CN103904235B - Organic electroluminescence device and preparation method thereof - Google Patents
Organic electroluminescence device and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000005401 electroluminescence Methods 0.000 title abstract 6
- 230000004888 barrier function Effects 0.000 claims abstract description 122
- 238000002347 injection Methods 0.000 claims abstract description 61
- 239000007924 injection Substances 0.000 claims abstract description 61
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- 150000004767 nitrides Chemical class 0.000 claims description 37
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 claims description 33
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 32
- 230000005525 hole transport Effects 0.000 claims description 30
- 238000007738 vacuum evaporation Methods 0.000 claims description 18
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical group C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 claims description 12
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical group F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 12
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- UEEXRMUCXBPYOV-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 UEEXRMUCXBPYOV-UHFFFAOYSA-N 0.000 claims description 9
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 9
- RKVIAZWOECXCCM-UHFFFAOYSA-N 2-carbazol-9-yl-n,n-diphenylaniline Chemical compound C1=CC=CC=C1N(C=1C(=CC=CC=1)N1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1 RKVIAZWOECXCCM-UHFFFAOYSA-N 0.000 claims description 8
- 238000010030 laminating Methods 0.000 claims description 8
- 229910004504 HfF4 Inorganic materials 0.000 claims description 7
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
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- 238000001771 vacuum deposition Methods 0.000 claims description 6
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 claims description 5
- -1 1-phenyl-1H-benzimidazole-2-yl Chemical group 0.000 claims description 3
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 claims description 3
- HONWGFNQCPRRFM-UHFFFAOYSA-N 2-n-(3-methylphenyl)-1-n,1-n,2-n-triphenylbenzene-1,2-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C(=CC=CC=2)N(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 HONWGFNQCPRRFM-UHFFFAOYSA-N 0.000 claims description 3
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 claims description 3
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 claims description 3
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 claims description 3
- DIVZFUBWFAOMCW-UHFFFAOYSA-N 4-n-(3-methylphenyl)-1-n,1-n-bis[4-(n-(3-methylphenyl)anilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 DIVZFUBWFAOMCW-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
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- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 11
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- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
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- 229910021332 silicide Inorganic materials 0.000 description 3
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
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- 229910021359 Chromium(II) silicide Inorganic materials 0.000 description 1
- 229910020968 MoSi2 Inorganic materials 0.000 description 1
- 229910020044 NbSi2 Inorganic materials 0.000 description 1
- 229910004217 TaSi2 Inorganic materials 0.000 description 1
- 229910008479 TiSi2 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DFJQEGUNXWZVAH-UHFFFAOYSA-N bis($l^{2}-silanylidene)titanium Chemical compound [Si]=[Ti]=[Si] DFJQEGUNXWZVAH-UHFFFAOYSA-N 0.000 description 1
- 125000004556 carbazol-9-yl group Chemical group C1=CC=CC=2C3=CC=CC=C3N(C12)* 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
- H10K50/8445—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/311—Flexible OLED
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention relates to a kind of organic electroluminescence device and preparation method thereof, this organic electroluminescence device is layer structure, this layer structure stacks gradually as anode conducting substrate, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer, to be laminated with by some layers of inorganic barrier layer and the alternately laminated mixing barrier layer formed of inorganic barrier layer on described cathode layer surface.Organic electroluminescence device of the present invention; the encapsulating material adopted is cheap; effectively can reduce outside water, oxygen isoreactivity material to the erosion of organic electroluminescence device; thus effective protection is defined to the organic functional material of organic electroluminescence device and electrode; meet the requirement of the sealing of encapsulation, the life-span of OLED can be improved significantly.
Description
Technical Field
The invention relates to the field of photoelectronic devices, in particular to an organic electroluminescent device. The invention also relates to a preparation method of the organic electroluminescent device.
Background
Organic electroluminescent devices (OLEDs) are a class of current-mode semiconductor light-emitting devices based on organic materials. The typical structure is that a luminescent layer with the thickness of dozens of nanometers is made on ITO glass by organic luminescent materials, and a metal electrode with low work function is arranged above the luminescent layer. When a voltage is applied across the electrodes, the light-emitting layer generates light radiation.
The OLED device has the advantages of active light emission, high light emitting efficiency, low power consumption, lightness, thinness, no viewing angle limitation, and the like, and is considered by the industry as a new generation device which is most likely to occupy an dominating position in the future illumination and display device market. As a new lighting and display technology, OLED technology has developed rapidly over the last decade, with great success. As more and more illumination and display manufacturers are increasingly invested in research and development in the world, the industrialization process of the OLED is greatly promoted, so that the growth speed of the OLED industry is remarkable, and the day before large-scale mass production is reached.
Flexible products are the development trend of organic electroluminescent devices, but the problem of short service life generally exists at present, so the service life of the devices is directly influenced by the quality of the packaging technology. The invention mainly aims to provide an organic electroluminescent device and a preparation method thereof, and the packaging technology has the advantages of simple process, strong water and oxygen resistance (WVTR) and obviously prolonged service life of the flexible OLED device.
Disclosure of Invention
The invention aims to solve the problems and the defects in the prior art and provides an organic electroluminescent device and a preparation method thereof.
The first technical solution proposed by the present invention to solve the above technical problems is: an organic electroluminescent device, the organic electroluminescent device is a laminated structure, the laminated structure is sequentially laminated as follows: an anode conductive substrate, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode layer; the cathode layer is characterized in that a mixed barrier layer formed by alternately laminating a plurality of organic barrier layers and inorganic barrier layers is laminated on the surface of the cathode layer; wherein the material of the organic barrier layer is one of copper phthalocyanine, N ' -diphenyl-N, N ' -di (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine, 8-hydroxyquinoline aluminum, 4',4' ' -tri (N-3-methylphenyl-N-phenylamino) triphenylamine or 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline.
The inorganic barrier layer is made of a mixture consisting of a telluride layer, a nitride layer and fluoride; the telluride layer is made of Sb2Te3、Bi2Te、CdTe、In2Te3One of SnTe or PbTe; the material of the nitride layer is Si3N4AlN, BN, SiN, TaN or TiN, the material of the fluoride layer is AlF3、HfF4、ZrF4、LiF、CeF2Or YF3One kind of (1). The telluride accounts for 10-30 wt% of the inorganic barrier layer, the nitride accounts for 40-80 wt% of the inorganic barrier layer, and the fluoride accounts for 10-30 wt% of the inorganic barrier layer.
The thickness of the inorganic barrier layer is 100 nm-200 nm. The thickness of the organic barrier layer is 200 nm-300 nm.
The number of the organic barrier layers and the inorganic barrier layers which are alternately stacked is 4-6.
The hole injection layer is made of MoO3The doped mixed material is formed by doping N, N '-diphenyl-N, N' -di (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine according to the doping concentration of 30 wt%.
The material of the hole transport layer adopts 4,4',4' ' -tri (carbazole-9-yl) triphenylamine.
The material of the luminescent layer is a doped mixed material formed by doping tris (2-phenylpyridine) iridium into 1,3, 5-tris (1-phenyl-1H-benzimidazole-2-yl) according to the doping concentration of 5 wt%.
The material of the electron transport layer is 4, 7-diphenyl-1, 10-phenanthroline.
The electron injection layer is made of CsN3The mixed material is formed by doping 4, 7-diphenyl-1, 10-phenanthroline according to the doping concentration of 25 wt%.
Another technical solution proposed by the present invention to solve the above technical problem is: a preparation method of an organic electroluminescent device comprises the following steps: (a) and sequentially laminating a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer, an electron injection layer and a metal cathode layer on the anode conducting layer of the cleaned anode conducting substrate by adopting a vacuum evaporation method.
(b) On the metal cathode layer, firstly, preparing an organic barrier layer by adopting a vacuum evaporation method; preparing an inorganic barrier layer on the organic barrier layer by adopting a magnetron sputtering method; then, preparing an organic barrier layer and an inorganic barrier layer by sequentially and alternately laminating for a plurality of times, and finally forming a mixed barrier layer; wherein the organic barrier layer is made of CuPc, NPB and Alq3m-MTDATA or BCP.
The inorganic barrier layer is made of a mixture consisting of a telluride layer, a nitride layer and fluoride; the telluride layer is made of Sb2Te3、Bi2Te、CdTe、In2Te3One of SnTe or PbTe; the material of the nitride layer is Si3N4AlN, BN, SiN, TaN or TiN, the material of the fluoride layer is AlF3、HfF4、ZrF4、LiF、CeF2Or YF3One kind of (1).
The telluride accounts for 10-30 wt% of the inorganic barrier layer, the nitride accounts for 40-80 wt% of the inorganic barrier layer, and the fluoride accounts for 10-30 wt% of the inorganic barrier layer.
The thickness of the inorganic barrier layer is 100 nm-200 nm; the thickness of the organic barrier layer is 200 nm-300 nm.
In the step (a), the vacuum degree of the vacuum evaporation of the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, the electron injection layer and the cathode layer is 3 × 10-5Pa, evaporation rate of 0.1 Å/s.
In the step (b), the number of times of alternation of the organic barrier layer and the inorganic barrier layer is 4-6 times.
In the step (b), when the vacuum evaporation is used for preparing the organic barrier layer, the vacuum degree of the vacuum evaporation is 1 × 10-5Pa～1×10-3Pa, the evaporation speed of the vacuum evaporation is 0.5 Å/s-5 Å/s, and the vacuum degree is 1 × 10 when the magnetron sputtering is used for preparing the inorganic barrier layer-5Pa～1×10-3Pa。
Compared with the prior art, the organic electroluminescent device and the preparation method thereof have the following advantages: 1. the packaging material adopted by the organic electroluminescent device is low in cost, and can effectively reduce the erosion of active substances such as external water, oxygen and the like to the organic electroluminescent device, so that the organic functional material and the electrode of the organic electroluminescent device are effectively protected, the requirement on the sealing property of the packaging is met, and the service life of the OLED device can be obviously prolonged. The water oxygen resistance (WVTR) reaches 10－ 4g/m2Day, the lifetime of the OLED light emitting device made therefrom also reached an average of more than 8500 hours.
2. The preparation method of the organic electroluminescent device is simple in preparation process and easy for large-area preparation, is particularly suitable for application of the flexible OLED device, solves the packaging problem of the flexible OLED, and promotes the development of flexible OLED products.
Drawings
Fig. 1 is a schematic view of the structure of an organic electroluminescent device of the present invention.
Detailed Description
The present invention will be further described in detail with reference to the following examples.
The organic electroluminescent device of the present invention has a layered structure, and as shown in fig. 1, the layered structure includes an anode conductive substrate 101, a hole injection layer 102, a hole transport layer 103, a light emitting layer 104, an electron transport layer 105, an electron injection layer 106, a cathode layer 107, an organic barrier layer 108, and an inorganic barrier layer 109, which are sequentially stacked.
In the organic electroluminescent device, a mixed barrier layer formed by alternately laminating a plurality of organic barrier layers and inorganic barrier layers is laminated on the surface of the cathode layer. The number of the organic barrier layers and the inorganic barrier layers which are alternately stacked is 4-6.
The inorganic barrier layer is made of a mixture consisting of a telluride layer, a nitride layer and fluoride; the telluride layer is made of Sb2Te3、Bi2Te、CdTe、In2Te3One of SnTe or PbTe; the material of the nitride layer is Si3N4AlN, BN, SiN, TaN or TiN, the material of the fluoride layer is AlF3、HfF4、ZrF4、LiF、CeF2Or YF3One kind of (1). The telluride accounts for 10-30 wt% of the inorganic barrier layer, the nitride accounts for 40-80 wt% of the inorganic barrier layer, and the fluoride accounts for 10-30 wt% of the inorganic barrier layer.
The organic barrier layer is made of one of copper phthalocyanine, N ' -diphenyl-N, N ' -di (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine, 8-hydroxyquinoline aluminum, 4',4' ' -tri (N-3-methylphenyl-N-phenylamino) triphenylamine or 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline.
The thickness of the inorganic barrier layer is 100 nm-200 nm. The thickness of the organic barrier layer is 200 nm-300 nm.
In the organic electroluminescent device, the anode conductive substrate 101 includes an anode conductive layer and a substrate, the substrate may be a glass substrate or an organic thin film substrate, the anode conductive layer may be made of conductive oxides, such as Indium Tin Oxide (ITO), aluminum-doped zinc oxide (AZO), indium-doped zinc oxide (IZO) or fluorine-doped zinc oxide (FTO), and the conductive oxides are prepared on the glass substrate, which are abbreviated as ITO glass, AZO glass, IZO glass, and FTO glass. The anode conductive substrate may be made by itself or may be commercially available. In practical applications, other suitable materials can be selected as the anode conductive substrate 101 according to requirements. In practical applications, a desired anode pattern of the organic electroluminescent device can be prepared on the anode conductive substrate 101. The anode conductive substrate 101 is conventional and will not be described herein.
In the organic electroluminescent device, the materials and thicknesses of other functional layers are as follows: the hole injection layer is made of MoO3Doping the mixed material into N, N '-diphenyl-N, N' -di (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine according to the doping concentration of 30 wt%; the thickness is 10 nm.
The material of the hole transport layer adopts 4,4',4' ' -tri (carbazole-9-yl) triphenylamine; thickness of 30nm
The material of the luminescent layer is a doped mixed material formed by doping tris (2-phenylpyridine) iridium into 1,3, 5-tris (1-phenyl-1H-benzimidazole-2-yl) according to the doping concentration of 5 wt%; the thickness is 20 nm.
The material of the electron transport layer is 4, 7-diphenyl-1, 10-phenanthroline; the thickness is 10 nm.
The electron injection layer is made of CsN3A mixed material formed by doping 4, 7-diphenyl-1, 10-phenanthroline according to the doping concentration of 25 wt%; the thickness is 20 nm.
The metal cathode layer is made of aluminum (Al) and is 100nm thick.
The preparation method of the organic electroluminescent device comprises the following steps: (a) and sequentially laminating a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer, an electron injection layer and a metal cathode layer on the anode conducting layer of the cleaned anode conducting substrate by adopting a vacuum evaporation method.
The vacuum degree of the hole injection layer, the hole transport layer, the luminescent layer, the electron transport layer, the electron injection layer and the cathode layer is 3 × 10 during vacuum evaporation preparation-5Pa, evaporation rate of 0.1 Å/s.
(b) On the metal cathode layer, firstly, preparing an organic barrier layer by adopting a vacuum evaporation method; preparing an inorganic barrier layer on the organic barrier layer by adopting a magnetron sputtering method; then, preparing an organic barrier layer and an inorganic barrier layer by sequentially and alternately laminating for a plurality of times, and finally forming a mixed barrier layer; the organic barrier layer and the inorganic barrier layer are alternated for 4-6 times.
When the vacuum evaporation is used for preparing the organic barrier layer, the vacuum degree of the vacuum evaporation is 1 × 10-5Pa～1×10-3Pa, the evaporation speed of the vacuum evaporation is 0.5 Å/s-5 Å/s, and the vacuum degree is 1 × 10 when the magnetron sputtering is used for preparing the inorganic barrier layer-5Pa～1×10-3Pa。
Wherein the organic barrier layer is made of CuPc, NPB and Alq3One of m-MTDATA or BCP; the inorganic barrier layer is made of a mixture of oxide, nitride and silicide; the oxide is SiO2、Al2O3、TiO2、ZrO2、HfO2Or Ta2O5The nitride is Si3N4AlN, BN, SiN, TaN or TiN, the silicide being CrSi2、TaSi2、HfSi2、TiSi2、MoSi2Or NbSi2One kind of (1).
The oxide accounts for 10wt% -30 wt% of the inorganic barrier layer, the silicide accounts for 10wt% -25 wt% of the inorganic barrier layer, and the nitride accounts for 45wt% -80 wt% of the inorganic barrier layer. The thickness of the inorganic barrier layer is 100 nm-150 nm; the thickness of the organic barrier layer is 200 nm-300 nm.
The organic electroluminescent element and the production process thereof according to the present invention will be specifically described below in examples 1 to 6.
Examples 1 ：The organic electroluminescent device in this embodiment is a layered structure, and the layered structure sequentially includes: anode conductive substrate layer/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode layer/organic barrier layer/inorganic barrier layer.
In this embodiment, the following steps are specifically performed in sequence: ITO glass substrate/MoO3-NPB layer/TCTA layer/TPBI-Ir (ppy)3layer/Bphen layer/CsN3-Bphen layer/Al layer/CuPc layer/Sb2Te3-Si3N4-AlF3And (3) a layer.
The organic electroluminescent device is prepared by adopting the following steps: a) pretreatment of the ITO glass substrate: acetone cleaning → ethanol cleaning → deionized water cleaning → ethanol cleaning, wherein the cleaning is carried out by an ultrasonic cleaning machine, each time for 5 minutes, then blowing dry by nitrogen, and then baking by an oven for standby; the cleaned ITO glass needs to be subjected to surface activation treatment so as to increase the oxygen content of the conductive surface layer and improve the work function of the surface of the conductive layer; the thickness of the ITO glass substrate was 100 nm.
b) Preparation of hole injection layer: adding MoO3Doping NPB as hole injection material with doping concentration of 30wt%, thickness of 10nm, and vacuum degree of 3 × 10-5Pa, evaporation rate of 0.1 Å/s.
c) Preparation of hole transport layer: using 4,4',4' ' -tri (carbazol-9-yl) triphenylamine (TCT)A) Vacuum 3 × 10 as a hole transport material-5Pa, evaporation rate 0.1 Å/s, evaporation thickness 30 nm.
d) Light-emitting layer: 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBI) is used as a host material, and tri (2-phenylpyridine) iridium (Ir (ppy) is used as a guest material3) Doping concentration of 5% and degree of vacuum of 3 × 10-5Pa, evaporation rate 0.2 Å/s, evaporation thickness 20 nm.
e) Preparing electron transport layer by vapor-depositing a layer of 4, 7-diphenyl-1, 10-phenanthroline (Bphen) as electron transport layer on the luminescent layer with vacuum degree of 3 × 10-5Pa, evaporation rate 0.1 Å/s, evaporation thickness 10 nm.
f) Preparation of an electron injection layer: taking a Bphen electron injection layer as a host material of CsN3Doped into Bphen with the doping concentration of 30wt% and the vacuum degree of 3 × 10-5Pa, the evaporation speed is 0.2 Å/s, and the evaporation thickness is 20 nm;
g) preparing cathode layer by using aluminum (Al) as metal cathode with thickness of 100nm and vacuum degree of 5 × 10-5Pa, evaporation rate 5 Å/s.
h) Preparing an organic barrier layer by preparing a layer of CuPc on the cathode layer by vacuum evaporation with a vacuum degree of 1 × 10-5Pa, evaporation rate 5 Å/s, thickness 300 nm.
i) Manufacturing an inorganic barrier layer: the telluride layer is Sb2Te3The nitride layer is Si3N4The fluoride layer is AlF3The tellurium-fluorine nitride film is manufactured by adopting a magnetron sputtering method, and the background vacuum degree is 1 × 10-5Pa, the target material is corresponding telluride, nitride and nitride, the telluride accounts for 30wt%, the fluoride accounts for 30wt%, the nitride accounts for 40wt%, and the thickness of the inorganic barrier layer is 200 nm.
j) Repeating the steps h) and i)6 times alternately.
Examples 2 ：The organic electroluminescent device in this embodiment is a layered structure, and the layered structure sequentially includes: anode conductive substrate layer/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode layer/organic barrier layer/inorganic barrier layer.
In this embodiment, the following steps are specifically performed in sequence: ITO glass substrate/MoO3-NPB layer/TCTA layer/TPBI-Ir (ppy)3layer/Bphen layer/CsN3-Bphen layer/Al layer/CuPc layer/Bi2Te-AlN- HfF4And (3) a layer.
The organic electroluminescent device is prepared by adopting the following steps: a) pretreatment of the ITO glass substrate: acetone cleaning → ethanol cleaning → deionized water cleaning → ethanol cleaning, wherein the cleaning is carried out by an ultrasonic cleaning machine, each time for 5 minutes, then blowing dry by nitrogen, and then baking by an oven for standby; the cleaned ITO glass needs to be subjected to surface activation treatment so as to increase the oxygen content of the conductive surface layer and improve the work function of the surface of the conductive layer; the thickness of the ITO glass substrate was 100 nm.
b) Preparation of hole injection layer: adding MoO3Doping NPB as hole injection material with doping concentration of 30wt%, thickness of 10nm, and vacuum degree of 3 × 10-5Pa, evaporation rate of 0.1 Å/s;
c) preparing a hole transport layer by adopting 4,4',4' ' -tri (carbazole-9-yl) triphenylamine (TCTA) as a hole transport material and the vacuum degree of 3 × 10-5Pa, evaporation rate 0.1 Å/s, evaporation thickness 30 nm.
d) Light-emitting layer: 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBI) is used as a host material, and tri (2-phenylpyridine) iridium (Ir (ppy) is used as a guest material3) Doping concentration of 5% and degree of vacuum of 3 × 10-5Pa, evaporation rate 0.2 Å/s, evaporation thickness 20 nm.
e) Preparing electron transport layer by vapor-depositing a layer of 4, 7-diphenyl-1, 10-phenanthroline (Bphen) as electron transport layer on the luminescent layer with vacuum degree of 3 × 10-5Pa, evaporation rate0.1 Å/s, evaporation thickness 10 nm.
f) Preparation of an electron injection layer: taking a Bphen electron injection layer as a host material of CsN3Doped into Bphen with the doping concentration of 30wt% and the vacuum degree of 3 × 10-5Pa, evaporation rate 0.2 Å/s, evaporation thickness 20 nm.
g) Preparing cathode layer by using aluminum (Al) as metal cathode with thickness of 100nm and vacuum degree of 5 × 10-5Pa, evaporation rate 5 Å/s.
h) Preparing an organic barrier layer by preparing a layer of CuPc on the cathode layer by vacuum evaporation with a vacuum degree of 1 × 10-5Pa, evaporation rate 5 Å/s, thickness 300 nm.
i) Manufacturing an inorganic barrier layer: the telluride layer is Bi2Te, fluoride layer is HfF4The nitride layer is AlN, and is made into a tellurium-fluorine nitride film by a magnetron sputtering method, the background vacuum degree is 5 × 10-5Pa, the target material is corresponding telluride, nitride and fluoride, the telluride accounts for 10wt%, the fluoride accounts for 10wt%, the nitride accounts for 80wt%, and the thickness of the inorganic barrier layer is 100 nm.
j) Repeating steps i) and j)6 times alternately.
Examples 3 ：The organic electroluminescent device in this embodiment is a layered structure, and the layered structure sequentially includes: anode conductive substrate layer/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode layer/organic barrier layer/inorganic barrier layer.
In this embodiment, the following steps are specifically performed in sequence: ITO glass substrate/MoO3-NPB layer/TCTA layer/TPBI-Ir (ppy)3layer/Bphen layer/CsN3-Bphen layer/Al layer/CuPc layer/CdTe-BN-ZrF4And (3) a layer.
The organic electroluminescent device is prepared by adopting the following steps: a) pretreatment of the ITO glass substrate: acetone cleaning → ethanol cleaning → deionized water cleaning → ethanol cleaning, wherein the cleaning is carried out by an ultrasonic cleaning machine, each time for 5 minutes, then blowing dry by nitrogen, and then baking by an oven for standby; the cleaned ITO glass needs to be subjected to surface activation treatment so as to increase the oxygen content of the conductive surface layer and improve the work function of the surface of the conductive layer; the thickness of the ITO glass substrate was 100 nm.
b) Preparation of hole injection layer: adding MoO3Doping NPB as hole injection material with doping concentration of 30wt%, thickness of 10nm, and vacuum degree of 3 × 10-5Pa, evaporation rate of 0.1 Å/s.
c) Preparing a hole transport layer by adopting 4,4',4' ' -tri (carbazole-9-yl) triphenylamine (TCTA) as a hole transport material and the vacuum degree of 3 × 10-5Pa, evaporation rate 0.1 Å/s, evaporation thickness 30 nm.
d) Light-emitting layer: 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBI) is used as a host material, and tri (2-phenylpyridine) iridium (Ir (ppy) is used as a guest material3) Doping concentration of 5% and degree of vacuum of 3 × 10-5Pa, evaporation rate 0.2 Å/s, evaporation thickness 20 nm.
e) Preparing electron transport layer by vapor-depositing a layer of 4, 7-diphenyl-1, 10-phenanthroline (Bphen) as electron transport layer on the luminescent layer with vacuum degree of 3 × 10-5Pa, evaporation rate 0.1 Å/s, evaporation thickness 10 nm.
f) Preparation of an electron injection layer: taking a Bphen electron injection layer as a host material of CsN3Doped into Bphen with the doping concentration of 30wt% and the vacuum degree of 3 × 10-5Pa, the evaporation speed is 0.2 Å/s, and the evaporation thickness is 20 nm;
g) preparing cathode layer by using aluminum (Al) as metal cathode with thickness of 100nm and vacuum degree of 5 × 10-5Pa, evaporation rate 5 Å/s.
h) Preparing an organic barrier layer by preparing a layer of CuPc on the cathode layer by vacuum evaporation with a vacuum degree of 1 × 10-5Pa, evaporation rate 5 Å/s, thickness 300 nm.
i) Manufacturing an inorganic barrier layer: the telluride layer is CdTe, the nitride layer is BN, and the fluoride layer is ZrF4The tellurium-fluorine nitride film is manufactured by a magnetron sputtering method, and the background vacuum degree is 5 × 10-5Pa, the target material is corresponding telluride, nitride and fluoride, the telluride accounts for 15 wt%, the fluoride accounts for 15 wt%, the nitride accounts for 70wt%, and the inorganic barrier layer has a thickness of 150 nm.
j) Repeating steps i) and j)6 times alternately.
Examples 4 ：The organic electroluminescent device in this embodiment is a layered structure, and the layered structure sequentially includes: anode conductive substrate layer/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode layer/organic barrier layer/inorganic barrier layer.
In this embodiment, the following steps are specifically performed in sequence: ITO glass substrate/MoO3-NPB layer/TCTA layer/TPBI-Ir (ppy)3layer/Bphen layer/CsN3-Bphen layer/Al layer/CuPc layer/In2Te3-a HfN-LiF layer.
The organic electroluminescent device is prepared by adopting the following steps: a) pretreatment of the ITO glass substrate: acetone cleaning → ethanol cleaning → deionized water cleaning → ethanol cleaning, wherein the cleaning is carried out by an ultrasonic cleaning machine, each time for 5 minutes, then blowing dry by nitrogen, and then baking by an oven for standby; the cleaned ITO glass needs to be subjected to surface activation treatment so as to increase the oxygen content of the conductive surface layer and improve the work function of the surface of the conductive layer; the thickness of the ITO glass substrate was 100 nm.
b) Preparation of hole injection layer: adding MoO3Doping NPB as hole injection material with doping concentration of 30wt%, thickness of 10nm, and vacuum degree of 3 × 10-5Pa, evaporation rate of 0.1 Å/s.
c) Preparation of hole transport layer: using 4,4',4' ' -tris (carbazol-9-yl) trisAniline (TCTA) as hole transport material, vacuum 3 × 10-5Pa, evaporation rate 0.1 Å/s, evaporation thickness 30 nm.
d) Light-emitting layer: 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBI) is used as a host material, and tri (2-phenylpyridine) iridium (Ir (ppy) is used as a guest material3) Doping concentration of 5% and degree of vacuum of 3 × 10-5Pa, evaporation rate 0.2 Å/s, evaporation thickness 20 nm.
e) Preparing electron transport layer by vapor-depositing a layer of 4, 7-diphenyl-1, 10-phenanthroline (Bphen) as electron transport layer on the luminescent layer with vacuum degree of 3 × 10-5Pa, evaporation rate 0.1 Å/s, evaporation thickness 10 nm.
f) Preparation of an electron injection layer: taking a Bphen electron injection layer as a host material of CsN3Doped into Bphen with the doping concentration of 30wt% and the vacuum degree of 3 × 10-5Pa, evaporation rate 0.2 Å/s, evaporation thickness 20 nm.
g) Preparing cathode layer by using aluminum (Al) as metal cathode with thickness of 100nm and vacuum degree of 5 × 10-5Pa, evaporation rate 5 Å/s.
h) Preparing an organic barrier layer by preparing a layer of CuPc on the cathode layer by vacuum evaporation with a vacuum degree of 1 × 10-5Pa, evaporation rate 5 Å/s, thickness 300 nm.
i) Manufacturing an inorganic barrier layer: the telluride layer is In2Te3The nitride layer is HfN, the fluoride layer is LiF, the tellurium-fluorine nitride film is manufactured by a magnetron sputtering method, the background vacuum degree is 5 × 10-5Pa, the target material is corresponding telluride, nitride and fluoride, the telluride accounts for 15 wt%, the fluoride accounts for 20 wt%, the nitride accounts for 65wt%, and the thickness of the inorganic barrier layer is 130 nm.
j) Repeating steps d) and e) alternately 5 times.
Examples 5 ：In the present embodimentThe organic electroluminescent device is of a laminated structure, and the laminated structure sequentially comprises: anode conductive substrate layer/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode layer/organic barrier layer/inorganic barrier layer.
In this embodiment, the following steps are specifically performed in sequence: ITO glass substrate/MoO3-NPB layer/TCTA layer/TPBI-Ir (ppy)3layer/Bphen layer/CsN3-Bphen layer/Al layer/CuPc layer/SnTe-TaN-CeF2And (3) a layer.
The organic electroluminescent device is prepared by adopting the following steps: a) pretreatment of the ITO glass substrate: acetone cleaning → ethanol cleaning → deionized water cleaning → ethanol cleaning, wherein the cleaning is carried out by an ultrasonic cleaning machine, each time for 5 minutes, then blowing dry by nitrogen, and then baking by an oven for standby; the cleaned ITO glass needs to be subjected to surface activation treatment so as to increase the oxygen content of the conductive surface layer and improve the work function of the surface of the conductive layer; the thickness of the ITO glass substrate was 100 nm.
b) Preparation of hole injection layer: adding MoO3Doping NPB as hole injection material with doping concentration of 30wt%, thickness of 10nm, and vacuum degree of 3 × 10-5Pa, evaporation rate of 0.1 Å/s;
c) preparing a hole transport layer by adopting 4,4',4' ' -tri (carbazole-9-yl) triphenylamine (TCTA) as a hole transport material and the vacuum degree of 3 × 10-5Pa, evaporation rate 0.1 Å/s, evaporation thickness 30 nm.
d) Light-emitting layer: 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBI) is used as a host material, and tri (2-phenylpyridine) iridium (Ir (ppy) is used as a guest material3) Doping concentration of 5% and degree of vacuum of 3 × 10-5Pa, evaporation rate 0.2 Å/s, evaporation thickness 20 nm.
e) Preparing electron transport layer by vapor-depositing a layer of 4, 7-diphenyl-1, 10-phenanthroline (Bphen) as electron transport layer on the luminescent layer with vacuum degree of 3 × 10-5Pa, evaporation rate 0.1 Å/s, evaporation thickness 10 nm.
f) Preparation of an electron injection layer: taking a Bphen electron injection layer as a host material of CsN3Doped into Bphen with the doping concentration of 30wt% and the vacuum degree of 3 × 10-5Pa, evaporation rate 0.2 Å/s, evaporation thickness 20 nm.
g) Preparing cathode layer by using aluminum (Al) as metal cathode with thickness of 100nm and vacuum degree of 5 × 10-5Pa, evaporation rate 5 Å/s.
h) Preparing an organic barrier layer by preparing a layer of CuPc on the cathode layer by vacuum evaporation with a vacuum degree of 1 × 10-5Pa, evaporation rate 5 Å/s, thickness 300 nm.
i) Manufacturing an inorganic barrier layer: the telluride layer is SnTe, the nitride layer is TaN, and the fluoride layer is CeF2The tellurium-fluorine nitride film is manufactured by a magnetron sputtering method, and the background vacuum degree is 5 × 10-5Pa, the target material is corresponding telluride, nitride and fluoride, the telluride accounts for 18 wt%, the fluoride accounts for 20 wt%, the nitride accounts for 62wt%, and the thickness of the inorganic barrier layer is 150 nm.
j) Repeating steps d) and e) alternately 5 times.
Examples 6 ：The organic electroluminescent device in this embodiment is a layered structure, and the layered structure sequentially includes: anode conductive substrate layer/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode layer/organic barrier layer/inorganic barrier layer.
In this embodiment, the following steps are specifically performed in sequence: ITO glass substrate/MoO3-NPB layer/TCTA layer/TPBI-Ir (ppy)3layer/Bphen layer/CsN3-Bphen layer/Al layer/CuPc layer/PbTe-TiN-YF3And (3) a layer.
The organic electroluminescent device is prepared by adopting the following steps: a) pretreatment of the ITO glass substrate: acetone cleaning → ethanol cleaning → deionized water cleaning → ethanol cleaning, wherein the cleaning is carried out by an ultrasonic cleaning machine, each time for 5 minutes, then blowing dry by nitrogen, and then baking by an oven for standby; the cleaned ITO glass needs to be subjected to surface activation treatment so as to increase the oxygen content of the conductive surface layer and improve the work function of the surface of the conductive layer; the thickness of the ITO glass substrate was 100 nm.
b) Preparation of hole injection layer: adding MoO3Doping NPB as hole injection material with doping concentration of 30wt%, thickness of 10nm, and vacuum degree of 3 × 10-5Pa, evaporation rate of 0.1 Å/s.
c) Preparing a hole transport layer by adopting 4,4',4' ' -tri (carbazole-9-yl) triphenylamine (TCTA) as a hole transport material and the vacuum degree of 3 × 10-5Pa, evaporation rate 0.1 Å/s, evaporation thickness 30 nm.
d) Light-emitting layer: 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBI) is used as a host material, and tri (2-phenylpyridine) iridium (Ir (ppy) is used as a guest material3) Doping concentration of 5% and degree of vacuum of 3 × 10-5Pa, evaporation rate 0.2 Å/s, evaporation thickness 20 nm.
e) Preparing electron transport layer by vapor-depositing a layer of 4, 7-diphenyl-1, 10-phenanthroline (Bphen) as electron transport layer on the luminescent layer with vacuum degree of 3 × 10-5Pa, evaporation rate 0.1 Å/s, evaporation thickness 10 nm.
f) Preparation of an electron injection layer: taking a Bphen electron injection layer as a host material of CsN3Doped into Bphen with the doping concentration of 30wt% and the vacuum degree of 3 × 10-5Pa, evaporation rate 0.2 Å/s, evaporation thickness 20 nm.
g) Preparing cathode layer by using aluminum (Al) as metal cathode with thickness of 100nm and vacuum degree of 5 × 10-5Pa, evaporation rate 5 Å/s.
h) Preparing an organic barrier layer by preparing a layer of CuPc on the cathode layer by vacuum evaporation with a vacuum degree of 1 × 10-5Pa, evaporation rate 5 Å/s, thickness 300 nm.
i) Of inorganic barrier layersPreparation: the telluride layer is PbTe, the nitride layer is TiN, and the fluoride layer is YF3The tellurium-fluorine nitride film is manufactured by a magnetron sputtering method, and the background vacuum degree is 1 × 10-3Pa, the target material is corresponding telluride, nitride and fluoride, the telluride accounts for 20 wt%, the fluoride accounts for 20 wt%, the nitride accounts for 60wt%, and the inorganic barrier layer has a thickness of 150 nm.
j) Repeating steps d) and e) alternately 4 times.
And (3) performance testing:the organic electroluminescent device of the present invention was tested for resistance to water and oxygen (WVTR) for the above examples 1 to 6, and it reached 10 as can be seen from table 1 below－ 4g/m2Performance above day, the lifetime of OLED light emitting devices made therefrom also reaches an average of above 8500 hours.
Table 1.
| TABLE 1 | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| WVTR(g/m2/day) | 2.5E-4 | 2.9 E-4 | 3.4E-4 | 3.6E-4 | 3.7E-4 | 4.2E-4 |
| Life (hours) | 8619 | 8581 | 8552 | 8521 | 8513 | 8461 |
Therefore, the organic electroluminescent device and the preparation method thereof have the following advantages: 1. the packaging material adopted by the organic electroluminescent device is low in cost, and can effectively reduce the erosion of active substances such as external water, oxygen and the like to the organic electroluminescent device, so that the organic functional material and the electrode of the organic electroluminescent device are effectively protected, the requirement on the sealing property of the packaging is met, and the service life of the OLED device can be obviously prolonged. The water and oxygen resistance of the paint reaches 10－ 4g/m2Day, the lifetime of the OLED light emitting device made therefrom also reached an average of more than 8500 hours.
2. The preparation method of the organic electroluminescent device is simple in preparation process and easy for large-area preparation, is particularly suitable for application of the flexible OLED device, solves the packaging problem of the flexible OLED, and promotes the development of flexible OLED products.
The above-mentioned embodiments are merely preferred examples of the present invention, and not intended to limit the present invention, and those skilled in the art can easily make various changes and modifications according to the main concept and spirit of the present invention, so that the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. An organic electroluminescent device, the organic electroluminescent device is a laminated structure, the laminated structure is sequentially laminated as follows: an anode conductive substrate, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode layer; the cathode layer is characterized in that a mixed barrier layer formed by alternately laminating a plurality of organic barrier layers and inorganic barrier layers is laminated on the surface of the cathode layer; wherein,
the organic barrier layer is made of one of copper phthalocyanine, N ' -diphenyl-N, N ' -di (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine, 8-hydroxyquinoline aluminum, 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine or 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline;
the inorganic barrier layer is made of a mixture consisting of telluride, nitride and fluoride; the telluride is Sb2Te3、Bi2Te、CdTe、In2Te3One of SnTe or PbTe; the nitride is Si3N4AlN, BN, SiN, TaN or TiN, and the fluoride is AlF3、HfF4、ZrF4、LiF、CeF2Or YF3One of (1);
the telluride accounts for 10-30 wt% of the inorganic barrier layer, the nitride accounts for 40-80 wt% of the inorganic barrier layer, and the fluoride accounts for 10-30 wt% of the inorganic barrier layer.
2. The organic electroluminescent device according to claim 1, wherein the inorganic barrier layer has a thickness of 100nm to 200 nm.
3. The organic electroluminescent device according to claim 1, wherein the organic barrier layer has a thickness of 200nm to 300 nm.
4. The organic electroluminescent device according to claim 1, wherein: the number of the organic barrier layers and the inorganic barrier layers which are alternately stacked is 4-6.
5. The organic electroluminescent device according to claim 1, wherein:
the hole injection layer is made of MoO3Doping the mixed material into N, N '-diphenyl-N, N' -di (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine according to the doping concentration of 30 wt%;
the hole transport layer is made of 4,4' -tris (carbazole-9-yl) triphenylamine;
the material of the luminescent layer is a doped mixed material formed by doping tris (2-phenylpyridine) iridium into 1,3, 5-tris (1-phenyl-1H-benzimidazole-2-yl) according to the doping concentration of 5 wt%;
the material of the electron transport layer is 4, 7-diphenyl-1, 10-phenanthroline;
the electron injection layer is made of CsN3The mixed material is formed by doping 4, 7-diphenyl-1, 10-phenanthroline according to the doping concentration of 25 wt%.
6. A preparation method of an organic electroluminescent device comprises the following steps:
(a) preparing a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer, an electron injection layer and a metal cathode layer in sequence on an anode conducting layer of a cleaned anode conducting substrate by adopting a vacuum evaporation method;
(b) on the metal cathode layer, firstly, preparing an organic barrier layer by adopting a vacuum evaporation method; preparing an inorganic barrier layer on the organic barrier layer by adopting a magnetron sputtering method; then, preparing an organic barrier layer and an inorganic barrier layer by sequentially and alternately laminating for a plurality of times, and finally forming a mixed barrier layer; wherein,
the organic barrier layer is made of CuPc, NPB and Alq3One of m-MTDATA or BCP;
the inorganic barrier layer is made of a mixture consisting of telluride, nitride and fluoride; the telluride is Sb2Te3、Bi2Te、CdTe、In2Te3One of SnTe or PbTe; the nitride is Si3N4AlN, BN, SiN, TaN or TiN, and the fluoride is AlF3、HfF4、ZrF4、LiF、CeF2Or YF3One of (1);
the telluride accounts for 10-30 wt% of the inorganic barrier layer, the nitride accounts for 40-80 wt% of the inorganic barrier layer, and the fluoride accounts for 10-30 wt% of the inorganic barrier layer.
7. The production method according to claim 6, wherein the inorganic barrier layer has a thickness of 100nm to 200 nm; the thickness of the organic barrier layer is 200 nm-300 nm.
8. The production method according to claim 6, wherein in the step (a), the vacuum degree of the vacuum evaporation production of the hole injection layer, the hole transport layer, the light-emitting layer, the electron transport layer, the electron injection layer and the cathode layer is 3 × 10-5Pa, evaporation rate of
9. The method according to claim 6, wherein in the step (b), the number of times of alternation of the organic barrier layer and the inorganic barrier layer is 4 to 6.
10. The method according to claim 6, wherein in the step (b), the vacuum degree of vacuum evaporation is 1 × 10 when the vacuum evaporation is used for preparing the organic barrier layer-5Pa～1×10-3Pa, the evaporation rate of the vacuum evaporation isWhen the inorganic barrier layer is prepared by magnetron sputtering, the vacuum degree is 1 × 10-5Pa～1×10-3Pa。
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| KR100943185B1 (en) * | 2008-04-24 | 2010-02-19 | 삼성모바일디스플레이주식회사 | Organic light emitting display device |
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| CN1395323A (en) * | 2001-07-03 | 2003-02-05 | 株式会社半导体能源研究所 | Luminescent device, method and electronic equipment for manufacturing luminescent device |
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