CN109686852A - A kind of inversion Organic Light Emitting Diode and preparation method thereof - Google Patents
A kind of inversion Organic Light Emitting Diode and preparation method thereof Download PDFInfo
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- CN109686852A CN109686852A CN201811599713.9A CN201811599713A CN109686852A CN 109686852 A CN109686852 A CN 109686852A CN 201811599713 A CN201811599713 A CN 201811599713A CN 109686852 A CN109686852 A CN 109686852A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010410 layer Substances 0.000 claims abstract description 217
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000004305 biphenyl Substances 0.000 claims abstract description 39
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 33
- 238000002347 injection Methods 0.000 claims abstract description 30
- 239000007924 injection Substances 0.000 claims abstract description 30
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 26
- 230000005540 biological transmission Effects 0.000 claims abstract description 24
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical group [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910000024 caesium carbonate Inorganic materials 0.000 claims abstract description 12
- 238000001704 evaporation Methods 0.000 claims description 40
- 230000008020 evaporation Effects 0.000 claims description 38
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 20
- -1 8- hydroxyl Quinoline aluminum Chemical group 0.000 claims description 19
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 229960003540 oxyquinoline Drugs 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 8
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 5
- XSUNFLLNZQIJJG-UHFFFAOYSA-N 2-n-naphthalen-2-yl-1-n,1-n,2-n-triphenylbenzene-1,2-diamine Chemical class C1=CC=CC=C1N(C=1C(=CC=CC=1)N(C=1C=CC=CC=1)C=1C=C2C=CC=CC2=CC=1)C1=CC=CC=C1 XSUNFLLNZQIJJG-UHFFFAOYSA-N 0.000 claims description 3
- 150000005360 2-phenylpyridines Chemical class 0.000 claims description 3
- RNKGDBXXIBUOTR-UHFFFAOYSA-N 3,6-dioxocyclohexa-1,4-diene-1-carbonitrile Chemical compound O=C1C=CC(=O)C(C#N)=C1 RNKGDBXXIBUOTR-UHFFFAOYSA-N 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 239000002344 surface layer Substances 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000002356 single layer Substances 0.000 abstract description 2
- 238000007740 vapor deposition Methods 0.000 description 18
- 239000011521 glass Substances 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 15
- 238000007738 vacuum evaporation Methods 0.000 description 10
- YLYPIBBGWLKELC-RMKNXTFCSA-N 2-[2-[(e)-2-[4-(dimethylamino)phenyl]ethenyl]-6-methylpyran-4-ylidene]propanedinitrile Chemical compound C1=CC(N(C)C)=CC=C1\C=C\C1=CC(=C(C#N)C#N)C=C(C)O1 YLYPIBBGWLKELC-RMKNXTFCSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000007747 plating Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CMCRGQKDYIVDCV-UHFFFAOYSA-N NCC1=CC=C(C=C1)NC1=CC=C(C2=CC=C(NC3=CC=C(C=C3)CN)C=C2)C=C1 Chemical class NCC1=CC=C(C=C1)NC1=CC=C(C2=CC=C(NC3=CC=C(C=C3)CN)C=C2)C=C1 CMCRGQKDYIVDCV-UHFFFAOYSA-N 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 101150075675 tatC gene Proteins 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
- H10K50/171—Electron injection 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
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
-
- 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
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/321—Inverted OLED, i.e. having cathode between substrate and anode
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Optics & Photonics (AREA)
- Manufacturing & Machinery (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention relates to LED technology fields, more particularly to a kind of inversion Organic Light Emitting Diode and preparation method thereof, inversion Organic Light Emitting Diode provided by the invention successively includes cathode plate layer, electron injecting layer, electron transfer layer, luminescent layer, hole transmission layer, hole injection layer and anode from bottom to top；The electron injecting layer includes that contact with cathode plate ZnS layer and the doped layer that contacts with ZnS layers；The material of the doped layer is Cs2CO3 and 4,7- diphenyl -1,10- ferrosin.Record according to the embodiment, the maximum current efficiency >=30cd/A provided by the invention for being inverted Organic Light Emitting Diode, the maximum current efficiency 26.1cd/A compared with the inversion Organic Light Emitting Diode of single layer electronic implanted layer are significantly improved.The present invention also provides the preparation method for being inverted Organic Light Emitting Diode, which can be improved product quality, obtains complete Organic Light Emitting Diode.
Description
Technical field
The present invention relates to LED technology field more particularly to a kind of inversion Organic Light Emitting Diode and its preparation sides
Method.
Background technique
Currently, organic luminescent device has been widely used in actual production life, it is especially big in lighting area
Put extraordinary splendor.What the organic material in organic luminescent device was largely made of carbon and hydrogen, being used to do electronic device has
Many benefits, for example, it is easy to manufacture, at low cost, chemical reconcile it is transparent flexible etc..
Organic luminescent device generallys use the mode just set, and is that following luminous form shines, light passes through the substrate current situation
TFT and the metal wire circuit that must be based upon on substrate block, so actually luminous area will be restricted, reduction hair
Ratio shared by light area.And inverted organic luminescent device then can solve the above problem.But the organic hair of traditional inversion
Optical device successively includes that substrate, transparent cathode, OLED, HIL and reflection anode, the major defect of the structure are electricity from the bottom to top
The injection barrier of son is high, and the injection of electronics is extremely difficult, seriously limits the development for being inverted organic luminescent device.
Summary of the invention
The inversion Organic Light Emitting Diode that the purpose of the present invention is to provide a kind of electron transport abilities is good, current efficiency is high
And preparation method thereof.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of inversion Organic Light Emitting Diodes, from bottom to top successively include cathode plate layer, electron injection
Layer, electron transfer layer, luminescent layer, hole transmission layer, hole injection layer and anode；
The electron injecting layer includes that contact with cathode plate ZnS layer and the doped layer that contacts with ZnS layers；
The material of the doped layer is Cs2CO3With 4,7- diphenyl -1,10- ferrosin.
Preferably, the material of the electron transfer layer is 4,7- diphenyl -1,10- ferrosin, 8-hydroxyquinoline, 1,3,5-
Three (1- phenyl -1H- benzimidazolyl-2 radicals-yl) one or more of benzene and three (8-hydroxyquinoline) aluminium.
Preferably, the material of the luminescent layer is 8-hydroxyquinoline, 4- (dimercapto methylene) -2- methyl -6- (to diformazan
Aminostyryl) -4H- pyrans, 9,10- bis- (2- naphthalene) anthracene, three (2- phenylpyridines) conjunction iridium, 4,4- bis- (9- carbazole) biphenyl
With 4- [1- [4- [two (4- aminomethyl phenyl) amino] phenyl] cyclohexyl]-N- (3- aminomethyl phenyl)-N- (4- aminomethyl phenyl) aniline
One or more of.
Preferably, the material of the hole transmission layer be N, N'- diphenyl-N, N'- (1- naphthalene)-biphenyl -4 1,1'-,
4'- diamines, N, bis- (3- the aminomethyl phenyl)-N of N'-, N'- diphenyl-[1,1'- biphenyl] -4,4'- diamines, 4- [1- [4- [two (4-
Aminomethyl phenyl) amino] phenyl] cyclohexyl]-N- (3- aminomethyl phenyl)-N- (4- aminomethyl phenyl) aniline and N, N'- diphenyl-N,
One or more of bis- (4- aminomethyl phenyl) -4,4'- benzidines of N'-.
Preferably, the material of the hole injection layer is MoO3, 4,4', 4 "-three (2- naphthylphenyl amino) triphenylamines
One or more of with 7,7,8,8- four cyano benzoquinone's bismethane.
Preferably, the material of the anode is one or more of Al, Ag and Au.
Preferably, described ZnS layers with a thickness of 1~3nm, the doped layer with a thickness of 25~35nm.
Preferably, Cs in the doped layer2CO3Mass ratio with 4,7- diphenyl -1,10- ferrosin is 1:(8~10).
The present invention also provides the preparation methods for being inverted Organic Light Emitting Diode, comprising the following steps:
ZnS layers, doped layer, electron transfer layer, luminescent layer, hole transmission layer, hole is successively deposited in cathode plate layer surface
Implanted layer and anode obtain being inverted Organic Light Emitting Diode.
Preferably, ZnS layers of the evaporation rate, which is deposited, is
The evaporation rate that the doped layer is deposited is
The evaporation rate that the electron transfer layer, luminescent layer, hole transmission layer and hole injection layer is deposited is independently
The evaporation rate that the anode is deposited is
The present invention provides a kind of inversion Organic Light Emitting Diodes, from bottom to top successively include cathode plate layer, electron injection
Layer, electron transfer layer, luminescent layer, hole transmission layer, hole injection layer and anode；The electron injecting layer includes connecing with cathode plate
Touching ZnS layer and the doped layer that contacts with ZnS layers；The material of the doped layer is Cs2CO3With 4,7- diphenyl -1,10- phenanthrene hello
Quinoline.The electron injecting layer that the present invention is arranged between cathode and electron transfer layer is double-layer structure, improves the transmittability of electronics,
The balance quality for increasing carrier, thus to resist roll-offing for device efficiency.Meanwhile through two layers of electron injecting layer on material
Being arranged contact with cathode plate ZnS layer and the doped layer that contacts with ZnS layers, reduces single energy level difference by step structure, drops
Low electron injection barrier, keeps electron injection more smooth.Record according to the embodiment, inversion organic light emission provided by the invention
Maximum current efficiency >=30cd/A of diode, compared with the maximum current effect of the inversion Organic Light Emitting Diode of single layer electronic implanted layer
Rate 26.1cd/A is significantly improved.
The present invention also provides the preparation method for being inverted Organic Light Emitting Diode, which can be improved product quality,
Obtain complete Organic Light Emitting Diode.
Detailed description of the invention
Fig. 1 is the structural schematic diagram provided by the invention for being inverted Organic Light Emitting Diode；
Fig. 2 is the current efficiency for the inversion Organic Light Emitting Diode that embodiment 1 and comparative example 1 are prepared in different brightness
Under curve graph.
Specific embodiment
The present invention provides a kind of inversion Organic Light Emitting Diodes, from bottom to top successively include cathode plate layer, electron injection
Layer, electron transfer layer, luminescent layer, hole transmission layer, hole injection layer and anode；
The electron injecting layer includes that contact with cathode plate ZnS layer and the doped layer that contacts with ZnS layers；
The material of the doped layer is Cs2CO3With 4,7- diphenyl -1,10- ferrosin.
In the present invention, if without specified otherwise, all raw materials are commercial product well known to those skilled in the art.
In the present invention, the inversion Organic Light Emitting Diode includes cathode plate layer；In the present invention, the cathode plate layer
Material be preferably indium tin oxide (ITO) electro-conductive glass；In the present invention, the thickness of the cathode plate layer be preferably 140~
160nm, more preferably 145~155nm, most preferably 148~152nm.
In the present invention, the inversion Organic Light Emitting Diode further includes electron injecting layer；The electron injecting layer is double
Layer ZnS layer and the doped layer that contacts with ZnS layers including what is contacted with cathode plate.In the present invention, the electron injecting layer is total
Thickness is preferably 26~38nm, more preferably 28~35nm, most preferably 30~32nm；ZnS layers of the thickness is preferably 1~
3nm, more preferably 1.5~2.5nm；The Cs2CO3Thickness with doped layer is preferably 25~35nm, more preferably 28~
32nm.In the present invention, Cs in the doped layer2CO3Mass ratio with 4,7- diphenyl -1,10- ferrosin be preferably 1:(8~
10), more preferably 1:(8.5~9.5).
In the present invention, the electron injecting layer is double-layer structure, and ZnS layers and doped layer match, and can improve electronics
Transmittability increases the balance quality of carrier, so as to resist roll-offing for device efficiency, the selection of material can reduce electronics
Energy level potential barrier is injected, keeps electron injection more smooth.
In the present invention, the inversion Organic Light Emitting Diode further includes electron transfer layer；In the present invention, the electronics
The overall thickness of transport layer is preferably 15~25nm, more preferably 18~22nm.In a specific embodiment of the present invention, the electronics
Transport layer is preferably one layer or bilayer；When the electron transfer layer is double-deck, the present invention is to each layer of the electron transfer layer
Thickness does not have any special restriction, makes the sum of two layers thickness in the total thickness of above-mentioned electron transfer layer；Institute
The material for stating each layer of electron transfer layer is preferably 4,7- diphenyl -1,10- ferrosin, 8-hydroxyquinoline aluminium (Alq), 1,3,5- tri-
(1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene (TPBi) and three (8-hydroxyquinoline) aluminium (Alq3One or more of)；Work as institute
State electron transfer layer material be above-mentioned specific choice in it is two or more when, the present invention does not have the proportion of the specific substance
Any special restriction, is mixed by any proportion.
In the present invention, the effect of the electron transfer layer is transmission electronics.
In the present invention, the inversion Organic Light Emitting Diode further includes luminescent layer；In the present invention, the luminescent layer
Material is preferably 8-hydroxyquinoline aluminium (Alq), 4- (dimercapto methylene) -2- methyl -6- (to dimethylaminostyryl) -
4H- pyrans (DCM1), 9,10- bis- (2- naphthalene) anthracene (ADN), three (2- phenylpyridines) close iridium (Ir (ppy)3), 4, (the 9- click of 4- bis-
Azoles) biphenyl (CBP) and 4- [1- [4- [two (4- aminomethyl phenyl) amino] phenyl] cyclohexyl]-N- (3- aminomethyl phenyl)-N- (4- first
One or more of base phenyl) aniline (TATC)；In the present invention, when the material of the luminescent layer is in above-mentioned specific choice
It is two or more when, proportion no any special restriction of the present invention to the specific substance can be mixed by any proportion
Conjunction.
In the present invention, the thickness of the luminescent layer is preferably 15~25nm, more preferably 18~22nm.
In the present invention, electrons and holes meet to shine in luminescent layer.
In the present invention, the inversion Organic Light Emitting Diode further includes hole transmission layer, the material of the hole transmission layer
Material is preferably N, N'- diphenyl-N, N'- (1- naphthalene) -1,1'- biphenyl -4,4'- diamines (NPB), N, bis- (the 3- methylbenzenes of N'-
Base)-N, N'- diphenyl-[1,1'- biphenyl] -4,4'- diamines (TPD), 4- [1- [4- [two (4- aminomethyl phenyl) amino] phenyl]
Cyclohexyl]-N- (3- aminomethyl phenyl)-N- (4- aminomethyl phenyl) aniline (TAPC) and bis- (the 4- methylbenzenes of N, N'- diphenyl-N, N'-
One or more of base) -4,4'- benzidine (p-TPD)；In the present invention, when the material of the hole transmission layer is upper
When stating two or more in specific choice, proportion no any special restriction of the present invention to the specific substance can be by appointing
Meaning proportion is mixed.
In the present invention, the thickness of the hole transmission layer is preferably 25~35nm, more preferably 28~32nm.
In the present invention, the effect of the hole transmission layer is transporting holes.
In the present invention, the inversion Organic Light Emitting Diode further includes hole injection layer, the material of the hole injection layer
Material is preferably MoO3, 4,4', 4 "-three (2- naphthylphenyl amino) triphenylamines (TCNQ) and 7,7,8,8- four cyano benzoquinone
One or more of bismethane (2T-NATA)；In the present invention, when the material of the hole injection layer is above-mentioned specific choice
In it is two or more when, proportion no any special restriction of the present invention to the specific substance can be carried out by any proportion
Mixing.
In the present invention, the thickness of the hole injection layer is preferably 3~8nm, more preferably 4~6nm.
In the present invention, the effect of the hole injection layer is to aid in hole injection.
In the present invention, the inversion Organic Light Emitting Diode further includes anode；In the present invention, the material of the anode
Preferably one or more of Al, Ag and Au；When the material of the anode be above-mentioned specific choice in it is two or more when, this
Proportion no any special restriction of the invention to the specific substance, can be mixed by any proportion.
In the present invention, the thickness of the anode is preferably 120~180nm, more preferably 130~170nm, most preferably
140~160nm.
In the present invention, the effect of the anode acts as anode and generates hole.
The present invention also provides the preparation methods for being inverted Organic Light Emitting Diode, comprising the following steps:
ZnS layers, doped layer, electron transfer layer, luminescent layer, hole transmission layer, hole is successively deposited in cathode plate layer surface
Implanted layer and anode obtain being inverted Organic Light Emitting Diode.
Before being deposited, the present invention preferably pre-processes cathode plate；In the present invention, the preferred packet of the pretreatment
Include cleaning, drying and ultraviolet lighting processing.The present invention is to the no any special restriction of cleaning, using those skilled in the art
Cleaning process known to member carries out.The present invention any special restriction no to the drying, using those skilled in the art
Drying process known to member carries out.
In the present invention, the time of the treatment with ultraviolet light is preferably 10~20min, more preferably 12~18min, optimal
It is selected as 14~16min；The present invention does not have any special restriction to the other conditions parameter of the treatment with ultraviolet light, using ability
Conditional parameter known to field technique personnel is handled.
In the present invention, the vapor deposition preferably carries out under conditions of vacuum；The vacuum degree of the vacuum is preferably≤10- 5mbar。
In the present invention, the vapor deposition preferably carries out in vacuum evaporation instrument, preferably includes the evaporation and plating successively carried out
Film.
In the present invention, the evaporation rate of ZnS layers of the vapor deposition is preferablyMore preferablyMost preferablyThe present invention does not have any special limit to the plated film of ZnS layers of the vapor deposition
It is fixed, it is carried out using coating process well known to those skilled in the art.
In the present invention, described ZnS layers of material ZnS is preferably disposed in open boat source, and is fixed in vacuum evaporation instrument
Boat position on.
In the present invention, the detailed process of the vapor deposition doped layer is preferably by Cs2CO3Evaporation rate stablize existAfterwards, 4,7- diphenyl -1,10- ferrosin is evaporated, and makes Cs2CO3With 4,7- diphenyl -1,10- ferrosin
Evapo tranpiration rate reachesCarry out plated film；More preferably by Cs2CO3Evaporation rate stablize existAfterwards, it evaporates 4,7- diphenyl -1,10- ferrosin and makes Cs2CO3With 4,7- diphenyl -1,10- ferrosin
Evapo tranpiration rate reachCarry out plated film.The present invention does not have any spy to the plated film in the vapor deposition doped layer
Different restriction is carried out using coating process well known to those skilled in the art.
In the present invention, the Cs2CO3On the boat position for being preferably disposed in open boat source, and being fixed in vacuum evaporation instrument；
4,7- diphenyl -1,10- ferrosin is preferably disposed in closing boat source, and on the boat position being fixed in vacuum evaporation instrument.
In the present invention, the evaporation rate of the vapor deposition electron transfer layer, luminescent layer, hole transmission layer and hole injection layer
It is independent to be preferablyMore preferablyMost preferably
In the present invention, the material of the electron transfer layer, luminescent layer, hole transmission layer and hole injection layer is independent excellent
It selects on the boat position for being placed in open boat source, and being fixed in vacuum evaporation instrument.
In the present invention, the evaporation rate of the vapor deposition anode is preferablyMore preferably Most
PreferablyThe present invention does not have any special restriction to the plated film of the vapor deposition anode, using those skilled in the art
Coating process known to member carries out.
In the present invention, the material of the vapor deposition anode is preferably disposed in open boat source, and is fixed in vacuum evaporation instrument
Boat position on.
In the present invention, in the preparation process, the thickness of each layer preferably passes through film-thickness monitoring and is controlled.
Inversion Organic Light Emitting Diode provided by the invention and preparation method thereof is carried out below with reference to embodiment detailed
Illustrate, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Structure as shown in Figure 1: cathode plate layer is ITO electro-conductive glass；Electron injecting layer is ZnS layers and doped layer (10wt%
Cs2CO3- 90wt%4,7- diphenyl -1,10- ferrosin)；Electron transfer layer be 4,7- diphenyl -1,10- ferrosin layer and
Alq；Luminescent layer is 10wt%DCM1-90wt%Alq doped layer；Hole transmission layer is NPB layers；Hole injection layer is MoO3；Sun
Extremely Al layers；
After the ITO electro-conductive glass of 150nm thickness is cleaned and dried, carries out ultraviolet lighting and handle 15min, obtain pre- place
ITO electro-conductive glass after reason；
Pretreated ITO electro-conductive glass is placed in vacuum evaporation instrument, is 1 × 10 in vacuum degree-6Under conditions of mbar,
Heating evaporation is placed in the ZnS in open boat source, and evaporation rate isPlated film after control film thickness reaches 2nm, stops steaming
Boat source is closed in plating；
Heating evaporation is placed in the Cs in open boat source2CO3, evaporation rate stabilizes toAfterwards, heating evaporation is placed in envelope
4,7- diphenyl -1,10- ferrosin in boat source is closed, Cs is made2CO3With the evapo tranpiration rate of 4,7- diphenyl -1,10- ferrosin
ForPlated film stops vapor deposition after control film thickness reaches 30nm, closes boat source；
Successively heating evaporation be placed in 4,7- diphenyl -1,10- ferrosin in open boat source, Alq, Alq, DCM1, NPB,
MoO3And Al, evaporation rate are respectively WithPlated film stops vapor deposition after control film thickness respectively reaches 10nm, 10nm, 20nm, 30nm, 5nm and 150nm respectively,
Boat source is closed respectively, obtains being inverted Organic Light Emitting Diode.
Embodiment 2
Structure as shown in Figure 1: cathode plate layer is ITO electro-conductive glass；Electron injecting layer is ZnS layers and doped layer (10wt%
Cs2CO3- 90wt%4,7- diphenyl -1,10- ferrosin)；Electron transfer layer is 4,7- diphenyl -1,10- ferrosin；Luminescent layer
For 90wt%ADN-10wt%DCM1 doped layer；Hole transmission layer is NPB layers；Hole injection layer is MoO3；Anode is Al；
After the ITO electro-conductive glass of 160nm thickness is cleaned and dried, carries out ultraviolet lighting and handle 20min, obtain pre- place
ITO electro-conductive glass after reason；
Pretreated ITO electro-conductive glass is placed in vacuum evaporation instrument, is 1 × 10 in vacuum degree-6Under conditions of mbar,
Heating evaporation is placed in the ZnS in open boat source, and evaporation rate isPlated film after control film thickness reaches 1.5nm, stops steaming
Boat source is closed in plating；
Heating evaporation is placed in the Cs in open boat source2CO3, evaporation rate stabilizes toAfterwards, heating evaporation is placed in envelope
4,7- diphenyl -1,10- ferrosin in boat source is closed, Cs is made2CO3With the evapo tranpiration rate of 4,7- diphenyl -1,10- ferrosin
ForPlated film stops vapor deposition after control film thickness reaches 33nm, closes boat source；
Successively the 4,7- diphenyl -1,10- ferrosin in the open boat source of heating evaporation, ADN, DCM1, NPB, MoO3And Al,
Evaporation rate is respectively0.03/S, WithPlated film controls film thickness
After respectively reaching 20nm, 20nm, 30nm, 5nm and 150nm, stop vapor deposition respectively, closes boat source respectively, obtain being inverted organic hair
Optical diode.
Embodiment 3
Structure as shown in Figure 1: cathode plate layer is ITO electro-conductive glass；Electron injecting layer is ZnS layers and doped layer (10wt%
Cs2CO3- 90wt%4,7- diphenyl -1,10- ferrosin)；Electron transfer layer be 4,7- diphenyl -1,10- ferrosin layer and
Alq；Luminescent layer is 10wt%DCM1-90wt%Alq doped layer；Hole transmission layer is NPB layers；Hole injection layer is MoO3；Sun
Extremely Al layers；
After the ITO electro-conductive glass of 160nm thickness is cleaned and dried, carries out ultraviolet lighting and handle 20min, obtain pre- place
ITO electro-conductive glass after reason；
Pretreated ITO electro-conductive glass is placed in vacuum evaporation instrument, is 1 × 10 in vacuum degree-6Under conditions of mbar,
Heating evaporation is placed in the ZnS in open boat source, and evaporation rate isPlated film after control film thickness reaches 1.5nm, stops steaming
Boat source is closed in plating；
Heating evaporation is placed in the Cs in open boat source2CO3, evaporation rate stabilizes toAfterwards, heating evaporation is placed in envelope
4,7- diphenyl -1,10- ferrosin in boat source is closed, Cs is made2CO3With the evapo tranpiration rate of 4,7- diphenyl -1,10- ferrosin
ForPlated film stops vapor deposition after control film thickness reaches 33nm, closes boat source；
Successively the 4,7- diphenyl -1,10- ferrosin in the open boat source of heating evaporation, Alq, Alq, DCM1, NPB, MoO3
And Al, evaporation rate are respectively WithPlated film stops vapor deposition after control film thickness respectively reaches 10nm, 10nm, 20nm, 30nm, 5nm and 150nm respectively, point
Not Guan Bi boat source, obtain be inverted Organic Light Emitting Diode.
Comparative example 1
According to sequence from the bottom to top, being followed successively by cathode plate layer is ITO electro-conductive glass；Electron injecting layer is doped layer
(10wt%Cs2CO3- 90wt%4,7- diphenyl -1,10- ferrosin)；Electron transfer layer is 4,7- diphenyl -1,10- ferrosin
Layer and Alq layers；Luminescent layer is that 10wt%Alq-90wt%DCM1 is adulterated layer by layer；Hole transmission layer is NPB layers；Hole injection layer is
MoO3；Anode is Al layers；
After the ITO electro-conductive glass of 160nm thickness is cleaned and dried, carries out ultraviolet lighting and handle 20min, obtain pre- place
ITO electro-conductive glass after reason；
Pretreated ITO electro-conductive glass is placed in vacuum evaporation instrument, is 1 × 10 in vacuum degree-6Under conditions of mbar,
Heating evaporation is placed in the Cs in open boat source2CO3, evaporation rate stabilizes toAfterwards, heating evaporation is placed in closing boat source
4,7- diphenyl -1,10- ferrosin, make Cs2CO3Evapo tranpiration rate with 4,7- diphenyl -1,10- ferrosin is
Plated film stops vapor deposition after control film thickness reaches 33nm, closes boat source；
Successively the 4,7- diphenyl -1,10- ferrosin in the open boat source of heating evaporation, Alq, Alq, DCM1, NPB, MoO3
And Al, evaporation rate are respectively WithPlated film stops vapor deposition respectively, closes respectively after control film thickness respectively reaches 10nm, 20nm, 30nm, 5nm and 150nm
Zhou Yuan is closed, obtains being inverted Organic Light Emitting Diode.
Fig. 2 is the current efficiency curve of embodiment 1 and the inversion light emitting diode at different brightnesses, as seen from the figure,
Maximum current efficiency >=the 30cd/A provided by the invention for being inverted light emitting diode has compared with the 26.1cd/A of comparative example 1 significantly to be mentioned
It is high.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of inversion Organic Light Emitting Diode, successively include from bottom to top cathode plate layer, electron injecting layer, electron transfer layer,
Luminescent layer, hole transmission layer, hole injection layer and anode；
The electron injecting layer includes that contact with cathode plate ZnS layer and the doped layer that contacts with ZnS layers；
The material of the doped layer is Cs2CO3With 4,7- diphenyl -1,10- ferrosin.
2. being inverted Organic Light Emitting Diode as described in claim 1, which is characterized in that the material of the electron transfer layer is 4,
7- diphenyl -1,10- ferrosin, 8-hydroxyquinoline aluminium, (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene of 1,3,5- tri- and three (8-
One or more of oxyquinoline) aluminium.
3. being inverted Organic Light Emitting Diode as described in claim 1, which is characterized in that the material of the luminescent layer is 8- hydroxyl
Quinoline aluminum, 4- (dimercapto methylene) -2- methyl -6- (to dimethylaminostyryl) -4H- pyrans, 9,10- bis- (2- naphthalene)
Anthracene, three (2- phenylpyridines) conjunction iridium, 4, (9- carbazole) biphenyl of 4- bis- and 4- [1- [4- [two (4- aminomethyl phenyl) amino] phenyl] ring
One or more of hexyl]-N- (3- aminomethyl phenyl)-N- (4- aminomethyl phenyl) aniline.
4. being inverted Organic Light Emitting Diode as described in claim 1, which is characterized in that the material of the hole transmission layer is N,
N'- diphenyl-N, N'- (1- naphthalene) -1,1'- biphenyl -4,4'- diamines, N, bis- (3- the aminomethyl phenyl)-N of N'-, N'- diphenyl -
[1,1'- biphenyl] -4,4'- diamines, 4- [1- [4- [two (4- aminomethyl phenyl) amino] phenyl] cyclohexyl]-N- (3- methylbenzene
Base) one of-N- (4- aminomethyl phenyl) aniline and bis- (4- the aminomethyl phenyl) -4,4'- benzidines of N, N'- diphenyl-N, N'-
Or it is several.
5. being inverted Organic Light Emitting Diode as described in claim 1, which is characterized in that the material of the hole injection layer is
MoO3, 4,4', one of 4 "-three (2- naphthylphenyl amino) triphenylamines and 7,7,8,8- four cyano benzoquinone's bismethane
Or it is several.
6. as described in claim 1 be inverted Organic Light Emitting Diode, which is characterized in that the material of the anode be Al, Ag and
One or more of Au.
7. being inverted Organic Light Emitting Diode as described in claim 1, which is characterized in that described ZnS layers with a thickness of 1~3nm,
The doped layer with a thickness of 25~35nm.
8. inversion light emitting diode as claimed in claim 1 or 7, which is characterized in that Cs in the doped layer2CO3With 4,7- bis-
The mass ratio of phenyl -1,10- ferrosin is 1:(8~10).
9. the preparation method according to any one of claims 1 to 8 for being inverted Organic Light Emitting Diode, comprising the following steps:
ZnS layers, doped layer, electron transfer layer, luminescent layer, hole transmission layer, hole injection is successively deposited in cathode plate layer surface
Layer and anode obtain being inverted Organic Light Emitting Diode.
10. preparation method as claimed in claim 9, which is characterized in that ZnS layers of the evaporation rate, which is deposited, is
The evaporation rate that the doped layer is deposited is
The evaporation rate that the electron transfer layer, luminescent layer, hole transmission layer and hole injection layer is deposited is independently
The evaporation rate that the anode is deposited is
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| CN105322098A (en) * | 2015-11-03 | 2016-02-10 | Tcl集团股份有限公司 | Quantum dot light-emitting diode capable of improving charge injection balance and preparation method for quantum dot light-emitting diode |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130285022A1 (en) * | 2012-04-25 | 2013-10-31 | Innolux Corporation | Organic light-emitting diode and display device employing the same |
| CN104659250A (en) * | 2013-11-19 | 2015-05-27 | 海洋王照明科技股份有限公司 | Organic electroluminescent device and preparation method thereof |
| CN104600202A (en) * | 2015-02-05 | 2015-05-06 | 苏州大学 | Inverted oled device structure |
| CN105226199A (en) * | 2015-10-14 | 2016-01-06 | 上海大学 | Be applied to the bielectron implanted layer structure of organic electroluminescence device, be inverted organic electroluminescence device and preparation method thereof |
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