明有机电致发光器件的封装层的制备流程图。
本发明的实施方式
以下所述是本发明的优选实施方式。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和调整，这些改进和调整也视为在本发明的保护范围内。
根据图 1 本发明提供了一种有机电致发光器件 100 ，包括依次层叠的基板 10 、阳极 20 、功能层 30 、阴极 40 、封装层 50 及封装盖 60 ，基板 10 和封装盖 60 形成封闭空间，将阳极 20 、功能层 30 、阴极 40 及封装层 50 封装在该空间内。
在本实施例中，基板 10 为玻璃基板或有机薄膜，该有机薄膜具体为：聚对苯二甲酸乙二酯；
在本实施例中，在基板 10 上设置阳极 20 ，阳极 20 为铟锡氧化物；
在本实施例中，功能层 30 形成于阳极 20 表面。功能层 30 包括依次层叠的空穴注入层、空穴传输层、发光层、电子传输层、电子注入层。可以理解，空穴注入层、空穴传输层、电子传输层、电子注入层可以省略，此时功能层 30 仅包括发光层 ；
空穴注入层为 N,N′- 二 (1- 萘基 )-N,N′- 二苯基 -1, 1′- 联苯 -4-4′- 二胺（ NPB ）及掺杂在 NPB 中的氧化钼（ MoO3 ）。 MoO3 的质量百分含量为 30% 。空穴注入层的厚度为 10nm ；
空穴传输层 为 4,4',4''- 三（咔唑 -9- 基）三苯胺（ TCTA ）。空穴传输层的厚度为 30nm 。
发光层材料 包括主体材料及掺杂在主体材料中的客体材料。主体材料为 1,3,5- 三 (1- 苯基 -1H- 苯并咪唑 -2- 基 ) 苯（ TPBI ），客体材料为三（ 2- 苯基吡啶）合铱 (Ir(ppy)3) 。客体材料的质量百分含量为 5% 。发光层的厚度为 20nm 。
电子传输层的材料为 4,7- 二苯基 -1,10- 菲罗啉（ Bphen ）。电子传输层的厚度为 10nm 。
电子注入层的材料包括 Bphen 及掺杂在 Bphen 中的叠氮铯（ CsN3 ）。 CsN3 的质量百分含量为 30% 。电子注入层的厚度为 20nm 。
需要说明的是，空穴注入层、空穴传输层、发光层、电子传输层、电子注入层也可以根据需要采用其他材料。
在本实施例中，在功能层 30 上设置 阴极 40 ，阴极 40 可以为单层金属层，该单层金属为铝、银及金；也可以是层叠透明阴极，该透明阴极为 ITO/Ag/ITO 或 ZnS/Ag/ZnS 。
在本实施例中， 在阴极 40 上设置封装层 50 ，该封装层 50 包括保护层 501 、氧氮碳化合物膜 502 、有机阻挡层 503 、湿气吸收层 504 及散热层 505 。
保护层 501 ，保护层 501 的材料为酞菁铜、 N ， N'- （ 1- 萘基） - N ， N'- 二苯基 -4,4'- 联苯二胺、八羟基喹啉铝、氧化硅、氟化镁或硫化锌，保护层的厚度为 200 ～ 300nm 。
在本实施例中， 在保护层 501 上设置氧氮碳化合物膜 502 ，氧氮碳化合物膜 502 为掺杂有氧化物和碳化物的氮化物膜，其中，所述氧化物材料为二氧化硅、三氧化铝、二氧化锆、二氧化铪、二氧化钛或五氧化二钽，所述氮化物材料为四氮化三硅、氮化铝、氮化硼、氮化硅、氮化钽或氮化钛，所述碳化物材料为碳化硅、碳化钨、碳化钽、碳化硼、碳化钛或碳化铪，所述氧化物、所述碳化物与所述氮化物的质量比为 2 ～ 6 ： 1 ～ 5 ： 9 ～ 17;
在本实施例中， 氧氮碳化合物膜 502 的厚度为 100 ～ 150nm 。
在本实施例中， 在氧氮碳化合物膜 502 表面设置有机阻挡层 503 ，有机阻挡层 503 的材料为聚四氟乙烯、甲基丙烯酸树脂或环脂肪环氧树脂，厚度为 1 ～ 1.5µm 。
在本实施例中， 所述氧氮碳化合物膜 502 和有机阻挡层 503 交替层叠设置，交替层叠层数为大于等于 3 层。
将氧氮碳化合物膜和有机阻挡层交替层叠设置能够延长水氧渗透路径，交替设置可弥补孔隙，使有机物和无机物结合从而可缓解应力。
在本实施例中，在有机阻挡层 503 表面设置湿气吸收层 504 ，湿气吸收层 504 的材料为氧化钙、氧化钡、氧化锶或氧化镁，厚度为 100nm ～ 200nm 。
在本实施例中，在湿气吸收层 504 表面设置散热层 505 ，散热层 505 的材料为铝、银、铜或他们的组合物，厚度为 200 ～ 500nm 。
在本实施例中，以基底 10 为界采用封装盖 60 进行封装，使基底 10 与封装盖 60 之间形成密闭空间，将上述各层设置在该密闭空间内，所述封装盖 60 为金属薄片，金属薄片包括银、铝或铜薄片。
根据图 2 可知本发明提供的有机电致发光器件 100 的制备方法，具体步骤包括：
S101 在基板 10 上制备阳极 20 ，并在阳极 20 上形成功能层 30 。
功能层 30 包括依次层叠的空穴注入层、空穴传输层、发光层、电子传输层、电子注入层。
基底 10 可以为玻璃基底或有机聚对苯二甲酸乙二醇酯 （ PET ）薄膜基板。基底 10 具有制备有阳极 20 ，阳极 20 为 ITO 层。 ITO 层的厚度为 100 nm ~150nm 。
基板 10 表面在形成阳极 20 和功能层 30 之前先进行预处理以去除基底 10 表面的污染物，并进行表面活化增加基底 10 表面的含氧量以提高基底 10 表面的功函数。具体为，将基底 10 依次采用去丙酮、乙醇、离子水及乙醇各超声波清洗 5min ，之后用氮气吹干，烤箱烘干。
本实施方式中，空穴注入层的材料包括 N,N′- 二 (1- 萘基 )-N,N′- 二苯基 -1, 1′- 联苯 -4-4′- 二胺（ NPB ）及掺杂在 NPB 中的氧化钼（ MoO3 ）。 MoO3 的质量百分含量为 30% 。空穴注入层的厚度为 10nm 。空穴注入层由真空蒸镀形成，真空度为 3×10-5Pa ，蒸发速度为 0.1Å/s 。
空穴传输层的材料为 4,4',4''- 三（咔唑 -9- 基）三苯胺（ TCTA ）。空穴传输层的厚度为 30nm 。空穴传输层由真空蒸镀形成，真空度为 3× 10-5 Pa ，蒸发速度为 0.1Å/s 。
发光层的材料包括主体材料及掺杂在主体材料中的客体材料。主体材料为 1,3,5- 三 (1- 苯基 -1H- 苯并咪唑 -2- 基 ) 苯（ TPBI ），客体材料为三（ 2- 苯基吡啶）合铱 (Ir(ppy)3) 。客体材料的质量百分含量为 5% 。发光层的厚度为 20nm 。发光层由真空蒸镀形成，真空度为 3×10-5Pa ，蒸发速度为 0.2Å/s 。
电子传输层的材料为 4,7- 二苯基 -1,10- 菲罗啉（ Bphen ）。电子传输层的厚度为 10nm 。电子传输层由真空蒸镀形成，真空度为 3×10-5Pa ，蒸发速度为 0.1Å/s 。
电子注入层的材料包括 Bphen 及掺杂在 Bphen 中的叠氮铯（ CsN3 ）， CsN3 的质量百分含量为 30% 。电子注入层的厚度为 20nm 。电子注入层由真空蒸镀形成，真空度为 3×10-5Pa ，蒸发速度为 0.2Å/s 。
需要说明的是，空穴注入层、空穴传输层、发光层、电子传输层、电子注入层也可以根据需要采用其他材料。空穴注入层、空穴传输层、电子传输层、电子注入层可以省略，此时功能层 20 仅包括发光层。
步骤 S120 、在功能层 30 表面形成阴极 40 。
阴极 30 可以为单层结构。阴极 30 的厚度为 100nm 。阴极 30 的材料为铝（ Al ）、银（ Ag ）或金（ Au ），阴极 30 由真空蒸镀形成，真空度为 5×10-5Pa ，蒸发速度为 5Å/s 。也可以是层叠透明阴极，该透明阴极为 ITO/Ag/ITO 或 ZnS/Ag/ZnS 。
步骤 S130 、在阴极 40 上蒸镀形成封装层。
根据图 3 可知，封装层的制备步骤如下：
封装层依次包括保护层 501 、氧氮碳化合物膜 502 、有机阻挡层 503 、湿气吸收层 504 及散热层 505 。
步骤 S1301 、在阴极 40 上蒸镀形成保护层 501 ，保护层 501 的材料为酞菁铜、 N ， N'- （ 1- 萘基） - N ， N'- 二苯基 -4,4'- 联苯二胺、八羟基喹啉铝、氧化硅、氟化镁或硫化锌，保护层的厚度为 200 ～ 300nm 。蒸镀条件为，真空度为 8×10-5Pa ～ 3×10-5Pa ， 蒸发速度为 0.5Å /s ～ 5 Å /s ；
步骤 S1302 、在保护层 502 上采用磁控溅射制作氧氮碳化合物膜 502 ，氧氮碳化合物膜 502 为掺杂有氧化物和碳化物的氮化物膜，其中，所述氧化物材料为二氧化硅、三氧化铝、二氧化锆、二氧化铪、二氧化钛或五氧化二钽，所述氮化物材料为四氮化三硅、氮化铝、氮化硼、氮化硅、氮化钽或氮化钛，所述碳化物材料为碳化硅、碳化钨、碳化钽、碳化硼、碳化钛或碳化铪，所述氧化物、所述碳化物与所述氮化物的质量比为 2 ～ 6 ： 1 ～ 5 ： 9 ～ 17 。其中，磁控溅射条件为：采用三靶磁控溅射沉积***，设置本底真空度为 1 × 10-5Pa ～ 1 × 10-3Pa ，膜层厚度设置为 80nm ～ 150nm ，所述氧化物、所述碳化物与所述氮化物的质量比为 2 ～ 6 ： 1 ～ 5 ： 9 ～ 17 作为靶材 , 在溅射速率为 5nm/min - 40nm/min 进行磁控溅射得到氧氮碳化合物膜 502 。
步骤 S1303 、在氧氮碳化合物膜 502 旋涂有机阻挡层 503 ，然后在惰性气氛下采用紫外光固化，紫外光固化条件为波长 200 nm ～ 400nm ，光强 10 mW/cm2 ～ 15 mW/cm2 ，曝光时间 200 s ～ 300s ，有机阻挡层 503 厚度为 1µm ～ 1.5µm ；
步骤 S1304 、在有机阻挡层 503 上采用溅射方式制备湿气吸收层 504 ，湿气吸收层 504 的材料为氧化钙、氧化钡、氧化锶或氧化镁，厚度为 100nm ～ 200nm 。溅射条件为 所述溅射方式具体为真空度 1×10-5Pa ～ 1×10-3Pa ， 蒸射速度 1Å ～ 5Å/s ；
步骤 S1305 、在湿气吸收层 504 上采用蒸镀方式制备散热层 505 ，散热层 505 的材料为铝、银、铜或他们的组合物，厚度为 200 nm ～ 500nm 。蒸镀条件为，真空度为 8×10-5Pa ～ 3×10-5Pa ，蒸发速度 1Å /s ～ 5 Å /s ；
在优选的实施例中，通过交替重复步骤 S1303 和步骤 S1304 制备层叠设置的氧氮碳化合物膜 502 和有机阻挡层 503 ，交替层叠层数为大于等于 3 层；
通过步骤 S1302 到步骤 S1305 形成封装层；
步骤 S140 、在封装层 50 表面形成封装盖 60 。
在封装盖边缘涂敷布封装胶，采用紫外光固化干燥的方式硬化封装胶，紫外光波长为 200 nm ～ 400nm ，光强为 10 mW/cm2 ～ 15 mW/cm2 ，曝光时间 300s ～ 400s ，使封装盖 60 与基板 10 之间形成密闭空间。
实施例 1 ：
一种有机电致发光器件的制备方法，包括以下步骤：
1 、基板前处理及阳极的制备：依次采用丙酮、乙醇、去离子水和乙醇采用超声波清洗机进行清洗，每次洗涤清洗时间为 5 分钟，然后用氮气吹干，使用烘箱烤干后待用；在基板上设置 ITO 玻璃，对负载有 ITO 玻璃的基板进行表面活化处理，以增表面层的含氧量，提高阳极表面的功函数； ITO 玻璃厚度为 100nm ；
2 、功能层的制备：
在阳极上蒸镀空穴注入层；
空穴注入层的材料包括 N,N′- 二 (1- 萘基 )-N,N′- 二苯基 -1, 1′- 联苯 -4-4′- 二胺（ NPB ）及掺杂在 NPB 中的氧化钼（ MoO3 ）。 MoO3 的质量百分含量为 30% 。空穴注入层的厚度为 10nm 。空穴注入层由真空蒸镀形成，真空度为 3×10-5Pa ，蒸发速度为 0.1Å/s 。 ;
在空穴注入层上蒸镀空穴传输层；
空穴传输层的材料为 4,4',4''- 三（咔唑 -9- 基）三苯胺（ TCTA ）。空穴传输层的厚度为 30nm 。空穴传输层由真空蒸镀形成，真空度为 3×10-5Pa ，蒸发速度为 0.1Å/s 。
在空穴传输层上蒸镀发光层；
发光层的材料包括主体材料及掺杂在主体材料中的客体材料。主体材料为 1,3,5- 三 (1- 苯基 -1H- 苯并咪唑 -2- 基 ) 苯（ TPBI ），客体材料为三（ 2- 苯基吡啶）合铱 (Ir(ppy)3) 。客体材料的质量百分含量为 5% 。发光层的厚度为 20nm 。发光层由真空蒸镀形成，真空度为 3×10-5Pa ，蒸发速度为 0.2Å/s 。
在发光层上蒸镀电子传输层
电子传输层的材料为 4,7- 二苯基 -1,10- 菲罗啉（ Bphen ）。电子传输层的厚度为 10nm 。电子传输层由真空蒸镀形成，真空度为 3×10-5Pa ，蒸发速度为 0.1Å/s 。
在电子传输层上蒸镀电子注入层
电子注入层的材料包括 Bphen 及掺杂在 Bphen 中的叠氮铯（ CsN3 ）， CsN3 的质量百分含量为 30% 。电子注入层的厚度为 20nm 。电子注入层由真空蒸镀形成，真空度为 3×10-5Pa ，蒸发速度为 0.2Å/s 。
3 、在电子注入层上蒸镀阴极
金属阴极采用铝（ Al ），厚度为 100nm ，蒸镀真空度为 5×10-5Pa ，蒸发速度为 5Å/s ；
4 、封装层的制备
在阴极上设置封装层，封装层包括保护层、氧氮碳化合物膜、有机阻挡层、湿气吸收层及散热层 ;
在阴极上蒸镀形成保护层，保护层的材料为酞菁铜，保护层的厚度为 200nm 。蒸镀条件为，真空度为 3×10-5Pa ， 蒸发速度为 0.5Å /s ；
在保护层上采用磁控溅射制作氧氮碳化合物膜，氧氮碳化合物膜为掺杂有氧化物和碳化物的氮化物膜，其中，氧化物材料为二氧化硅，氮化物材料为四氮化三硅，碳化物材料为碳化硅，氧化物、碳化物与氮化物的质量比为 4:3:13 。其中，磁控溅射条件为：采用三靶磁控溅射沉积***，设置本底真空度为 1 × 10-5Pa ，膜层厚度设置为 120nm ，在溅射速率为 5nm/min 进行磁控溅射得到氧氮碳化合物膜。
在氧氮碳化合物膜旋涂有机阻挡层，有机阻挡层材料为聚四氟乙烯，然后在惰性气氛下采用紫外光固化，紫外光固化条件为波长 365nm ，光强 10 mW/cm2 ，曝光时间 200 s ，有机阻挡层厚度为 1µm ；
氧氮碳化合物膜和有机阻挡层交替制备三次；
在有机阻挡层上采用溅射方式制备湿气吸收层，湿气吸收层的材料为氧化钙，厚度为 200nm 。溅射条件为 所述溅射方式具体为真空度 2×10-4Pa ， 蒸射速度 5Å/s ;
在湿气吸收层上采用蒸镀方式制备散热层，散热层的材料为铝，厚度为 200 nm 。蒸镀条件为，真空度为 5×10-5Pa ，蒸发速度 1Å /s ；
5 、封装盖的制备
在封装盖边缘涂敷布封装胶，采用紫外光固化干燥的方式硬化封装胶，紫外光波长为 365nm ，光强为 11 mW/cm2 ，曝光时间 350s ，使封装盖与基板之间形成密闭空间。
实施例 2 ：
一种有机电致发光器件的制备方法，包括以下步骤：
1 、 2 、 3 同实施例 1 ；
4 、封装层的制备
在阴极上设置封装层，封装层包括保护层、氧氮碳化合物膜、有机阻挡层、湿气吸收层及散热层 ;
在阴极上蒸镀形成保护层，保护层的材料为 N ， N'- （ 1- 萘基） - N ， N'- 二苯基 -4,4'- 联苯二胺，保护层的厚度为 300nm 。蒸镀条件为，真空度为 3×10-5Pa ， 蒸发速度为 5Å /s ；
在保护层上采用磁控溅射制作氧氮碳化合物膜，氧氮碳化合物膜为掺杂有氧化物和碳化物的氮化物膜，其中，氧化物材料为三氧化铝，氮化物材料为氮化铝，碳化物材料为碳化钨，氧化物、碳化物与氮化物的质量比为 2:1:17 。其中，磁控溅射条件为：采用三靶磁控溅射沉积***，设置本底真空度为 2 × 10-4Pa ，膜层厚度设置为 10 0nm ，在溅射速率为 1nm/min 进行磁控溅射得到氧氮碳化合物膜。
在氧氮碳化合物膜旋涂有机阻挡层，有机阻挡层材料为甲基丙烯酸树脂，然后在惰性气氛下采用紫外光固化，紫外光固化条件为波长 365nm ，光强 15 mW/cm2 ，曝光时间 200 s ，有机阻挡层厚度为 1.5µm ；
氧氮碳化合物膜和有机阻挡层交替制备三次；
在有机阻挡层上采用溅射方式制备湿气吸收层，湿气吸收层的材料为氧化钡，厚度为 200nm 。溅射条件为 所述溅射方式具体为真空度 2×10-4Pa ， 蒸射速度 5Å/s ;
在湿气吸收层上采用蒸镀方式制备散热层，散热层的材料为银，厚度为 500 nm 。蒸镀条件为，真空度为 5×10-5Pa ，蒸发速度 5Å /s ；
5 、封装盖的制备
在封装盖边缘涂敷布封装胶，封装盖的材料为铝薄片，采用紫外光固化干燥的方式硬化封装胶，紫外光波长为 365nm ，光强为 10 mW/cm2 ，曝光时间 400s ，使封装盖与基板之间形成密闭空间。
实施例 3 ：
一种有机电致发光器件的制备方法，包括以下步骤：
1 、 2 、 3 同实施例 1 ；
4 、封装层的制备
在阴极上设置封装层，封装层包括保护层、氧氮碳化合物膜、有机阻挡层、湿气吸收层及散热层 ;
在阴极上蒸镀形成保护层，保护层的材料为八羟基喹啉铝，保护层的厚度为 250nm 。蒸镀条件为，真空度为 3×10-5Pa ， 蒸发速度为 2Å /s ；
在保护层上采用磁控溅射制作氧氮碳化合物膜，氧氮碳化合物膜为掺杂有氧化物和碳化物的氮化物膜，其中，氧化物材料为二氧化钛，氮化物材料为氮化硼，碳化物材料为碳化钽，氧化物、碳化物与氮化物的质量比为 6:5:9 。其中，磁控溅射条件为：采用三靶磁控溅射沉积***，设置本底真空度为 2 × 10-4Pa ，膜层厚度设置为 150 nm ，在溅射速率为 40nm/min 进行磁控溅射得到氧氮碳化合物膜。
在氧氮碳化合物膜旋涂有机阻挡层，有机阻挡层材料为环脂肪环氧树脂，然后在惰性气氛下采用紫外光固化，紫外光固化条件为波长 365nm ，光强 11 mW/cm2 ，曝光时间 230 s ，有机阻挡层厚度为 1.2µm ；
氧氮碳化合物膜和有机阻挡层交替制备四次；
在有机阻挡层上采用溅射方式制备湿气吸收层，湿气吸收层的材料为氧化锶，厚度为 150nm 。溅射条件为 所述溅射方式具体为真空度 2×10-4Pa ， 蒸射速度 5Å/s ;
在湿气吸收层上采用蒸镀方式制备散热层，散热层的材料为铜，厚度为 300 nm 。蒸镀条件为，真空度为 5×10-5Pa ，蒸发速度 2Å /s ；
5 、封装盖的制备
在封装盖边缘涂敷布封装胶，封装盖的材料为铜薄片，采用紫外光固化干燥的方式硬化封装胶，紫外光波长为 365nm ，光强为 15 mW/cm2 ，曝光时间 300s ，使封装盖与基板之间形成密闭空间。
实施例 4 ：
一种有机电致发光器件的制备方法，包括以下步骤：
1 、 2 、 3 同实施例 1 ；
4 、封装层的制备
在阴极上设置封装层，封装层包括保护层、氧氮碳化合物膜、有机阻挡层、湿气吸收层及散热层 ;
在阴极上蒸镀形成保护层，保护层的材料为氧化硅，保护层的厚度为 200nm 。蒸镀条件为，真空度为 5×10-5Pa ， 蒸发速度为 0.5Å /s ；
在保护层上采用磁控溅射制作氧氮碳化合物膜，氧氮碳化合物膜为掺杂有氧化物和碳化物的氮化物膜，其中，氧化物材料为二氧化锆，氮化物材料为氮化硅，碳化物材料为碳化硼，氧化物、碳化物与氮化物的质量比为 2:1:7 。其中，磁控溅射条件为：采用三靶磁控溅射沉积***，设置本底真空度为 2 × 10-4Pa ，膜层厚度设置为 130 nm ，在溅射速率为 20nm/min 进行磁控溅射得到氧氮碳化合物膜。
在氧氮碳化合物膜旋涂有机阻挡层，有机阻挡层材料为聚四氟乙烯，然后在惰性气氛下采用紫外光固化，紫外光固化条件为波长 365nm ，光强 10 mW/cm2 ，曝光时间 200 s ，有机阻挡层厚度为 1µm ；
氧氮碳化合物膜和有机阻挡层交替制备五次；
在有机阻挡层上采用溅射方式制备湿气吸收层，湿气吸收层的材料为氧化镁，厚度为 100nm 。溅射条件为 所述溅射方式具体为真空度 2×10-4Pa ， 蒸射速度 5Å/s ;
在湿气吸收层上采用蒸镀方式制备散热层，散热层的材料为铜铝合金，铜和铝的质量比为 3:1 ，厚度为 500 nm 。蒸镀条件为，真空度为 5×10-5Pa ，蒸发速度 2Å /s ；
5 、封装盖的制备
在封装盖边缘涂敷布封装胶，封装盖的材料为铜薄片，采用紫外光固化干燥的方式硬化封装胶，紫外光波长为 365nm ，光强为 11 mW/cm2 ，曝光时间 350s ，使封装盖与基板之间形成密闭空间。
实施例 5 ：
一种有机电致发光器件的制备方法，包括以下步骤：
1 、 2 、 3 同实施例 1 ；
4 、封装层的制备
在阴极上设置封装层，封装层包括保护层、氧氮碳化合物膜、有机阻挡层、湿气吸收层及散热层 ;
在阴极上蒸镀形成保护层，保护层的材料为氟化镁，保护层的厚度为 300nm 。蒸镀条件为，真空度为 5×10-5Pa ， 蒸发速度为 5Å /s ；
在保护层上采用磁控溅射制作氧氮碳化合物膜，氧氮碳化合物膜为掺杂有氧化物和碳化物的氮化物膜，其中，氧化物材料为二氧化铪，氮化物材料为氮化钽，碳化物材料为谈话钛，氧化物、碳化物与氮化物的质量比为 1:1:3 。其中，磁控溅射条件为：采用三靶磁控溅射沉积***，设置本底真空度为 2 × 10-4Pa ，膜层厚度设置为 140 nm ，在溅射速率为 1nm/min 进行磁控溅射得到氧氮碳化合物膜。
在氧氮碳化合物膜旋涂有机阻挡层，有机阻挡层材料为甲基丙烯酸树脂，然后在惰性气氛下采用紫外光固化，紫外光固化条件为波长 365nm ，光强 15 mW/cm2 ，曝光时间 200 s ，有机阻挡层厚度为 1.5µm ；
在有机阻挡层上采用溅射方式制备湿气吸收层，湿气吸收层的材料为氧化钙，厚度为 200nm 。溅射条件为 所述溅射方式具体为真空度 2×10-4Pa ， 蒸射速度 5Å/s ;
在湿气吸收层上采用蒸镀方式制备散热层，散热层的材料为铜铝合金，铜和铝的质量比为 3:1 ，厚度为 500 nm 。蒸镀条件为，真空度为 5×10-5Pa ，蒸发速度 2Å /s ；
5 、封装盖的制备
在封装盖边缘涂敷布封装胶，封装盖的材料为铜薄片，采用紫外光固化干燥的方式硬化封装胶，紫外光波长为 365nm ，光强为 15 mW/cm2 ，曝光时间 400s ，使封装盖与基板之间形成密闭空间。
实施例 6 ：
一种有机电致发光器件的制备方法，包括以下步骤：
1 、 2 、 3 同实施例 1 ；
4 、封装层的制备
在阴极上设置封装层，封装层包括保护层、氧氮碳化合物膜、有机阻挡层、湿气吸收层及散热层 ;
在阴极上蒸镀形成保护层，保护层的材料为硫化锌，保护层的厚度为 250nm 。蒸镀条件为，真空度为 5×10-5Pa ， 蒸发速度为 2Å /s ；
在保护层上采用磁控溅射制作氧氮碳化合物膜，氧氮碳化合物膜为掺杂有氧化物和碳化物的氮化物膜，其中，氧化物材料为五氧化二钽，氮化物材料为氮化钛，碳化物材料为碳化铪，氧化物、碳化物与氮化物的质量比为 1:1:3 。其中，磁控溅射条件为：采用三靶磁控溅射沉积***，设置本底真空度为 2 × 10-4Pa ，膜层厚度设置为 120 nm ，在溅射速率为 5nm/min 进行磁控溅射得到氧氮碳化合物膜。
在氧氮碳化合物膜旋涂有机阻挡层，有机阻挡层材料为环脂肪环氧树脂，然后在惰性气氛下采用紫外光固化，紫外光固化条件为波长 365nm ，光强 11 mW/cm2 ，曝光时间 230 s ，有机阻挡层厚度为 1.2µm ；
在有机阻挡层上采用溅射方式制备湿气吸收层，湿气吸收层的材料为氧化钡，厚度为 150nm 。溅射条件为 所述溅射方式具体为真空度 2×10-4Pa ， 蒸射速度 5Å/s ;
在湿气吸收层上采用蒸镀方式制备散热层，散热层的材料为银，厚度为 300 nm 。蒸镀条件为，真空度为 5×10-5Pa ，蒸发速度 3Å /s ；
5 、封装盖的制备
在封装盖边缘涂敷布封装胶，封装盖的材料为铜薄片，采用紫外光固化干燥的方式硬化封装胶，紫外光波长为 365nm ，光强为 11 mW/cm2 ，曝光时间 350s ，使封装盖与基板之间形成密闭空间。
效果实施例
为有效证明本发明有机电致发光器件及其制备方法的有益效果，提供相关实验数据如下。
有机电致发光器件水氧渗透率的测试条件为：设备：吉时利公司的 Keithley2400 ，样品架；方法：测试 Ca 膜电阻的变化；条件：温度 20-25℃ ，湿度 40% ～ 60% 。结果如下：
表 1. 实施例 1~6 有机电致发光器件水氧渗透率
实施例1 实施例2 实施例3 实施例4 实施例5 实施例6
WVTR(g/m2/day) 4.4 E -5 3.1 E -5 5.3 E -5 4.0 E -5 2.1 E -5 3.7 E-5
表 1 是实施例 1~6 有机电致发光器件水氧渗透率，使防水性能（ WVTR ）达到 5.3E-5g/m2 · day 。
有机电致发光器件寿命测试条件：设备：吉时利公司的 Keithley2400 ，柯尼卡美能达公司的 CS-100A 色度计；方法：测试亮度从 1000cd/m2 降到 700cd/m2 所用的时间；条件：温度 20-25℃，湿度40% ～ 60% 。
表 2. 实施例 1~6 有机电致发光器件寿命情况
实施例1 实施例2 实施例3 实施例4 实施例5 实施例6
寿命（万小时）
（ T70@1000cd/m2 ）		 1.3001 1.3411 1.2812 1.3114 1.3813 1.3305
表 2 是实施例 1~6 有机电致发光器件寿命情况可以看出，本发明有机电致发光器件的寿命达 1.3813 万小时以上（ T70@1000cd/m2 ）。
综上，本发明提供的有机电致发光器件可有效地减少外部水、氧等活性物质对有机电致发光器件的侵蚀，从而对器件有机功能材料及电极形成有效的保护，满足封装的密封性要求，可显著地提高 OLED 器件的寿命。

Claims (10)

  1. 一种有机电致发光器件，包括依次层叠的基板、阳极、功能层、阴极、封装层和封装盖，基板和封装盖形成封闭空间，阳极、功能层、阴极、封装层容置在该封闭空间内，其特征在于，所述封装层依次包括保护层、氧氮碳化合物膜、有机阻挡层、湿气吸收层和散热层；
    所述氧氮碳化合物膜为掺杂有氧化物和碳化物的氮化物膜，其中，所述氧化物材料为二氧化硅、三氧化铝、二氧化锆、二氧化钛、二氧化铪或五氧化二钽，所述碳化物材料为碳化硅、碳化钨、碳化钽、碳化硼、碳化钛或碳化铪，所述氮化物材料为四氮化三硅、氮化铝、氮化硼、氮化硅、氮化钽或氮化钛，所述氧化物、所述碳化物与所述氮化物的质量比为 2 ～ 6 ： 1 ～ 5 ： 9 ～ 17 。
  2. 一种有机电致发光器件，包括依次层叠的基板、阳极、功能层、阴极、封装层和封装盖，基板和封装盖形成封闭空间，阳极、功能层、阴极、封装层容置在该封闭空间内，其特征在于，所述封装层依次包括保护层、氧氮碳化合物膜、有机阻挡层、湿气吸收层和散热层；
    所述氧氮碳化合物膜为掺杂有氧化物和碳化物的氮化物膜，其中，所述氧化物材料为二氧化硅、三氧化铝、二氧化锆、二氧化钛、二氧化铪或五氧化二钽，所述碳化物材料为碳化硅、碳化钨、碳化钽、碳化硼、碳化钛或碳化铪，所述氮化物材料为四氮化三硅、氮化铝、氮化硼、氮化硅、氮化钽或氮化钛，所述氧化物、所述碳化物与所述氮化物的质量比为 2 ～ 6 ： 1 ～ 5 ： 9 ～ 17 。
  3. 如权利要求 1 所述的有机电致发光器件，其特征在于，所述保护层的材料为酞菁铜、 N ， N'- （ 1- 萘基） - N ， N'- 二苯基 -4,4'- 联苯二胺、八羟基喹啉铝、氧化硅、氟化镁或硫化锌，保护层的厚度为 200 nm ～ 300nm ；
    所述有机阻挡层的材料为聚四氟乙烯、甲基丙烯酸树脂或环脂肪环氧树脂，所述有机阻挡层的厚度为 1 ～ 1.5µm 。
  4. 如权利要求 1 所述的有机电致发光器件，其特征在于，所述湿气吸收层的材料为氧化钙、氧化钡、氧化锶或氧化镁，所述湿气吸收层厚度为 100nm ～ 200nm ；
    所述散热层的材料为铝、银、铜或他们的组合物，所述散热层的厚度为 200nm ～ 500nm ；及 所述封装盖为金属薄片，金属薄片的材料为银、铝或铜。
  5. 如权利要求 1 所述的有机电致发光器件，其特征在于，所述氧氮碳化合物膜与所述有机阻挡层交替层叠设置，层叠层数大于等于三层。
  6. 一种有机电致发光器件的制备方法，其特征在于，包括以下步骤：
    在洁净的玻璃基板或有机薄膜基板上制备有机电致发光器件的阳极；采用真空蒸镀的方法在阳极导电基板上依次制备功能层、阴极和封装层，采用紫外光固化方式将封装盖进行封装，使所述基板和所述封装盖形成封闭空间；
    所述封装层的制备包括首先在阴极上采用真空蒸镀的方式制备所述保护层；
    在所述保护层上采用磁控溅射共溅制备所述氧氮碳化合物膜，其中，所述氧化物材料为二氧化硅、三氧化铝、二氧化锆、二氧化铪、二氧化钛或五氧化二钽，所述氮化物材料为四氮化三硅、氮化铝、氮化硼、氮化硅、氮化钽或氮化钛，所述碳化物材料为碳化硅、碳化钨、碳化钽、碳化硼、碳化钛或碳化铪，所述磁控溅射条件为：采用三靶磁控溅射沉积***，设置本底真空度为 1 × 10-5Pa ～ 1 × 10-3Pa ，膜层厚度设置为 10 0nm ～ 150nm ，将所述氧化物、所述碳化物与所述氮化物的质量比为 2 ～ 6 ： 1 ～ 5 ： 9 ～ 17 作为靶材，在溅射速率为 5nm/mi n ～ 40nm/min 条件下进行磁控溅射得到氧氮碳化合物膜；
    然后在所述氧氮碳化合物膜上采用先旋涂后曝光的工艺制备所述有机阻挡层，所述先旋涂后曝光的工艺过程为，将所述有机阻挡层材料旋涂，然后用波长为 200nm ～ 400nm 紫外光固化，光强为 10 mW/cm2 ～ 15 mW/cm2 ， 曝光时间 200s ～ 300s ；
    接着在所述有机阻挡层上采用溅射方式制备所述湿气吸收层，在所述湿气吸收层上真空蒸镀所述散热片 ；
    最后采用封装胶将金属薄片封装形成封装盖，使所述基板和所述封装盖形成密闭空间，将所述阳极、功能层、阴极和封装层容置在该封闭空间内。
  7. 如权利要求 6 所述的有机电致发光器件的制备方法，其特征在于，所述所述氧氮碳化合物膜的厚度为 100 ～ 150nm 。
  8. 如权利要求 6 所述的有机电致发光器件的制备方法，其特征在于，所述保护层的材料为酞菁铜、 N ， N'- （ 1- 萘基） - N ， N'- 二苯基 -4,4'- 联苯二胺、八羟基喹啉铝、氧化硅、氟化镁或硫化锌，保护层的厚度为 200 ～ 300nm ；
    所述有机挡层的材料为聚四氟乙烯、甲基丙烯酸树脂或环脂肪环氧树脂，所述有机挡层的厚度为 1 ～ 1.5µm 。
  9. 如权利要求 6 所述的有机电致发光器件的制备方法，其特征在于，所述湿气吸收层的材料为氧化钙、氧化钡、氧化锶或氧化镁，所述湿气吸收层的厚度为 100nm ～ 200nm ，所述散热层的材料为铝、银、铜或他们的组合物，所述散热层的厚度为 200 ～ 500nm ，所述封装盖为金属薄片，金属薄片的材料为银、铝或铜。
  10. 如权利要求 6 所述的有机电致发光器件的制备方法，其特征在于，重复制备所述氧氮碳化合物膜和有机阻挡层的制备工艺，使所述氧氮碳化合物膜和有机阻挡层层叠设置，交替层叠层数为大于等于 3 层。
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110459678A (zh) * 2019-08-14 2019-11-15 武汉华星光电半导体显示技术有限公司 柔性有机发光显示面板及其制备方法
CN111341940A (zh) * 2020-03-18 2020-06-26 上海晶合光电科技有限公司 一种oled器件封装结构及其制备方法
WO2022188193A1 (zh) * 2021-03-08 2022-09-15 武汉华星光电半导体显示技术有限公司 一种显示面板及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1399502A (zh) * 2001-07-20 2003-02-26 Lg电子株式会社 平板显示器及在其中形成保护层的方法
CN1416006A (zh) * 2001-11-02 2003-05-07 精工爱普生株式会社 电光装置、其制造方法以及电子设备
CN1652646A (zh) * 2005-02-22 2005-08-10 友达光电股份有限公司 有机电激发光元件的封合结构
US20070181872A1 (en) * 2006-02-03 2007-08-09 Lee Young-Gu Organic light emitting display and manufacturing method thereof
WO2009053886A2 (en) * 2007-10-25 2009-04-30 Koninklijke Philips Electronics N.V. Organic electro-optical device, light source, display device and solar cell

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1399502A (zh) * 2001-07-20 2003-02-26 Lg电子株式会社 平板显示器及在其中形成保护层的方法
CN1416006A (zh) * 2001-11-02 2003-05-07 精工爱普生株式会社 电光装置、其制造方法以及电子设备
CN1652646A (zh) * 2005-02-22 2005-08-10 友达光电股份有限公司 有机电激发光元件的封合结构
US20070181872A1 (en) * 2006-02-03 2007-08-09 Lee Young-Gu Organic light emitting display and manufacturing method thereof
WO2009053886A2 (en) * 2007-10-25 2009-04-30 Koninklijke Philips Electronics N.V. Organic electro-optical device, light source, display device and solar cell

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110459678A (zh) * 2019-08-14 2019-11-15 武汉华星光电半导体显示技术有限公司 柔性有机发光显示面板及其制备方法
CN110459678B (zh) * 2019-08-14 2022-08-23 武汉华星光电半导体显示技术有限公司 柔性有机发光显示面板及其制备方法
CN111341940A (zh) * 2020-03-18 2020-06-26 上海晶合光电科技有限公司 一种oled器件封装结构及其制备方法
WO2022188193A1 (zh) * 2021-03-08 2022-09-15 武汉华星光电半导体显示技术有限公司 一种显示面板及其制备方法
US11991917B2 (en) 2021-03-08 2024-05-21 Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. Display panel and manufacturing method thereof

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