CN104051640A - Organic electroluminescent device and manufacturing method thereof - Google Patents
Organic electroluminescent device and manufacturing method thereof Download PDFInfo
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- CN104051640A CN104051640A CN201310078182.XA CN201310078182A CN104051640A CN 104051640 A CN104051640 A CN 104051640A CN 201310078182 A CN201310078182 A CN 201310078182A CN 104051640 A CN104051640 A CN 104051640A
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- 238000004519 manufacturing process Methods 0.000 title abstract 3
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 55
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 239000010410 layer Substances 0.000 claims description 298
- 239000000463 material Substances 0.000 claims description 171
- 230000008020 evaporation Effects 0.000 claims description 60
- 238000001704 evaporation Methods 0.000 claims description 60
- 239000011521 glass Substances 0.000 claims description 44
- 238000005401 electroluminescence Methods 0.000 claims description 38
- 239000002346 layers by function Substances 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 27
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 12
- 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 10
- 239000010931 gold Substances 0.000 claims description 10
- 229910000510 noble metal Inorganic materials 0.000 claims description 10
- 230000005525 hole transport Effects 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- DISHRDNUYGLDMW-UHFFFAOYSA-N 3,6-dioxocyclohexa-1,4-diene-1-carbonitrile methane Chemical compound C.C.O=C1C=CC(=O)C(=C1)C#N DISHRDNUYGLDMW-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 abstract description 54
- 238000002347 injection Methods 0.000 abstract description 32
- 239000007924 injection Substances 0.000 abstract description 32
- 238000000149 argon plasma sintering Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000002834 transmittance Methods 0.000 abstract 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 48
- ZVFQEOPUXVPSLB-UHFFFAOYSA-N 3-(4-tert-butylphenyl)-4-phenyl-5-(4-phenylphenyl)-1,2,4-triazole Chemical group C1=CC(C(C)(C)C)=CC=C1C(N1C=2C=CC=CC=2)=NN=C1C1=CC=C(C=2C=CC=CC=2)C=C1 ZVFQEOPUXVPSLB-UHFFFAOYSA-N 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 12
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound 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 10
- 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 8
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 8
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- 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 description 7
- HXWWMGJBPGRWRS-CMDGGOBGSA-N 4- -2-tert-butyl-6- -4h-pyran Chemical compound O1C(C(C)(C)C)=CC(=C(C#N)C#N)C=C1\C=C\C1=CC(C(CCN2CCC3(C)C)(C)C)=C2C3=C1 HXWWMGJBPGRWRS-CMDGGOBGSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000003599 detergent Substances 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000001771 vacuum deposition Methods 0.000 description 5
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical class N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 4
- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
- CRHRWHRNQKPUPO-UHFFFAOYSA-N 4-n-naphthalen-1-yl-1-n,1-n-bis[4-(n-naphthalen-1-ylanilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 CRHRWHRNQKPUPO-UHFFFAOYSA-N 0.000 description 4
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical class C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 4
- VIZUPBYFLORCRA-UHFFFAOYSA-N 9,10-dinaphthalen-2-ylanthracene Chemical compound C12=CC=CC=C2C(C2=CC3=CC=CC=C3C=C2)=C(C=CC=C2)C2=C1C1=CC=C(C=CC=C2)C2=C1 VIZUPBYFLORCRA-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 description 2
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical group [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000000075 oxide glass Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/865—Intermediate layers comprising a mixture of materials of the adjoining active layers
-
- 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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
- H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
- H10K50/131—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit with spacer layers between the electroluminescent layers
-
- 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
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/311—Phthalocyanine
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- 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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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Optics & Photonics (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides an organic electroluminescent device and a manufacturing method thereof. The organic electroluminescent device comprises a charge generation layer, wherein the charge generation layer comprises a metal oxide layer, a metal layer and a p-type doped layer which are sequentially laminated, the metal oxide layer can effectively carry out hole injection and transmission and effectively improves light emitting efficiency and brightness of the device, the metal layer can improve light transmittance of the charger generation layer, the p-type layer can reinforce the light scattering effect, and light removal efficiency is improved. The organic electroluminescent device has a simple manufacturing method and is easy to control and operate, and raw materials are easy to acquire.
Description
Technical field
The invention belongs to organic electroluminescent field, be specifically related to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) is a kind ofly to take organic material as luminescent material, the energy conversion device that can be luminous energy the electric energy conversion applying.It has the outstanding properties such as ultra-thin, self-luminous, response are fast, low-power consumption, in fields such as demonstration, illuminations, has application prospect very widely.
The structure of organic electroluminescence device is sandwich structure, and in containing the device of sandwich construction, inner side, the two poles of the earth mainly comprises luminescent layer, implanted layer and transport layer.Organic electroluminescence device is carrier injection type luminescent device, at the two poles of the earth, add after operating voltage, hole and electronics are injected into the organic material layer of device work from the two poles of the earth respectively, and it is luminous that two kinds of charge carriers form hole-duplet in luminous organic material, and then light sends from electrode.
At present, in order to improve luminosity and luminous efficiency, increasing research is to take laminated device as main, this structure normally uses charge generation layer as articulamentum, several light emitting functional layer (luminescence unit) to be together in series, compare with unit component, multilayer devices often has current efficiency and luminosity at double.In laminated device, conventionally utilize two or more material with hole injectability or electronic injection ability as charge generation layer (as Cs:BCP/V
2o
5), or utilize N-shaped and p-type doped layer as charge generation layer (as N-shaped (Alq
3: Li) and p-type (NPB:FeCl
3)) be linked in sequence a plurality of luminescence units and form, but adopt the luminous efficiency of this charge generation layer laminated organic electroluminescent device lower.
Summary of the invention
In order to address the above problem, the present invention aims to provide a kind of organic electroluminescence device having compared with high light-emitting efficiency.The present invention also provides a kind of preparation method of organic electroluminescence device.
First aspect, the invention provides a kind of organic electroluminescence device, comprises the conductive anode substrate of glass, the first light emitting functional layer, charge generation layer, the second light emitting functional layer and the negative electrode that stack gradually;
Described charge generation layer comprises metal oxide layer, metal level and the p-type doped layer stacking gradually; The material of described metal oxide layer is bipolarity metal oxide; The material of described metal level is aluminium or noble metal; The material of described p-type doped layer is the mixture that hole guest materials and hole mobile material form, and the mass fraction of described hole guest materials duty hole transport materials is 0.5～5%;
Described hole guest materials is 2,3,5,6-tetrafluoro-7,7,8,8, and-four cyano-benzoquinone bismethane, 4,4, a kind of in 4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine and 4,4,4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine; Described hole mobile material is 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4, a kind of in 4 '-benzidine and CuPc.
Preferably, the material of conductive anode substrate of glass is a kind of in indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) and indium-zinc oxide glass (IZO).More preferably, the material of conductive anode substrate of glass is ITO.
The first light emitting functional layer is arranged in conductive anode substrate of glass.
The first light emitting functional layer comprises the first luminescent layer, also comprises at least one in the first hole injection layer, the first hole transmission layer and the first electron transfer layer.
Preferably, the first light emitting functional layer comprises the first hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer stacking gradually.
Preferably, the material of the first hole injection layer is molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) in a kind of.More preferably, the material of the first hole injection layer is MoO
3.
Preferably, the thickness of the first hole injection layer is 20～80nm.More preferably, the thickness of the first hole injection layer is 40nm.
Preferably, the material of the first hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, a kind of in 4'-diamines (NPB).More preferably, the material of the first hole transmission layer is TCTA.
Preferably, the thickness of the first hole transmission layer is 20～60nm.More preferably, the thickness of the first hole transmission layer is 40nm.
Preferably, the material of the first luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis-(betanaphthyl) anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq
3) in a kind of.More preferably, the material of the first luminescent layer is ADN.
Preferably, the thickness of the first luminescent layer is 5～40nm.More preferably, the thickness of the first luminescent layer is 25nm.
Preferably, the material of the first electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, a kind of in 4-triazole derivative and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).
More preferably, 1,2,4-triazole derivative is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).More preferably, the material of the first electron transfer layer is TBPi.
Preferably, the thickness of the first electron transfer layer is 40～200nm.More preferably, the thickness of the first electron transfer layer is 60nm.
In the first light emitting functional layer, set gradually metal oxide layer, metal level and p-type doped layer.
In the present invention, metal oxide layer, metal level and p-type doped layer are charge generation layer.
Preferably, the material of metal oxide layer is bipolarity metal oxide.
More preferably, bipolarity metal oxide is a kind of in molybdenum trioxide, tungstic acid and vanadic oxide.
Preferably, the thickness of metal oxide layer is 5～40nm.
The material of metal level is aluminium or noble metal, and wherein, preferably, noble metal is a kind of in silver, platinum and gold.
Preferably, the thickness of metal level is 1～10nm.
The material of p-type doped layer is the mixture that hole guest materials and hole mobile material form, and wherein, hole guest materials is guest materials, and hole mobile material is material of main part.
In the material of p-type doped layer, the quality of guest materials is 0.5～5% of material of main part quality, and the mass fraction of hole guest materials duty hole transport materials is 0.5～5%.
Hole guest materials is the guest materials being usually used in this area with hole mobile material doping, has good cooperative ability with hole mobile material, improves hole transport efficiency.
In the present invention, the hole guest materials of selecting is 2,3,5,6-tetrafluoro-7,7,8,8 ,-four cyano-benzoquinone bismethane (F4-TCNQ), 4,4,4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine (1T-NATA) and 4,4,4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine (2T-NATA).
Hole mobile material is 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4, a kind of in 4 '-benzidine (TPD) and CuPc (CuPc).
Preferably, the thickness of p-type doped layer is 10～50nm.
Charge generation layer is comprised of the metal oxide layer stacking gradually, metal level and p-type doped layer, the work function of the metal oxide using in metal oxide layer is lower, there is the generation of good hole and can effectively carry out injection and the transmission in hole with the bipolarity metal oxide of transmittability, improve hole regeneration injectability, effectively improve device luminous efficiency and brightness; And the existence of metal in metal level can improve the light transmission rate of charge generation layer; P-type doped layer can farthest improve the speed of injection and the transmission in hole, strengthens light scattering effect simultaneously, improves light and takes out efficiency.
The second light emitting functional layer is arranged on p-type doped layer.
The second light emitting functional layer comprises the second luminescent layer, also comprises at least one in the second hole transmission layer, the second electron transfer layer and the second electron injecting layer.
Preferably, the second light emitting functional layer comprises the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the second electron injecting layer stacking gradually.
Preferably, the material of the second hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, a kind of in 4'-diamines (NPB).More preferably, the material of the second hole transmission layer is NPB.
Preferably, the thickness of the second hole transmission layer is 20～60nm.More preferably, the thickness of the second hole transmission layer is 40nm.
Preferably, the material of the second luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis-(betanaphthyl) anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq
3) in a kind of.More preferably, the material of the second luminescent layer is ADN.
Preferably, the thickness of the second luminescent layer is 5～40nm.More preferably, the thickness of the second luminescent layer is 25nm.
Preferably, the material of the second electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, a kind of in 4-triazole derivative and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).
More preferably, 1,2,4-triazole derivative is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).More preferably, the material of the second electron transfer layer is TAZ.
Preferably, the thickness of the second electron transfer layer is 40～200nm.More preferably, the thickness of the second electron transfer layer is 80nm.
Preferably, the material of the second electron injecting layer is cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) and lithium fluoride (LiF) in a kind of.More preferably, the material of the second electron injecting layer is CsN
3.
Preferably, the thickness of the second electron injecting layer is 0.5～10nm.More preferably, the thickness of the second electron injecting layer is 1nm.
Negative electrode is arranged in the second light emitting functional layer.
Preferably, the material of negative electrode is a kind of in silver, aluminium, platinum and gold.More preferably, the material of negative electrode is silver.
Preferably, the thickness of negative electrode is 60～300nm.More preferably, the thickness of negative electrode is 120nm.
Second aspect, the invention provides a kind of preparation method of organic electroluminescence device, comprises the following steps:
Conductive anode substrate of glass is provided;
In described conductive anode substrate of glass, thermal resistance evaporation is prepared the first light emitting functional layer, charge generation layer, the second light emitting functional layer and negative electrode successively, obtains organic electroluminescence device;
Described charge generation layer comprises metal oxide layer, metal level and the p-type doped layer stacking gradually, and the material of described metal oxide layer is bipolarity metal oxide; The material of described metal level is aluminium or noble metal; The material of described p-type doped layer is the mixture that hole guest materials and hole mobile material form, and the mass fraction of described hole guest materials duty hole transport materials is 0.5～5%;
Described hole guest materials is 2,3,5,6-tetrafluoro-7,7,8,8, and-four cyano-benzoquinone bismethane, 4,4,4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine and 4,4,4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine; Described hole mobile material is 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4, a kind of in 4 '-benzidine and CuPc.
By the cleaning to conductive anode substrate of glass, remove the organic pollution of conductive anode glass basic surface.
Particularly, the clean operation of conductive anode substrate of glass is: conductive anode substrate of glass is used to distilled water, alcohol flushing successively, then be placed on soaked overnight in isopropyl alcohol, remove the organic pollution of conductive anode glass surface, obtain clean conductive anode substrate of glass.
Preferably, the material of conductive anode substrate of glass is a kind of in indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) and indium-zinc oxide glass (IZO).More preferably, the material of conductive anode substrate of glass is ITO.
The first light emitting functional layer is arranged in conductive anode substrate of glass by the method for thermal resistance evaporation.
When preferably, thermal resistance evaporation is prepared the first light emitting functional layer, condition is pressure 2 * 10
-4～5 * 10
-3pa, speed 0.1～1nm/s.
The first light emitting functional layer comprises the first luminescent layer, also comprises at least one in the first hole injection layer, the first hole transmission layer and the first electron transfer layer.
Preferably, the first light emitting functional layer comprises the first hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer stacking gradually.
Preferably, the material of the first hole injection layer is molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) in a kind of.More preferably, the material of the first hole injection layer is MoO
3.
Preferably, the thickness of the first hole injection layer is 20～80nm.More preferably, the thickness of the first hole injection layer is 40nm.
Preferably, the material of the first hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, a kind of in 4'-diamines (NPB).More preferably, the material of the first hole transmission layer is TCTA.
Preferably, the thickness of the first hole transmission layer is 20～60nm.More preferably, the thickness of the first hole transmission layer is 40nm.
Preferably, the material of the first luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis-(betanaphthyl) anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq
3) in a kind of.More preferably, the material of the first luminescent layer is ADN.
Preferably, the thickness of the first luminescent layer is 5～40nm.More preferably, the thickness of the first luminescent layer is 25nm.
Preferably, the material of the first electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, a kind of in 4-triazole derivative and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).
More preferably, 1,2,4-triazole derivative is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).More preferably, the material of the first electron transfer layer is TBPi.
Preferably, the thickness of the first electron transfer layer is 40～200nm.More preferably, the thickness of the first electron transfer layer is 60nm.
In the first light emitting functional layer, thermal resistance evaporation arranges metal oxide layer, metal level and p-type doped layer successively.
In the present invention, metal oxide layer, metal level and p-type doped layer are charge generation layer.
When preferably, thermal resistance evaporation is prepared metal oxide layer and metal level, condition is pressure 2 * 10
-4～5 * 10
-3pa, speed 1～10nm/s.
Preferably, the material of metal oxide layer is bipolarity metal oxide.
More preferably, bipolarity metal oxide is a kind of in molybdenum trioxide, tungstic acid and vanadic oxide.
Preferably, the thickness of metal oxide layer is 5～40nm.
The material of metal level is aluminium or noble metal, and wherein, preferably, noble metal is a kind of in silver, platinum and gold.
Preferably, the thickness of metal level is 1～10nm.
When preferably, thermal resistance evaporation is prepared p-type doped layer, condition is pressure 2 * 10
-4～5 * 10
-3pa, speed 0.1～1nm/s.
The material of p-type doped layer is the mixture that hole guest materials and hole mobile material form, and wherein, hole guest materials is guest materials, and hole mobile material is material of main part.
In the material of p-type doped layer, the quality of guest materials is 0.5～5% of material of main part quality, and the mass fraction of hole guest materials duty hole transport materials is 0.5～5%.
Hole guest materials is the guest materials being usually used in this area with hole mobile material doping, has good cooperative ability with hole mobile material, improves hole transport efficiency.
In the present invention, the hole guest materials of selecting is 2,3,5,6-tetrafluoro-7,7,8,8, and-four cyano-benzoquinone bismethane, 4,4,4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine and 4,4,4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine.
Hole mobile material is 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4, a kind of in 4 '-benzidine and CuPc.
Preferably, the thickness of p-type doped layer is 10～50nm.
Charge generation layer is comprised of the metal oxide layer stacking gradually, metal level and p-type doped layer, the work function of the metal oxide using in metal oxide layer is lower, there is the generation of good hole and can effectively carry out injection and the transmission in hole with the bipolarity metal oxide of transmittability, improve hole regeneration injectability, effectively improve device luminous efficiency and brightness; And the existence of metal in metal level can improve the light transmission rate of charge generation layer; P-type doped layer can farthest improve the speed of injection and the transmission in hole, strengthens light scattering effect simultaneously, improves light and takes out efficiency.
The second light emitting functional layer is arranged on p-type doped layer by thermal resistance evaporation.
When preferably, thermal resistance evaporation is prepared the second light emitting functional layer, condition is pressure 2 * 10
-4～5 * 10
-3pa, speed 0.1～1nm/s.
The second light emitting functional layer comprises the second luminescent layer, also comprises at least one in the second hole transmission layer, the second electron transfer layer and the second electron injecting layer.
Preferably, the second light emitting functional layer comprises the second hole transmission layer, the second luminescent layer, the second electron transfer layer and the second electron injecting layer stacking gradually.
Preferably, the material of the second hole transmission layer is 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA) and N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4, a kind of in 4'-diamines (NPB).More preferably, the material of the second hole transmission layer is NPB.
Preferably, the thickness of the second hole transmission layer is 20～60nm.More preferably, the thickness of the second hole transmission layer is 40nm.
Preferably, the material of the second luminescent layer is 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans (DCJTB), 9,10-bis-(betanaphthyl) anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq
3) in a kind of.More preferably, the material of the second luminescent layer is ADN.
Preferably, the thickness of the second luminescent layer is 5～40nm.More preferably, the thickness of the second luminescent layer is 25nm.
Preferably, the material of the second electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, a kind of in 4-triazole derivative and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).
More preferably, 1,2,4-triazole derivative is 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ).More preferably, the material of the second electron transfer layer is TAZ.
Preferably, the thickness of the second electron transfer layer is 40～200nm.More preferably, the thickness of the second electron transfer layer is 80nm.
Preferably, the material of the second electron injecting layer is cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) and lithium fluoride (LiF) in a kind of.More preferably, the material of the second electron injecting layer is CsN
3.
Preferably, the thickness of the second electron injecting layer is 0.5～10nm.More preferably, the thickness of the second electron injecting layer is 1nm.
Negative electrode is arranged in the second light emitting functional layer by thermal resistance evaporation.
When preferably, thermal resistance evaporation is prepared negative electrode, condition is pressure 2 * 10
-4～5 * 10
-3pa, speed 1～10nm/s.
Preferably, the material of negative electrode is a kind of in silver, aluminium, platinum and gold.More preferably, the material of negative electrode is silver.
Preferably, the thickness of negative electrode is 60～300nm.More preferably, the thickness of negative electrode is 120nm.
The present invention has following beneficial effect:
Organic electroluminescence device prepared by the present invention, charge generation layer is comprised of the metal oxide layer stacking gradually, metal level and p-type doped layer, the work function of the metal oxide using in metal oxide layer is lower, there is the generation of good hole and can effectively carry out injection and the transmission in hole with the bipolarity metal oxide of transmittability, improve hole regeneration injectability, effectively improve device luminous efficiency and brightness; And the existence of metal in metal level can improve the light transmission rate of charge generation layer; P-type doped layer can farthest improve the speed of injection and the transmission in hole, strengthens light scattering effect simultaneously, improves light and takes out efficiency.
Meanwhile, preparation method of the present invention is simple, be easy to control and operation, and raw material easily obtains.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the structure chart of the organic electroluminescence device that provides of the embodiment of the present invention 1;
Fig. 2 is organic electroluminescence device and the current density of comparative example and the graph of a relation of current efficiency that the embodiment of the present invention 1 provides.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
A preparation method for organic electroluminescence device, comprises the following steps:
(1) ito glass substrate is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 5 * 10
-4under the condition of Pa, evaporation speed thermal resistance evaporation first light emitting functional layer in clean ito glass substrate with 0.6nm/s, comprises the first hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer that stack gradually;
Particularly, the material of the first hole injection layer is MoO
3, thickness is 40nm; The material of the first hole transmission layer is TCTA, and thickness is 40nm; The material of the first luminescent layer is ADN, and thickness is 25nm; The material of the first electron transfer layer is TPBi, and thickness is 60nm;
(3) at pressure, be 5 * 10
-4under the condition of Pa, on the first electron transfer layer, thermal resistance evaporation is prepared metal oxide layer, metal level and p-type doped layer as charge generation layer successively, wherein, with evaporation speed evaporation metal oxide skin(coating) and the metal level of 6nm/s, with the evaporation speed evaporation p-type doped layer of 0.6nm/s:
Particularly, the material of metal oxide layer is MoO
3, thickness is 20nm; The material of metal level is Ag, and thickness is 2nm; The material of p-type doped layer is the composite material that F4-TCNQ and m-MTDATA form, and the mass fraction that F4-TCNQ accounts for m-MTDATA is 1%, and thickness is 20nm;
(4) at pressure, be 5 * 10
-4under the condition of Pa, evaporation speed thermal resistance evaporation on p-type doped layer with 0.6nm/s is prepared the second light emitting functional layer, comprise the second hole transmission layer, the second luminescent layer, the second electron transfer layer, the second electron injecting layer that stack gradually, evaporation speed evaporation on the second electron injecting layer with 6nm/s is prepared negative electrode, obtains needed electroluminescent device;
Particularly, the material of the second hole transmission layer is NPB, and thickness is 40nm; The material of the second luminescent layer is ADN, and thickness is 25nm; The material of the second electron transfer layer is TAZ, and thickness is 80nm; The material of the second electron injecting layer is CsN
3, thickness is 1nm; The material of negative electrode is Ag, and thickness is 120nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: ito glass/MoO
3/ TCTA/ADN/TPBi/MoO
3/ Ag/m-MTDATA:F4-TCNQ/NPB/ADN/TAZ/CsN
3/ Ag.
Fig. 1 is the structural representation of the organic electroluminescence device of the present embodiment.As shown in Figure 1, the structure of this organic electroluminescence device comprises that the conductive anode substrate of glass 10, the second light emitting functional layer 20(that stack gradually comprise the first hole injection layer 201, the first hole transport 202, the first luminescent layer 203 and the first electron transfer layer 204), charge generation layer 30(comprises metal oxide layer 301, metal level 302, p-type doped layer 303), the second light emitting functional layer 40(comprises the second hole transmission layer 401, the second luminescent layer 402, the second electron transfer layer 403 and the second electron injecting layer 404) and negative electrode 50.
Embodiment 2
A preparation method for organic electroluminescence device, comprises the following steps:
(1) AZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 2 * 10
-4under the condition of Pa, evaporation speed thermal resistance evaporation first light emitting functional layer in clean AZO substrate of glass with 1nm/s, comprises the first hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer that stack gradually;
Particularly, the material of the first hole injection layer is V
2o
5, thickness is 80nm; The material of the first hole transmission layer is NPB, and thickness is 60nm; The material of the first luminescent layer is DCJTB, and thickness is 5nm; The material of the first electron transfer layer is TAZ, and thickness is 40nm;
(3) at pressure, be 2 * 10
-4under the condition of Pa, on the first electron transfer layer, thermal resistance evaporation is prepared metal oxide layer, metal level and p-type doped layer as charge generation layer successively, wherein, with evaporation speed evaporation metal oxide skin(coating) and the metal level of 10nm/s, with the evaporation speed evaporation p-type doped layer of 1nm/s;
Particularly, the material of metal oxide layer is V
2o
5, thickness is 5nm; The material of metal level is Au, and thickness is 10nm; The material of p-type doped layer is the composite material that CuPc and 2T-NATA form, and the mass fraction that 2T-NATA accounts for CuPc is 5%.Thickness is 50nm;
(4) at pressure, be 2 * 10
-4under the condition of Pa, evaporation speed thermal resistance evaporation second light emitting functional layer on p-type doped layer with 1nm/s, comprise the second hole transmission layer, the second luminescent layer, the second electron transfer layer, the second electron injecting layer that stack gradually, evaporation speed evaporation on the second electron injecting layer with 10nm/s is prepared negative electrode, obtains needed electroluminescent device;
Particularly, the material of the second hole transmission layer is TAPC, and thickness is 20nm; The material of the second luminescent layer is BCzVBi, and thickness is 40nm; The material of the second electron transfer layer is Bphen, and thickness is 200nm; The material of the second electron injecting layer is LiF, and thickness is 0.5nm; The material of negative electrode is Pt, and thickness is 60nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: AZO glass/V
2o
5/ NPB/DCJTB/TAZ/V
2o
5/ Au/CuPc:2T-NATA/TAPC/BCzVBi/Bphen/LiF/Pt.
Embodiment 3
A preparation method for organic electroluminescence device, comprises the following steps:
(1) IZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 5 * 10
-3under the condition of Pa, evaporation speed thermal resistance evaporation first light emitting functional layer in clean IZO substrate of glass with 0.1nm/s, comprises the first hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer that stack gradually;
Particularly, the material of the first hole injection layer is WO
3, thickness is 20nm; The material of the first hole transmission layer is TAPC, and thickness is 30nm; The material of the first luminescent layer is Alq
3, thickness is 10nm; The material of the first electron transfer layer is Bphen, and thickness is 200nm;
(3) at pressure, be 5 * 10
-3under the condition of Pa, on the first electron transfer layer, thermal resistance evaporation is prepared metal oxide layer, metal level and p-type doped layer as charge generation layer successively, wherein, with evaporation speed evaporation metal oxide skin(coating) and the metal level of 1nm/s, with the evaporation speed evaporation p-type doped layer of 0.1nm/s;
Particularly, the material of metal oxide layer is WO
3, thickness is 40nm; The material of metal level is Pt, and thickness is 1nm; P-type doped layer is TPD, 1T-NATA and 2T-NATA.1T-NATA, 2T-NATA doping ratio is respectively 0.5%, thickness is 10nm;
(4) at pressure, be 5 * 10
-3under the condition of Pa, evaporation speed thermal resistance evaporation on p-type doped layer with 0.1nm/s is prepared the second light emitting functional layer, comprise the second hole transmission layer, the second luminescent layer, the second electron transfer layer, the second electron injecting layer that stack gradually, evaporation speed evaporation on the second electron injecting layer with 1nm/s is prepared negative electrode, obtains needed electroluminescent device;
Particularly, the material of the second hole transmission layer is NPB, and thickness is 60nm; The material of the second luminescent layer is Alq
3, thickness is 35nm; The material of the second electron transfer layer is TPBi, and thickness is 40nm; The material of the second electron injecting layer is Cs
2cO
3, thickness is 10nm; The material of negative electrode is Al, and thickness is 300nm;
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: IZO glass/WO
3/ TAPC/Alq
3/ Bphen/WO
3/ Pt/TPD:1T-NATA:2T-NATA/NPB/Alq
3/ TPBi/Cs
2cO
3/ Al.
Embodiment 4
A preparation method for organic electroluminescence device, comprises the following steps:
(1) IZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 5 * 10
-4under the condition of Pa, evaporation speed thermal resistance evaporation first light emitting functional layer in clean IZO substrate of glass with 0.5nm/s, comprises the first hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer that stack gradually;
Particularly, the material of the first hole injection layer is MoO
3, thickness is 30nm; The material of the first hole transmission layer is NPB, and thickness is 50nm; The material of the first luminescent layer is BCzVBi, and thickness is 40nm; The material of the first electron transfer layer is Bphen, and thickness is 40nm;
(3) at pressure, be 5 * 10
-4under the condition of Pa, on the first electron transfer layer, thermal resistance evaporation is prepared metal oxide layer, metal level and p-type doped layer as charge generation layer successively, wherein, with evaporation speed evaporation metal oxide skin(coating) and the metal level of 10nm/s, with the evaporation speed evaporation p-type doped layer of 1nm/s;
Particularly, the material of metal oxide layer is WO
3, thickness is 15nm; The material of metal level is Al, and thickness is 3nm; The material of p-type doped layer is the composite material that m-MTDATA and 2T-NATA form, and the mass fraction that 2T-NATA accounts for m-MTDATA is 1.5%.Thickness is 25nm;
(4) at pressure, be 5 * 10
-4under the condition of Pa, evaporation speed thermal resistance evaporation second light emitting functional layer on p-type doped layer with 0.5nm/s, comprise the second hole transmission layer, the second luminescent layer, the second electron transfer layer, the second electron injecting layer that stack gradually, evaporation speed evaporation on the second electron injecting layer with 5nm/s is prepared negative electrode, obtains needed electroluminescent device;
Particularly, the material of the second hole transmission layer is TAPC, and thickness is 50nm; The material of the second luminescent layer is BCzVBi, and thickness is 40nm; The material of the second electron transfer layer is TPBi, and thickness is 100nm; The material of the second electron injecting layer is CsF, and thickness is 2nm; The material of negative electrode is Au, and thickness is 180nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: IZO glass/MoO
3/ NPB/BCzVBi/Bphen/WO
3/ Al/m-MTDATA:2T-NATA/TAPC/BCzVBi/TPBi/CsF/Au.
Comparative example
A preparation method for organic electroluminescence device, comprises the following steps:
(1) ito glass substrate is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface;
(2) in high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), pressure is 5 * 10
-4under the condition of Pa, with the evaporation speed of 0.6nm/s in clean ito glass substrate successively thermal resistance evaporation prepare hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer, with evaporation speed thermal resistance evaporation on electron injecting layer of 6nm/s, prepare negative electrode;
Particularly, the material of hole injection layer is MoO
3, thickness is 40nm; The material of hole transmission layer is NPB, and thickness is 40nm; The material of luminescent layer is ADN, and thickness is 25nm; The material of electron transfer layer is TPBi, and thickness is 60nm; The material of electron injecting layer is CsN
3, thickness is 1nm; The material of negative electrode is Ag, and thickness is 120nm.
After above step completes, obtain a kind of organic electroluminescence device, structure is specifically expressed as: ito glass/MoO
3/ NPB/ADN/TPBi/CsN
3/ Ag.
Utilize the Keithley2400 test electric property of U.S. Keithley company, colorimeter (Japanese Konica Minolta company, model: CS-100A) test brightness and colourity.
Fig. 2 is the graph of a relation of the organic electroluminescence device of the present embodiment and the current density of comparative example and current efficiency.Wherein, curve 1 is the present embodiment the current density of organic electroluminescence device and the graph of a relation of current efficiency; For comparative example, (structure is specifically expressed as curve 2: ito glass/MoO
3/ NPB/ADN/TPBi/CsN
3/ Ag) current density and the graph of a relation of current efficiency.
As can see from Figure 2, under different current densities, the current efficiency of embodiment 1 is large than comparative example all, maximum current efficiency is 1.87cd/A, and that comparative example is only 1.09cd/A, this explanation, organic electroluminescence device provided by the invention, charge generation layer is comprised of metal oxide layer, metal level and p-type doped layer, improve the transmission rate of electronics, improve hole regeneration injectability, improve the transmitance of charge generation layer, strengthen light scattering effect, the final luminous efficiency that effectively improves.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (9)
1. an organic electroluminescence device, is characterized in that, comprises the conductive anode substrate of glass, the first light emitting functional layer, charge generation layer, the second light emitting functional layer and the negative electrode that stack gradually;
Described charge generation layer comprises metal oxide layer, metal level and the p-type doped layer stacking gradually; The material of described metal oxide layer is bipolarity metal oxide; The material of described metal level is aluminium or noble metal; The material of described p-type doped layer is the mixture that hole guest materials and hole mobile material form, and the mass fraction of described hole guest materials duty hole transport materials is 0.5～5%;
Described hole guest materials is 2,3,5,6-tetrafluoro-7,7,8,8, and-four cyano-benzoquinone bismethane, 4,4, a kind of in 4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine and 4,4,4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine; Described hole mobile material is 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4, a kind of in 4 '-benzidine and CuPc.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described p-type doped layer is 10～50nm.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, described noble metal is a kind of in silver, platinum and gold.
4. organic electroluminescence device as claimed in claim 1, is characterized in that, described bipolarity metal oxide is a kind of in molybdenum trioxide, tungstic acid and vanadic oxide.
5. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
Conductive anode substrate of glass is provided;
In described conductive anode substrate of glass, thermal resistance evaporation is prepared the first light emitting functional layer, charge generation layer, the second light emitting functional layer and negative electrode successively, obtains organic electroluminescence device;
Described charge generation layer comprises metal oxide layer, metal level and the p-type doped layer stacking gradually, and the material of described metal oxide layer is bipolarity metal oxide; The material of described metal level is aluminium or noble metal; The material of described p-type doped layer is the mixture that hole guest materials and hole mobile material form, and the mass fraction of described hole guest materials duty hole transport materials is 0.5～5%;
Described hole guest materials is 2,3,5,6-tetrafluoro-7,7,8,8, and-four cyano-benzoquinone bismethane, 4,4,4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine and 4,4,4-tri-(naphthyl-1-phenyl-ammonium) triphenylamine; Described hole mobile material is 4,4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine, N, N '-bis-(3-aminomethyl phenyl)-N, N '-diphenyl-4, a kind of in 4 '-benzidine and CuPc.
6. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, pressure prepared by described thermal resistance evaporation is 2 * 10
-4～5 * 10
-3pa.
7. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, the thickness of described p-type doped layer is 10～50nm.
8. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, described noble metal is a kind of in silver, platinum and gold.
9. the preparation method of organic electroluminescence device as claimed in claim 5, is characterized in that, described bipolarity metal oxide is a kind of in molybdenum trioxide, tungstic acid and vanadic oxide.
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Application publication date: 20140917 |