CN104078600A - Organic light-emitting diode device and manufacturing method thereof - Google Patents
Organic light-emitting diode device and manufacturing method thereof Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 230000004888 barrier function Effects 0.000 claims abstract description 175
- 238000002347 injection Methods 0.000 claims abstract description 69
- 239000007924 injection Substances 0.000 claims abstract description 69
- 239000000463 material Substances 0.000 claims abstract description 52
- 239000000758 substrate Substances 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000001704 evaporation Methods 0.000 claims description 101
- 230000008020 evaporation Effects 0.000 claims description 72
- 229910052751 metal Inorganic materials 0.000 claims description 42
- 239000002184 metal Substances 0.000 claims description 42
- 238000002360 preparation method Methods 0.000 claims description 36
- 230000005525 hole transport Effects 0.000 claims description 34
- 238000007738 vacuum evaporation Methods 0.000 claims description 27
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 24
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 24
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 22
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 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 claims description 12
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical compound F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 229910052737 gold Inorganic materials 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000005416 organic matter Substances 0.000 claims description 11
- 238000001771 vacuum deposition Methods 0.000 claims description 11
- 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
- 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 8
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 claims description 7
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 7
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 7
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 claims description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052960 marcasite Inorganic materials 0.000 claims description 7
- 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 7
- 229910052683 pyrite Inorganic materials 0.000 claims description 7
- 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 6
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 6
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- 239000007983 Tris buffer Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 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 5
- -1 1-phenyl-1H-benzimidazole-2-yl Chemical group 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 3
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
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- 238000007789 sealing Methods 0.000 abstract description 3
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- 239000011521 glass Substances 0.000 description 31
- 238000004140 cleaning Methods 0.000 description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- 239000000126 substance Substances 0.000 description 14
- 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 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 12
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- 238000007664 blowing Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000002344 surface layer Substances 0.000 description 6
- 238000004506 ultrasonic cleaning Methods 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 3
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical group C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 2
- 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 group 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 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000012536 packaging technology Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
- 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
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to an organic light-emitting diode device and a manufacturing method thereof. The organic light-emitting diode device is of a layer structure, the layer structure is formed by sequentially stacking an anode conductive substrate, a hole injection layer, a hole transmission layer, a light-emitting layer, an electron transmission layer, an electron injection layer and a cathode layer, and the surface of the cathode layer is provided with a mixed barrier layer and an inorganic barrier layer which are alternatively stacked. The organic light-emitting diode device adopts the mixed barrier layer and the inorganic barrier layer as mixtures, erosion of water, oxygen and other active substrate in the outside to the organic light-emitting diode device can be effectively reduced, accordingly an organic function material and electrodes of the organic light-emitting diode device are effectively protected, the sealing performance requirement of package is met, and the service life of the OLED device can be remarkably prolonged.
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 of the prior art and provides an organic electroluminescent device and a preparation method thereof.
The technical scheme provided by the invention aiming at the technical problems is as follows: 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 surface of the cathode layer is provided with a mixed barrier layer and an inorganic barrier layer which are alternately stacked; wherein,
the mixed barrier layer is made of a mixture of organic matters, metals and oxides; the organic matter is N, N '-diphenyl-N, N' -di (1)-naphthyl) -1,1' -biphenyl-4, 4' -diamine, 8-hydroxyquinoline aluminum, one of 4,4',4' ' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine, 4, 7-diphenyl-1, 10-phenanthroline or 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene, wherein the oxide is MoO3、V2O5、WO3、Cs2O、Ni2O or MnO2The metal is one of Ag, Al, Ni, Au, Cu or Pt, the metal accounts for 10-30 mol% of the mixed barrier layer, the oxide accounts for 30-50 mol% of the mixed barrier layer, and the organic matter accounts for 20-60 mol% of the mixed barrier layer;
the inorganic barrier layer is made of a mixture consisting of sulfide, fluoride and metal, wherein the sulfide is CdS, PbS or FeS2One of CuS, ZnS or NiS, and the fluoride is LiF or CeF2、MgF2、AlF3、CaF2Or BaF2The metal is one of Ag, Al, Ni, Au, Cu or Pt, the fluoride accounts for 10-30 mol% of the inorganic barrier layer, the sulfide accounts for 10-30 mol% of the inorganic barrier layer, and the metal accounts for 40-80 mol% of the inorganic barrier layer;
the thickness of the mixed barrier layer is 200 nm-300 nm; the thickness of the inorganic barrier layer is 100 nm-200 nm.
The number of the mixed barrier layers and the inorganic barrier layers which are alternately stacked is 4-6.
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 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 CsN3A mixed material formed by doping 4, 7-diphenyl-1, 10-phenanthroline according to the doping concentration of 30 wt%;
the cathode layer is made of ZnS, Ag and ZnS which are sequentially laminated by adopting a vacuum evaporation method.
The invention also comprises a preparation method of the organic electroluminescent device, which 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 cathode layer in sequence on an anode conducting layer of a cleaned anode conducting substrate by adopting a vacuum evaporation method;
(b) on the cathode layer, firstly, preparing a mixed barrier layer by adopting a vacuum evaporation method; preparing an inorganic barrier layer on the mixed barrier layer by adopting a vacuum evaporation method; then, alternately laminating for a plurality of times in sequence to prepare a mixed barrier layer and an inorganic barrier layer; wherein,
the mixed barrier layer is made of a mixture of organic matters, metals and oxides; the organic matter is one of N, 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, 4, 7-diphenyl-1, 10-phenanthroline or 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene, and the oxide is MoO3、V2O5、WO3、Cs2O、Ni2O or MnO2The metal is one of Ag, Al, Ni, Au, Cu or Pt, the metal accounts for 10-30 mol% of the mixed barrier layer, the oxide accounts for 30-50 mol% of the mixed barrier layer, and the organic matter accounts for 20-60 mol% of the mixed barrier layer;
the inorganic barrier layer is made of sulfide, fluoride and metalThe sulfide is CdS, PbS, FeS2One of CuS, ZnS or NiS, and the fluoride is LiF or CeF2、MgF2、AlF3、CaF2Or BaF2The metal is one of Ag, Al, Ni, Au, Cu or Pt, the fluoride accounts for 10-30 mol% of the inorganic barrier layer, the sulfide accounts for 10-30 mol% of the inorganic barrier layer, and the metal accounts for 40-80 mol% of the inorganic barrier layer;
the thickness of the mixed barrier layer is 200 nm-300 nm; the thickness of the inorganic barrier layer is 100 nm-200 nm.
In the step (a), the vacuum degree of the hole injection layer, the hole transport layer, the luminescent layer, the electron transport layer and the electron injection layer is 1 × 10-5Pa, the vacuum degree of the cathode layer is 3 multiplied by 10 during vacuum evaporation preparation-5Pa; the evaporation rate of the hole injection layer, the hole transport layer and the electron transport layer isThe evaporation rate of the luminescent layer and the electron injection layer isThe cathode layer has an evaporation rate of
In the step (b), the number of times of alternation of the mixed barrier layer and the inorganic barrier layer is 4-6 times.
In the step (b), when the vacuum evaporation is used for preparing the mixed barrier layer, the vacuum degree of the vacuum evaporation is 1 × 10-5Pa～1×10-3Pa, the evaporation rate of the vacuum evaporation isWhen the inorganic barrier layer is prepared by vacuum evaporation, the vacuum degree is 1 multiplied by 10-5Pa～1×10-3Pa。
Compared with the prior art, the organic electroluminescence device and the preparation method thereof have the following advantages: according to the organic electroluminescent device, the mixed barrier layer and the inorganic barrier layer are made of the mixture, so that the erosion of active substances such as external water, oxygen and the like to the organic electroluminescent device can be effectively reduced, the organic functional materials and the electrodes of the organic electroluminescent device are effectively protected, the requirement on the sealing property of encapsulation is met, and the service life of the OLED device can be remarkably prolonged.
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, a mixed barrier layer 108, and an inorganic barrier layer 109, which are sequentially stacked.
In the organic electroluminescent device, a plurality of mixed barrier layers and inorganic barrier layers which are alternately laminated are arranged on the surface of the cathode layer. The number of the mixed barrier layers and the inorganic barrier layers which are alternately stacked is 4-6.
The mixed barrier layer is made of a mixture of organic matters, metals and oxides; the organic substance is N, 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, 4, 7-diphenyl-1, 10-phenanthroline or 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene, the oxide is MoO3、V2O5、WO3、Cs2O、Ni2O or MnO2The metal is one of Ag, Al, Ni, Au, Cu or Pt, the metal accounts for 10-30 mol% of the mixed barrier layer, the oxide accounts for 30-50 mol% of the mixed barrier layer, and the organic matter accounts for 20-60 mol% of the mixed barrier layer;
the inorganic barrier layer is made of a mixture consisting of sulfide, fluoride and metal, wherein the sulfide is CdS, PbS or FeS2One of CuS, ZnS or NiS, and the fluoride is LiF or CeF2、MgF2、AlF3、CaF2Or BaF2The metal is one of Ag, Al, Ni, Au, Cu or Pt, the fluoride accounts for 10-30 mol% of the inorganic barrier layer, the sulfide accounts for 10-30 mol% of the inorganic barrier layer, and the metal accounts for 40-80 mol% of the inorganic barrier layer;
the thickness of the mixed barrier layer is 200 nm-300 nm; the thickness of the inorganic barrier layer is 100 nm-200 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 30 wt%; the thickness is 20 nm.
The cathode layer is made of ZnS, Ag and ZnS which are sequentially laminated, and the thickness of the cathode layer is 30 nm.
The preparation method of the 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 cathode layer in sequence on an anode conducting layer of a 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 and the electron injection layer is 1 multiplied by 10 when the hole injection layer, the hole transport layer, the luminescent layer, the electron transport layer and the electron injection layer are prepared by vacuum evaporation-5Pa, the vacuum degree of the cathode layer is 3 multiplied by 10 during vacuum evaporation preparation-5Pa; the evaporation rate of the hole injection layer, the hole transport layer and the electron transport layer isThe evaporation rate of the luminescent layer and the electron injection layer isThe cathode layer has an evaporation rate of
(b) On the cathode layer, firstly, preparing a mixed barrier layer by adopting a vacuum evaporation method; preparing an inorganic barrier layer on the mixed barrier layer by adopting a vacuum evaporation method; then, alternately laminating the prepared mixed barrier layer and the inorganic barrier layer for a plurality of times in sequence; the number of times of alternating the mixed barrier layer and the inorganic barrier layer is 4-6.
When the mixed barrier layer is prepared by vacuum evaporation, the vacuum degree of the vacuum evaporation is 1 multiplied by 10-5Pa～1×10-3Pa, the evaporation rate of the vacuum evaporation isWhen the inorganic barrier layer is prepared by vacuum evaporation, the vacuum degree is 1 multiplied by 10-5Pa～1×10-3Pa。
The mixed barrier layer is made of a mixture of organic matters, metals and oxides; the organic matter is one of N, 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, 4, 7-diphenyl-1, 10-phenanthroline or 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene, and the oxide is MoO3、V2O5、WO3、Cs2O、Ni2O or MnO2The metal is one of Ag, Al, Ni, Au, Cu or Pt, the metal accounts for 10-30 mol% of the mixed barrier layer, the oxide accounts for 30-50 mol% of the mixed barrier layer, and the organic matter accounts for 20-60 mol% of the mixed barrier layer;
the inorganic barrier layer is made of a mixture consisting of sulfide, fluoride and metal, wherein the sulfide is CdS, PbS or FeS2One of CuS, ZnS or NiS, and the fluoride is LiF or CeF2、MgF2、AlF3、CaF2Or BaF2The metal is one of Ag, Al, Ni, Au, Cu or Pt, the fluoride accounts for 10-30 mol% of the inorganic barrier layer, the sulfide accounts for 10-30 mol% of the inorganic barrier layer, and the metal accounts for 40-80 mol% of the inorganic barrier layer;
the thickness of the mixed barrier layer is 200 nm-300 nm; the thickness of the inorganic barrier layer is 100 nm-200 nm.
The organic electroluminescent device and the production steps thereof of the present invention are specifically described in examples 1 to 6 below:
example 1
The organic electroluminescent device in this embodiment is a layered structure, and the layered structure sequentially includes:
the organic electroluminescent device comprises an anode conductive substrate, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode layer, a mixed barrier layer and an inorganic barrier layer.
In this embodiment, the following steps are specifically performed in sequence: ITO glass substrate and MoO3-NPB layer, TCTA layer, TPBI-Ir (ppy)3Layer, Bphen layer, CsN3-Bphen layer, ZnS/Ag/ZnS, TAPC-MoO3-an Ag layer, LiF-CdS-Ag layer. (the diagonal "/" indicates a layered structure and the horizontal bar "-" indicates mutual doping.)
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 is 100 nm;
b) preparation of hole injection layer: adding MoO3Doping into NPB as hole injection material with doping concentration of 30wt%, thickness of 10nm, and vacuum degree of 1 × 10-5Pa, evaporation rate of
c) Preparation of hole transport layer: 4,4',4' ' -tri (carbazole-9-yl) triphenylamine (TCTA) is adopted as a hole transport material, and the vacuum degree is 1 multiplied by 10-5Pa, evaporation rateThe evaporation thickness is 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 5% and vacuum degree 1X 10-5Pa, evaporation rateEvaporation thickness 20 nm;
e) preparation of an electron transport layer: evaporating a layer of 4, 7-diphenyl-1, 10-phenanthroline (Bphen) as an electron transport layer on the luminescent layer, wherein the vacuum degree is 1 multiplied by 10-5Pa, evaporation rateThe evaporation thickness is 10 nm;
f) preparation of an electron injection layer: taking a Bphen electron injection layer as a host material of CsN3Doped into Bphen with doping concentration of 30wt% and vacuum degree of 1X 10-5Pa, evaporation rateEvaporation thickness 20 nm;
g) preparing a cathode layer: the cathode adopts ZnS/Ag/ZnS, the thickness is 100nm, the vacuum degree is 1 multiplied by 10-5Pa, evaporation rateDegree of rotation
h) Manufacturing a mixed barrier layer: preparing a mixed barrier layer on the cathode layer by adopting a vacuum evaporation mode, wherein the mixed barrier layer is prepared by doping and co-evaporating three substances, one is TAPC, and the other is MoO3The third is Ag, the ratio of metal Ag is 20mol%, the ratio of oxide is 40mol%, the ratio of TAPC is 40mol%, and the vacuum degree of the mixed barrier layer is 1X 10-5Pa, evaporation rateThe thickness is 250 nm;
i) manufacturing an inorganic barrier layer: preparing an inorganic barrier layer on the mixed barrier layer by adopting a vacuum evaporation mode, wherein the inorganic barrier layer is prepared by doping and co-evaporating three substances, one is LiF, the other is CdS, the third is Ag, the fluoride accounts for 20mol%, the sulfide accounts for 30mol%, the Ag accounts for 50mol%, and the vacuum degree of the inorganic barrier layer is 1 multiplied by 10-5Pa, evaporation rateThe thickness is 150 nm;
j) repeating the steps h) and i)6 times alternately.
Example 2
The organic electroluminescent device in this embodiment is a layered structure, and the layered structure sequentially includes:
the organic electroluminescent device comprises an anode conductive substrate, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode layer, a mixed barrier layer and an inorganic barrier layer.
In this embodiment, the following steps are specifically performed in sequence: ITO glass substrate and MoO3-NPB layer, TCTA layer, TPBI-Ir (ppy)3Layer, Bphen layer, CsN3-Bphen layer, ZnS/Ag/ZnS layer, NPB-V2O5Layer of-Al, CeF2-a PbS-Al layer. (the diagonal "/" indicates a layered structure and the horizontal bar "-" indicates mutual doping.)
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 is 100 nm;
b) preparation of hole injection layer: adding MoO3Doping into NPB as hole injection material with doping concentration of 30wt%, thickness of 10nm, and vacuum degree of 1 × 10-5Pa, evaporation rate of
c) Preparation of hole transport layer: 4,4',4' ' -tri (carbazole-9-yl) triphenylamine (TCTA) is adopted as a hole transport material, and the vacuum degree is 1 multiplied by 10-5Pa, evaporation rateThe evaporation thickness is 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 5% and vacuum degree 1X 10-5Pa, evaporation rateEvaporation thickness 20 nm;
e) preparation of an electron transport layer: evaporating a layer of 4, 7-diphenyl on the luminescent layerRadical-1, 10-phenanthroline (Bphen) as electron transport layer with vacuum degree of 1X 10-5Pa, evaporation rateThe evaporation thickness is 10 nm;
f) preparation of an electron injection layer: taking a Bphen electron injection layer as a host material of CsN3Doped into Bphen with doping concentration of 30wt% and vacuum degree of 1X 10-5Pa, evaporation rateEvaporation thickness 20 nm;
g) preparing a cathode layer: the cathode adopts ZnS/Ag/ZnS, the thickness is 100nm, the vacuum degree is 1 multiplied by 10-5Pa, evaporation rate
h) Manufacturing a mixed barrier layer: preparing a mixed barrier layer on the cathode layer by adopting a vacuum evaporation mode, wherein the mixed barrier layer is prepared by doping and co-evaporating three substances, one is NPB, and the other is V2O5The third is Al, the metal accounts for 30mol%, the oxide accounts for 40mol%, the NPB accounts for 30mol%, and the vacuum degree of the mixed barrier layer is 5 multiplied by 10-5Pa, evaporation rateThe thickness is 300 nm;
i) manufacturing an inorganic barrier layer: preparing an inorganic barrier layer on the mixed barrier layer by adopting a vacuum evaporation mode, wherein the inorganic barrier layer is prepared by doping and co-evaporating three substances, and one is CeF2The other is PbS, the third is Al, the proportion of sulfide is 15wt%, the proportion of fluoride is 15wt%, the proportion of Al is 70wt%, and the vacuum degree of the mixed barrier layer is 5 multiplied by 10-5Pa, evaporation rateThe thickness is 100 nm;
j) repeating the steps h) and i)5 times alternately.
Example 3
The organic electroluminescent device in this embodiment is a layered structure, and the layered structure sequentially includes:
the organic electroluminescent device comprises an anode conductive substrate, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode layer, a mixed barrier layer and an inorganic barrier layer.
In this embodiment, the following steps are specifically performed in sequence: ITO glass substrate and MoO3-NPB layer, TCTA layer, TPBI-Ir (ppy)3Layer, Bphen layer, CsN3-Bphen layer, ZnS/Ag/ZnS, Alq3-WO3-Ni layer, MgF2-FeS2-a Ni layer. (the diagonal "/" indicates a layered structure and the horizontal bar "-" indicates mutual doping.)
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 is 100 nm;
b) preparation of hole injection layer: adding MoO3Doping into NPB as hole injection material with doping concentration of 30wt%, thickness of 10nm, and vacuum degree of 1 × 10-5Pa, evaporation rate of
c) Preparation of hole transport layer: using 4,4',4' ' -tris (carbo)Azole-9-yl) triphenylamine (TCTA) as hole transport material with vacuum degree of 1 × 10-5Pa, evaporation rateThe evaporation thickness is 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 5% and vacuum degree 1X 10-5Pa, evaporation rateEvaporation thickness 20 nm;
e) preparation of an electron transport layer: evaporating a layer of 4, 7-diphenyl-1, 10-phenanthroline (Bphen) as an electron transport layer on the luminescent layer, wherein the vacuum degree is 1 multiplied by 10-5Pa, evaporation rateThe evaporation thickness is 10 nm;
f) preparation of an electron injection layer: taking a Bphen electron injection layer as a host material of CsN3Doped into Bphen with doping concentration of 30wt% and vacuum degree of 1X 10-5Pa, evaporation rateEvaporation thickness 20 nm;
g) preparing a cathode layer: the cathode adopts ZnS/Ag/ZnS, the thickness is 100nm, the vacuum degree is 1 multiplied by 10-5Pa, evaporation rate
h) Manufacturing a mixed barrier layer: preparing a mixed barrier layer on the cathode layer by vacuum evaporation, wherein the mixed barrier layer is prepared by doping and co-evaporating three substances, is prepared by vacuum evaporation, and is Alq3The other is WO3The third is Ni, Alq330mol% of metal, 10mol% of oxide, 30mol% of mixed barrier layer with vacuum degree of 5 × 10-5Pa, evaporation rateThe thickness is 200 nm;
i) manufacturing an inorganic barrier layer: preparing an inorganic barrier layer on the mixed barrier layer by adopting a vacuum evaporation mode, wherein the inorganic barrier layer is prepared by doping and co-evaporating four substances, and MgF is used as one of the inorganic barrier layers2The other is FeS2The third is Ni, the proportion of Ni is 66wt%, the proportion of sulfide is 18 mol%, the proportion of fluoride is 16wt%, and the vacuum degree of the inorganic barrier layer is 5 multiplied by 10-5Pa, evaporation rateThe thickness is 200 nm;
j) repeating the steps h) and i)6 times alternately.
Example 4
The organic electroluminescent device in this embodiment is a layered structure, and the layered structure sequentially includes:
the organic electroluminescent device comprises an anode conductive substrate, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode layer, a mixed barrier layer and an inorganic barrier layer.
In this embodiment, the following steps are specifically performed in sequence: ITO glass substrate and MoO3-NPB layer, TCTA layer, TPBI-Ir (ppy)3Layer, Bphen layer, CsN3-Bphen layer, ZnS/Ag/ZnS, m-MTDATA-Cs2O-Au layer, AlF3-a layer of CuS-Au. (the diagonal "/" indicates a layered structure and the horizontal bar "-" indicates mutual doping.)
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 is 100 nm;
b) preparation of hole injection layer: adding MoO3Doping into NPB as hole injection material with doping concentration of 30wt%, thickness of 10nm, and vacuum degree of 1 × 10-5Pa, evaporation rate of
c) Preparation of hole transport layer: 4,4',4' ' -tri (carbazole-9-yl) triphenylamine (TCTA) is adopted as a hole transport material, and the vacuum degree is 1 multiplied by 10-5Pa, evaporation rateThe evaporation thickness is 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 5% and vacuum degree 1X 10-5Pa, evaporation rateEvaporation thickness 20 nm;
e) preparation of an electron transport layer: evaporating a layer of 4, 7-diphenyl-1, 10-phenanthroline (Bphen) as an electron transport layer on the luminescent layer, wherein the vacuum degree is 1 multiplied by 10-5Pa, evaporation rateThe evaporation thickness is 10 nm;
f) preparation of an electron injection layer: taking a Bphen electron injection layer as a host material of CsN3Doped into Bphen with doping concentration of 30wt% and vacuum degree of 1X 10-5Pa, evaporation rateEvaporation thickness 20 nm;
g) preparing a cathode layer: the cathode adopts ZnS/Ag/ZnS, the thickness is 100nm, the vacuum degree is 1 multiplied by 10-5Pa, evaporation rate
h) Manufacturing a mixed barrier layer: preparing a mixed barrier layer on the cathode layer by adopting a vacuum evaporation mode, wherein the mixed barrier layer is prepared by doping and co-evaporating three substances, one is m-MTDATA, and the other is Cs2O, the third one is Au, the m-MTDATA accounts for 35mol percent, the metal accounts for 15mol percent, the oxide accounts for 50mol percent, and the vacuum degree of the mixed barrier layer is 5 multiplied by 10-5Pa, evaporation rateThe thickness is 240 nm;
i) manufacturing an inorganic barrier layer: preparing an inorganic barrier layer on the mixed barrier layer by adopting a vacuum evaporation mode, wherein the inorganic barrier layer is prepared by doping and co-evaporating three substances, and AlF is used as one of the three substances3The other is CuS, the third is Au, the fluoride accounts for 15mol percent, the sulfide accounts for 20mol percent, the Au accounts for 11wt percent, and the vacuum degree of the inorganic barrier layer is 5 multiplied by 10-5Pa, evaporation rateThe thickness is 180 nm;
j) repeating the steps h) and i) for 4 times alternately.
Example 5
The organic electroluminescent device in this embodiment is a layered structure, and the layered structure sequentially includes:
the organic electroluminescent device comprises an anode conductive substrate, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode layer, a mixed barrier layer and an inorganic barrier layer.
In this embodiment, the following steps are specifically performed in sequence: ITO glass substrate and MoO3-NPB layer, TCTA layer, TPBI-Ir (ppy)3Layer, Bphen layer, CsN3-Bphen layer, ZnS/Ag/ZnS, BCP-Ni2O-Cu layer, CaF2-a ZnS-Cu layer. (the diagonal "/" indicates a layered structure and the horizontal bar "-" indicates mutual doping.)
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 is 100 nm;
b) preparation of hole injection layer: adding MoO3Doping into NPB as hole injection material with doping concentration of 30wt%, thickness of 10nm, and vacuum degree of 1 × 10-5Pa, evaporation rate of
c) Preparation of hole transport layer: 4,4',4' ' -tri (carbazole-9-yl) triphenylamine (TCTA) is adopted as a hole transport material, and the vacuum degree is 1 multiplied by 10-5Pa, evaporation rateThe evaporation thickness is 30 nm;
d) light-emitting layer: 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBI) is adopted as a host material, and tri(2-Phenylpyridiniumiridium (Ir) (ppy)3) Doping concentration 5% and vacuum degree 1X 10-5Pa, evaporation rateEvaporation thickness 20 nm;
e) preparation of an electron transport layer: evaporating a layer of 4, 7-diphenyl-1, 10-phenanthroline (Bphen) as an electron transport layer on the luminescent layer, wherein the vacuum degree is 1 multiplied by 10-5Pa, evaporation rateThe evaporation thickness is 10 nm;
f) preparation of an electron injection layer: taking a Bphen electron injection layer as a host material of CsN3Doped into Bphen with doping concentration of 30wt% and vacuum degree of 1X 10-5Pa, evaporation rateEvaporation thickness 20 nm;
g) preparing a cathode layer: the cathode adopts ZnS/Ag/ZnS, the thickness is 100nm, the vacuum degree is 1 multiplied by 10-5Pa, evaporation rate
h) Manufacturing a mixed barrier layer: preparing a mixed barrier layer on the cathode layer by adopting a vacuum evaporation mode, wherein the mixed barrier layer is prepared by doping and co-evaporating three substances, one is BCP, and the other is Ni2O, Cu as the third component, 19mol% of metal, 45mol% of oxide, 36mol% of BCP, and 5X 10 vacuum degree of mixed barrier layer-5Pa, evaporation rateThe thickness is 260 nm;
i) manufacturing an inorganic barrier layer: preparing an inorganic barrier layer on the mixed barrier layer by vacuum evaporationIs prepared by mixing and co-steaming three substances, one is CaF2The other is ZnS, the third is Cu, the fluoride accounts for 30mol%, the sulfide accounts for 10mol%, and the vacuum degree of the inorganic barrier layer is 5 multiplied by 10-5Pa, evaporation rateThe thickness is 140 nm;
j) repeating the steps h) and i)6 times alternately.
Example 6
The organic electroluminescent device in this embodiment is a layered structure, and the layered structure sequentially includes:
the organic electroluminescent device comprises an anode conductive substrate, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode layer, a mixed barrier layer and an inorganic barrier layer.
In this embodiment, the following steps are specifically performed in sequence: ITO glass substrate and MoO3-NPB layer, TCTA layer, TPBI-Ir (ppy)3Layer, Bphen layer, CsN3-Bphen layer, ZnS/Ag/ZnS, TPBi-MnO2-Pt layer, BaF2-a NiS-Pt layer. (the diagonal "/" indicates a layered structure and the horizontal bar "-" indicates mutual doping.)
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 is 100 nm;
b) preparation of hole injection layer: adding MoO3Doped into NPB as hole-injecting material, doped heavilyDegree of 30wt%, thickness of 10nm, degree of vacuum of 1X 10-5Pa, evaporation rate of
c) Preparation of hole transport layer: 4,4',4' ' -tri (carbazole-9-yl) triphenylamine (TCTA) is adopted as a hole transport material, and the vacuum degree is 1 multiplied by 10-5Pa, evaporation rateThe evaporation thickness is 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 5% and vacuum degree 1X 10-5Pa, evaporation rateEvaporation thickness 20 nm;
e) preparation of an electron transport layer: evaporating a layer of 4, 7-diphenyl-1, 10-phenanthroline (Bphen) as an electron transport layer on the luminescent layer, wherein the vacuum degree is 1 multiplied by 10-5Pa, evaporation rateThe evaporation thickness is 10 nm;
f) preparation of an electron injection layer: taking a Bphen electron injection layer as a host material of CsN3Doped into Bphen with doping concentration of 30wt% and vacuum degree of 1X 10-5Pa, evaporation rateEvaporation thickness 20 nm;
g) preparing a cathode layer: the cathode adopts ZnS/Ag/ZnS, the thickness is 100nm, the vacuum degree is 1 multiplied by 10-5Pa, evaporation rate
h) Manufacturing a mixed barrier layer: preparing a mixed barrier layer on the cathode layer by adopting a vacuum evaporation mode, wherein the mixed barrier layer is prepared by doping and co-evaporating three substances, one is TPBi, and the other is MnO2The third one is Pt, the metal doping concentration is 25mol%, the oxide doping concentration is 40mol%, the TPBi doping concentration is 35mol%, and the vacuum degree of the mixed barrier layer is 1 multiplied by 10-3Pa, evaporation rateThe thickness is 220 nm;
i) manufacturing an inorganic barrier layer: preparing an inorganic barrier layer on the mixed barrier layer by adopting a vacuum evaporation mode, wherein the inorganic barrier layer is prepared by doping and co-evaporating three substances, and one is BaF2The other is NiS, the third is Pt, the fluoride accounts for 10mol%, the sulfide accounts for 20mol%, the Pt accounts for 70wt%, and the vacuum degree of the inorganic barrier layer is 1 multiplied by 10-3Pa, evaporation rateThe thickness is 150 nm;
j) repeating the steps h) and i)6 times alternately.
Performance testing
The organic electroluminescent devices according to the present invention of examples 1 to 6 above were subjected to the water oxygen resistance (WVTR) and transmittance test, and as can be seen from table 1 below, the water oxygen resistance reached 10－4g/m2The performance of the OLED is more than day, and the service life of the OLED light-emitting device manufactured by the OLED light-emitting device reaches more than 4080 hours on average.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| WVTR(g/m2/day) | 6.2E－4 | 6.5E－4 | 6.9E－4 | 7.1E－4 | 7.4E－4 | 7.9E－4 |
| Life (hours) | 4212 | 4151 | 4140 | 4122 | 4112 | 4080 |
Therefore, the organic electroluminescent device and the preparation method thereof have the following advantages:
1. the adopted mixed barrier layer and the inorganic barrier layer are made of a mixture, so that the external water can be effectively reducedAnd the active substances such as oxygen corrode 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 package is met, and the service life of the OLED device can be remarkably prolonged. The water and oxygen resistance of the paint reaches 10－4g/m2The service life of the OLED light-emitting device manufactured by the method/day is more than 4080 hours on average.
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 mixed barrier layers and inorganic barrier layers which are alternately stacked are arranged on the surface of the cathode layer; wherein,
the mixed barrier layer is made of a mixture of organic matters, metals and oxides; the organic matter is N, N '-diphenyl-N, N' -di (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine8-hydroxyquinoline aluminum, 4',4' ' -tri (N-3-methylphenyl-N-phenylamino) triphenylamine, 4, 7-diphenyl-1, 10-phenanthroline or 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene, wherein the oxide is MoO3、V2O5、WO3、Cs2O、Ni2O or MnO2The metal is one of Ag, Al, Ni, Au, Cu or Pt, the metal accounts for 10-30 mol% of the mixed barrier layer, the oxide accounts for 30-50 mol% of the mixed barrier layer, and the organic matter accounts for 20-60 mol% of the mixed barrier layer;
the inorganic barrier layer is made of a mixture consisting of sulfide, fluoride and metal, wherein the sulfide is CdS, PbS or FeS2One of CuS, ZnS or NiS, and the fluoride is LiF or CeF2、MgF2、AlF3、CaF2Or BaF2The metal is one of Ag, Al, Ni, Au, Cu or Pt, the fluoride accounts for 10-30 mol% of the inorganic barrier layer, the sulfide accounts for 10-30 mol% of the inorganic barrier layer, and the metal accounts for 40-80 mol% of the inorganic barrier layer.
2. The organic electroluminescent device according to claim 1, wherein the thickness of the hybrid barrier layer is 200nm to 300 nm.
3. The organic electroluminescent device according to claim 1, wherein the inorganic barrier layer has a thickness of 100nm to 200 nm.
4. The organic electroluminescent device according to claim 1, wherein: the number of the mixed 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 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 CsN3A mixed material formed by doping 4, 7-diphenyl-1, 10-phenanthroline according to the doping concentration of 30 wt%;
the cathode layer is made of ZnS, Ag and ZnS which are sequentially laminated by adopting a vacuum evaporation method.
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 cathode layer in sequence on an anode conducting layer of a cleaned anode conducting substrate by adopting a vacuum evaporation method;
(b) on the cathode layer, firstly, preparing a mixed barrier layer by adopting a vacuum evaporation method; preparing an inorganic barrier layer on the mixed barrier layer by adopting a vacuum evaporation method; then, alternately laminating for a plurality of times in sequence to prepare a mixed barrier layer and an inorganic barrier layer; wherein,
the mixed barrier layer is made of a mixture of organic matters, metals and oxides; the organic matter is one of N, 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, 4, 7-diphenyl-1, 10-phenanthroline or 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene, and the oxide is MoO3、V2O5、WO3、Cs2O、Ni2O or MnO2The metal is one of Ag, Al and,One of Ni, Au, Cu or Pt, wherein the metal accounts for 10-30 mol% of the mixed barrier layer, the oxide accounts for 30-50 mol% of the mixed barrier layer, and the organic matter accounts for 20-60 mol% of the mixed barrier layer;
the inorganic barrier layer is made of a mixture consisting of sulfide, fluoride and metal, wherein the sulfide is CdS, PbS or FeS2One of CuS, ZnS or NiS, and the fluoride is LiF or CeF2、MgF2、AlF3、CaF2Or BaF2The metal is one of Ag, Al, Ni, Au, Cu or Pt, the fluoride accounts for 10-30 mol% of the inorganic barrier layer, the sulfide accounts for 10-30 mol% of the inorganic barrier layer, and the metal accounts for 40-80 mol% of the inorganic barrier layer.
7. The production method according to claim 6, wherein the thickness of the mixed barrier layer is 200nm to 300 nm; the thickness of the inorganic barrier layer is 100 nm-200 nm.
8. The production method according to claim 6, wherein in the step (a), the degree of vacuum in the production of the hole injection layer, the hole transport layer, the light-emitting layer, the electron transport layer, and the electron injection layer is 1X 10-5Pa, the vacuum degree of the cathode layer is 3 multiplied by 10 during vacuum evaporation preparation-5Pa; the evaporation rate of the hole injection layer, the hole transport layer and the electron transport layer isThe evaporation rate of the luminescent layer and the electron injection layer isThe cathode layer has an evaporation rate of
9. The method according to claim 6, wherein in the step (b), the number of times of alternation of the mixed 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 the vacuum evaporation is 1 x 10 when the vacuum evaporation is used for preparing the mixed barrier layer-5Pa～1×10-3Pa, the evaporation rate of the vacuum evaporation isWhen the inorganic barrier layer is prepared by vacuum evaporation, the vacuum degree is 1 multiplied by 10-5Pa～1×10-3Pa。
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