WO2014082306A1

WO2014082306A1 - Organic light-emitting device and preparing method thereof

Info

Publication number: WO2014082306A1
Application number: PCT/CN2012/085678
Authority: WO
Inventors: 周明杰; 王平; 钟铁涛; 陈吉星
Original assignee: 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
Priority date: 2012-11-30
Filing date: 2012-11-30
Publication date: 2014-06-05

Abstract

An organic light-emitting device comprises a substrate, an anode, a functional layer, a cathode, a packaging layer and a packaging cover which are sequentially laminated. The substrate and the packaging cover form a closed space, and the anode, the functional layer, the cathode and the packaging layer are accommodated in the closed space. The packaging layer sequentially comprises a protection layer, an oxygen, nitrogen and fluorine compound film, an organic barrier layer, a moisture absorption layer and a heat dissipation layer. The oxygen, nitrogen and fluorine compound film is a nitride film doped with oxides and fluorides. The present invention also provides a method for preparing the organic light-emitting device. The method can effectively reduce erosion of moisture and oxygen to the organic light-emitting device, so as to effectively protect the organic functional material and electrodes of the device, and significantly improve the service life of the organic light-emitting device. The method of the present invention is especially suitable for packaging a flexible organic light-emitting device.

Description

Organic electroluminescent device and preparation method thereof

Technical field

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.

Background technique

An organic electroluminescent device (OLED) is a current-type semiconductor light-emitting device based on an organic material. Its typical structure is in ITO A tens of nanometer-thick organic light-emitting material is prepared on the glass as a light-emitting layer, and a metal electrode having a low work function is provided above the light-emitting layer. When a voltage is applied to the electrodes, the luminescent layer produces optical radiation.

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.

In the conventional technology, 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.

Summary of the invention

In order to overcome the above drawbacks of the prior art, 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.

In one aspect, 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. The anode, the functional layer, the cathode and the encapsulation layer are accommodated in the enclosed space, and the encapsulation layer comprises 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 fluorine compound, wherein the oxide material is silica, alumina, zirconia, titania, ceria or pentoxide钽, the nitride material is silicon nitride, aluminum nitride, boron nitride, silicon nitride, tantalum nitride or titanium nitride, and the fluoride material is aluminum fluoride, germanium tetrafluoride, and four Zirconium fluoride, barium fluoride or barium fluoride, the mass ratio of the oxide, fluoride to nitride is 2 to 6:1 to 5:9 to 17.

Preferably, the oxynitride film has a thickness of from 100 nm to 150 nm.

Preferably, 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 organic barrier layer has a thickness of 1 μm. ~ 1.5μm.

Preferably, 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.

Preferably, 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:

Preparing an 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;

Preparing the oxynitride film on the protective layer by magnetron sputtering co-sputtering, wherein the oxide material is silicon dioxide, aluminum oxide, zirconium dioxide, titanium dioxide, hafnium oxide or pentoxide Second, the nitride material is silicon nitride, aluminum nitride, boron nitride, silicon nitride, tantalum nitride or titanium nitride, and the fluoride material is aluminum fluoride, germanium tetrafluoride, The zirconium tetrafluoride, cesium fluoride or cesium fluoride, the magnetron sputtering condition is: using a three-target magnetron sputtering deposition system, setting the background vacuum to be 1 × 10 ^-5 Pa - 1 × 10 ^-3 Pa, the film thickness is set to be 10 nm to 150 nm, and the mass ratio of the oxide, fluoride and nitride is 2 to 6:1 to 5:9 to 17 as a target at a sputtering rate of 5 nm/mi. Magnetron sputtering under n to 40 nm/min to obtain an oxynitride film;

Then, the organic barrier layer is prepared on the oxynitride film by a spin coating and post-exposure process. 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.

Then, 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. ;

Finally, 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.

Preferably, the oxynitride film has a thickness of from 100 nm to 150 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 μm～ 1.5μm.

Preferably, 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.

Preferably, the material of the heat dissipation layer is aluminum, silver, copper or a combination thereof, and the thickness of the heat dissipation layer is 200 nm ～ 500nm.

Preferably, the package cover is a metal foil, and the material of the metal foil is silver, aluminum or copper.

Preferably, 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 alternately stacked layers is 3 or more.

The invention provides an organic electroluminescent device and a preparation method thereof having the following beneficial effects:

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 7.3E ^-5 g/m ² · day and the lifetime is over 11,411 hours. The organic electroluminescent device material of the invention is inexpensive, the packaging method is simple, and the preparation is easy for large area, and is suitable for industrial large-scale production. use.

DRAWINGS

1 is a schematic structural view of an organic electroluminescent device of the present invention;

2 is a flow chart showing the preparation of the organic electroluminescent device of the present invention;

3 is a flow chart showing the preparation of an encapsulation layer of the organic electroluminescent device of the present invention.

Embodiments of the invention

The following are preferred embodiments of the invention. It should be noted that a number of modifications and adaptations may be made by those skilled in the art without departing from the principles of the invention, and such modifications and adjustments are also considered to be within the scope of the invention.

According to Fig. 1, 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.

In this embodiment, the substrate 10 is a glass substrate or an organic film, and the organic film is specifically: polyethylene terephthalate;

In this embodiment, an anode 20 is disposed on the substrate 10, and the anode 20 is indium tin oxide;

In the present embodiment, 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.

In addition, 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.

In the present embodiment, 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.

In the present embodiment, an encapsulation layer 50 is disposed on the cathode 40, and the encapsulation layer 50 includes a protective layer 501. An oxynitride film 502, an organic barrier layer 503, a moisture absorbing layer 504, and a heat dissipation layer 505.

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 nm to 300 nm.

In the present embodiment, an oxynitride film 502, an oxynitride film 502, is provided on the protective layer 501. a nitride film doped with an oxide and a fluorine compound, wherein the oxide material is silicon dioxide, aluminum oxide, zirconium dioxide, titanium dioxide, hafnium oxide or tantalum pentoxide, the nitride material The silicon nitride, aluminum nitride, boron nitride, silicon nitride, tantalum nitride or titanium nitride, the fluoride material is aluminum fluoride, antimony tetrafluoride, zirconium tetrafluoride, antimony fluoride Or cesium fluoride, the mass ratio of the oxide, fluoride and nitride is 2 to 6:1 to 5:9 to 17;

In the present embodiment, the oxynitride film 502 has a thickness of 100 nm to 150 nm.

In the present embodiment, an organic barrier layer 503, an organic barrier layer 503, is disposed on the surface of the oxynitride film 502. The material is polytetrafluoroethylene, methacrylic resin or cycloaliphatic epoxy resin, and the thickness is from 1 μm to 1.5 μm.

In the present embodiment, the oxynitride film 502 and the organic barrier layer 503 Arranged alternately, the number of layers alternately stacked is 3 or more.

The alternate arrangement of the oxynitride film and the organic barrier layer can extend the water-oxygen permeation path, and the alternate arrangement can compensate for the pores, and the organic matter and the inorganic substance can be combined to relieve the stress.

In the present embodiment, 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.

In this embodiment, 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 nm to 500 nm.

In the present embodiment, 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.

In the present embodiment, 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 Å / 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 Å / 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 Å / 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 Å / 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 Å / s.

In addition, 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 Å / 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.

According to Figure 3, the preparation steps of the encapsulation layer are as follows:

The encapsulation layer sequentially includes a protective layer 501, an oxynitride 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 nm 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 Å / s to 5 Å / s ;

Step S1302, 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 fluorine compound, wherein the oxide material is two Silica, trialumina, zirconium dioxide, titanium dioxide, hafnium oxide or tantalum pentoxide, the nitride material being silicon nitride, aluminum nitride, boron nitride, silicon nitride, tantalum nitride or Titanium nitride, the fluoride material is aluminum fluoride, antimony tetrafluoride, zirconium tetrafluoride, antimony fluoride or antimony fluoride, and the mass ratio of the oxide, fluoride to nitride is 2 to 6: 1 to 5:9 to 17. Among them, the magnetron sputtering conditions are: using a three-target magnetron sputtering deposition system, the background vacuum is set to 1 × 10 ^-5 Pa to 1 × 10 ^-3 Pa, and the film thickness is set to 10 0 nm to 150 nm. The mass ratio of oxide, fluoride and nitride is from 2 to 6:1 to 5:9 to 17 as a target, and the oxygen oxyfluoride film is obtained by magnetron sputtering at a sputtering rate of 5 nm/min to 40 nm/min. 502.

Step S1303, spin-coating the organic barrier layer 503 on the oxynitride 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 μm to 1.5 μm;

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 Å to 5 Å/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 Å / s to 5 Å / s;

In a preferred embodiment, 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;

Forming an encapsulation layer through steps S1302 through S1305;

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.

Example 1

A method for preparing an organic electroluminescent device, comprising the steps of:

1 , 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;

2, the preparation of the functional layer:

Depositing a hole injection layer on the anode;

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 Å / s. ;

Depositing a hole transport layer on the hole injection layer;

Evaporating a light-emitting layer on the hole transport layer;

Evaporating an electron transport layer on the light emitting layer;

Evaporating an electron injection layer on the electron transport layer;

3. Vapor cathode on the electron injection layer:

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 Å/s;

4, the preparation of the encapsulation layer:

Providing an encapsulation layer on the cathode, the encapsulation layer comprising a protective layer, an oxynitride 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 Å / 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 fluorine compound, wherein the oxide material is silicon dioxide and the nitride material is four. The trisilicon nitride, the fluoride material is aluminum fluoride, and the mass ratio of the oxide, the fluoride to the nitride is 4:3:13. Among them, 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 oxynitride film was obtained by sputtering.

The organic barrier layer is spin-coated on the oxynitride 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 μm;

The oxynitride 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 Å/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 Å / s;

5, the preparation of the package cover:

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.

Example 2:

1, 2, 3 with the same embodiment 1;

4, the preparation of the encapsulation 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 Å / s;

An oxynitride film is formed by magnetron sputtering on the protective layer, and the oxynitride film is a nitride film of a doped oxide and a fluorine compound, wherein the oxide material is trialumina and the nitride material is nitrided. Aluminum, the fluoride material is barium tetrafluoride, and the mass ratio of oxide, fluoride and the nitride is 1:1:8. Among them, 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 oxynitride film, the organic barrier layer material is methacrylic resin, and then cured by ultraviolet light under an inert atmosphere, the ultraviolet curing condition is wavelength 365 nm, light intensity 15 mW/cm ² , exposure time 200 s, the thickness of the organic barrier layer is 1.5 μm;

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 Å/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 Å / s;

5, the preparation of the package cover:

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 , and the exposure time is 400 s. A sealed space is formed between the substrate and the substrate.

Example 3:

1, 2, 3 with the same embodiment 1;

4, the preparation of the encapsulation 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 Å / s;

An oxynitride film is formed by magnetron sputtering on the protective layer, and the oxynitride film is a nitride film of a doped oxide and a fluorine compound, wherein the oxide material is titanium dioxide and the nitride material is boron nitride. The fluoride material is zirconium tetrafluoride, and the mass ratio of oxide, fluoride to nitride is 6:5:9. Among them, 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 μm;

The oxynitride 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 Å/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 Å / s;

5, the preparation of the package cover:

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.

Example 4:

1, 2, 3 with the same embodiment 1;

4, the preparation of the encapsulation 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 Å / 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 fluorine compound, wherein the oxide material is cerium oxide and the nitride material is nitrogen. Silicon, fluoride material is barium fluoride, the mass ratio of oxide, fluoride and nitride is 4:3:13. Among them, the magnetron sputtering conditions are as follows: a three-target magnetron sputtering deposition system is used, the background vacuum is set to 2 × 10 ^-4 Pa, the film thickness is set to 120 nm, and the sputtering rate is 20 nm/min. Controlled sputtering to obtain an oxynitride film.

The oxynitride 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 Å/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 Å / s;

5, the preparation of the package cover:

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.

Example 5:

1, 2, 3 with the same embodiment 1;

4, the preparation of the encapsulation 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 Å / 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 fluorine compound, wherein the oxide material is cerium oxide and the nitride material is nitrogen. In bismuth, the fluoride material is barium fluoride, and the mass ratio of oxide, fluoride to nitride is 4:3:13. Among them, 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 1 nm/min. Controlled sputtering to obtain an oxynitride film.

5, the preparation of the package cover:

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.

Example 6:

1, 2, 3 with the same embodiment 1;

4, the preparation of the encapsulation 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 Å / 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 fluorine compound, wherein the oxide material is tantalum pentoxide, and the nitride material is Titanium nitride, the fluoride material is aluminum fluoride, and the mass ratio of oxide, fluoride to nitride is 4:3:13. Among them, the magnetron sputtering conditions are as follows: a three-target magnetron sputtering deposition system is used, the background vacuum is set to 2 × 10 ^-4 Pa, the film thickness is set to 140 nm, and the sputtering rate is 5 nm/min. Controlled sputtering to obtain an oxynitride film.

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 Å / s;

5, the preparation of the package cover:

Effect embodiment

In order to effectively prove the beneficial effects of the organic electroluminescent device of the present invention and the preparation method thereof, relevant experimental data is provided as follows.

The 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 ° C ~ 25 ° C, humidity 40% ~ 60%. The results are as follows:

Table 1. Examples 1~6 Organic Electroluminescent Devices Water Oxygen Permeability

	实施例1 Example 1	实施例2 Example 2	实施例3 Example 3	实施例4 Example 4	实施例5 Example 5	实施例6 Example 6
WVTR(g/m²/day)WVTR(g/m ² /day)	3.4 E^-5 3.4 E ^-5	2.1 E^-5 2.1 E ^-5	4.3 E^-5 4.3 E ^-5	3.0 E^-5 3.0 E ^-5	1.1 E^-5 1.1 E ^-5	2.7 E^-5 2.7 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 4.3 E ^-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 ° C ~ 25 ° C, humidity 40% ~ 60%.

Table 2. Example 1~6 Life of organic electroluminescent device

	实施例1 Example 1	实施例2 Example 2	实施例3 Example 3	实施例4 Example 4	实施例5 Example 5	实施例6 Example 6
寿命（万小时）（ T70@1000cd/m² ）Life (ten thousand hours) ( T70@1000cd/m ² )	1.4101 1.4101	1.4711 1.4711	1.4012 1.4012	1.4414 1.4414	1.4913 1.4913	1.4505 1.4505

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 149.31 million hours (T70@1000 cd/m ² ).

In summary, 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.

Claims

An organic electroluminescent device comprising a substrate, an anode, a functional layer, a cathode, an encapsulation layer and a package cover which are sequentially stacked, 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 The encapsulation layer includes a protective layer, an oxynitride film, an organic barrier layer, a moisture absorbing layer and a heat dissipation layer in sequence;

The oxynitride film is a nitride film doped with an oxide and a fluorine compound, wherein the oxide material is silica, alumina, zirconia, titania, ceria or pentoxide钽, the nitride material is silicon nitride, aluminum nitride, boron nitride, silicon nitride, tantalum nitride or titanium nitride, and the fluoride material is aluminum fluoride, germanium tetrafluoride, and four Zirconium fluoride, barium fluoride or barium fluoride, the mass ratio of the oxide, fluoride to nitride is 2 to 6:1 to 5:9 to 17.
The organic electroluminescent device according to claim 1, wherein the oxynitride film has a thickness of from 100 nm to 150 nm .
The organic electroluminescent device according to claim 1, wherein 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 ~ 300 nm;

The material of the organic barrier layer is polytetrafluoroethylene, methacrylic resin or cycloaliphatic epoxy resin, and the organic barrier layer has a thickness of 1 μm to 1.5 μm. .
Claims 1 The organic electroluminescent device is characterized in that the material of the moisture absorbing layer is calcium oxide, cerium oxide, cerium oxide or magnesium oxide, and the moisture absorbing layer has a thickness of 100 nm to 200 nm. ;

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 nm to 500 nm; The package cover is a metal foil, and the material of the metal foil is silver, aluminum or copper.
Claims 1 In the above organic electroluminescence device, the oxynitride film and the organic barrier layer are alternately laminated, and the number of laminated layers is three or more.
A method for preparing an organic electroluminescent device, comprising the steps of:

Preparing an 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;

Preparing the oxynitride film on the protective layer by magnetron sputtering co-sputtering, wherein the oxide material is silicon dioxide, aluminum oxide, zirconium dioxide, titanium dioxide, hafnium oxide or pentoxide Second, the nitride material is silicon nitride, aluminum nitride, boron nitride, silicon nitride, tantalum nitride or titanium nitride, and the fluoride material is aluminum fluoride, germanium tetrafluoride, The zirconium tetrafluoride, cesium fluoride or cesium fluoride, the magnetron sputtering condition is: using a three-target magnetron sputtering deposition system, setting the background vacuum to be 1 × 10 -5 Pa - 1 × 10 -3 Pa, the film thickness is set to be 100 nm to 150 nm, and the mass ratio of the oxide, fluoride and nitride is 2 to 6:1 to 5:9 to 17 as a target at a sputtering rate of 5 nm/min. Magnetron sputtering under ～40 nm/min to obtain an oxynitride film;

Then, the organic barrier layer is prepared on the oxynitride film by a spin coating and post-exposure process. 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, the light intensity is from 10 mW/cm 2 to 15 mW/cm 2 , and the exposure time is from 200s to 300s.

Then, the moisture absorption layer is prepared by sputtering on the organic barrier layer, and the heat sink is vacuum evaporated on the moisture absorption layer;

Finally, 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 method of preparing an organic electroluminescent device according to claim 6, wherein the oxynitride film has a thickness of 100 nm to 150 Nm.
The method of preparing an organic electroluminescent device according to claim 6, wherein 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 μm to 1.5 μm. .
Claim 6 The method for preparing an organic electroluminescent device, wherein the moisture absorbing layer is made of calcium oxide, cerium oxide, cerium oxide or magnesium oxide, and the moisture absorbing layer has a thickness of 100 nm to 200 nm. 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 nm to 500 nm. The package cover is a metal foil, and the material of the metal foil is silver, aluminum or copper.
Claim 6 The method for preparing an organic electroluminescent device, characterized in that the preparation process of the oxynitride film and the organic barrier layer is repeated, and the oxynitride film and the organic barrier layer are stacked and alternately laminated. The number of layers is greater than or equal to 3 layers.