CN104009166A - Organic electroluminescent device and preparation method - Google Patents
Organic electroluminescent device and preparation method Download PDFInfo
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- CN104009166A CN104009166A CN201310059602.XA CN201310059602A CN104009166A CN 104009166 A CN104009166 A CN 104009166A CN 201310059602 A CN201310059602 A CN 201310059602A CN 104009166 A CN104009166 A CN 104009166A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 106
- 239000002184 metal Substances 0.000 claims abstract description 106
- 239000011521 glass Substances 0.000 claims abstract description 40
- 229910000311 lanthanide oxide Inorganic materials 0.000 claims abstract description 40
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 239000010931 gold Substances 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- 239000004411 aluminium Substances 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052737 gold Inorganic materials 0.000 claims abstract description 11
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 11
- 229910052709 silver Inorganic materials 0.000 claims abstract description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004332 silver Substances 0.000 claims abstract description 9
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001954 samarium oxide Inorganic materials 0.000 claims abstract description 7
- 229940075630 samarium oxide Drugs 0.000 claims abstract description 7
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims description 66
- 230000008020 evaporation Effects 0.000 claims description 66
- 239000000463 material Substances 0.000 claims description 45
- 238000005401 electroluminescence Methods 0.000 claims description 39
- 230000005540 biological transmission Effects 0.000 claims description 22
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 20
- 239000011777 magnesium Substances 0.000 claims description 10
- 229910052792 caesium Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 6
- CIEHQLJGGPHJPU-UHFFFAOYSA-N [Pr+3].[O-2].[O-2].[Ti+4] Chemical compound [Pr+3].[O-2].[O-2].[Ti+4] CIEHQLJGGPHJPU-UHFFFAOYSA-N 0.000 claims description 6
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 6
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 6
- 229910003454 ytterbium oxide Inorganic materials 0.000 claims description 6
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical class N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 claims 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 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- MQCHTHJRANYSEJ-UHFFFAOYSA-N n-[(2-chlorophenyl)methyl]-1-(3-methylphenyl)benzimidazole-5-carboxamide Chemical compound CC1=CC=CC(N2C3=CC=C(C=C3N=C2)C(=O)NCC=2C(=CC=CC=2)Cl)=C1 MQCHTHJRANYSEJ-UHFFFAOYSA-N 0.000 claims description 4
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 7
- 238000002347 injection Methods 0.000 abstract description 2
- 239000007924 injection Substances 0.000 abstract description 2
- ZVADOHBJTZCNEM-UHFFFAOYSA-N [O-2].[O-2].[Pr+4] Chemical compound [O-2].[O-2].[Pr+4] ZVADOHBJTZCNEM-UHFFFAOYSA-N 0.000 abstract 1
- 230000005525 hole transport Effects 0.000 abstract 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 abstract 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 113
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000011010 flushing procedure Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 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 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 238000005036 potential barrier Methods 0.000 description 3
- GULMSHUCHQYPKF-UHFFFAOYSA-N 2,3,4-tri(carbazol-9-yl)-n,n-diphenylaniline Chemical compound C1=CC=CC=C1N(C=1C(=C(C(=CC=1)N1C2=CC=CC=C2C2=CC=CC=C21)N1C2=CC=CC=C2C2=CC=CC=C21)N1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1 GULMSHUCHQYPKF-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 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
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001771 vacuum deposition 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
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
An organic electroluminescent device comprises a glass substrate, an anode, a hole transport layer, a luminescent layer, an electron transport layer, an electron injection layer and a cathode which are successively laminated. The anode is composed of a first lanthanide oxide layer, a metal layer and a second lanthanide oxide layer which are successively laminated, wherein a first lanthanide oxide and a second lanthanide oxide are selected from at least one of praseodymium dioxide, praseodymium oxide, ytterbium trioxide and samarium oxide. The metal layer contains a first metal layer and a second metal layer doped in the first metal layer, wherein the first metal layer is selected from at least one of silver, aluminium, platinum and gold; the second metal layer is metal with work function being minus 4.0eV- minus 2.0eV; and mass of the second metal layer accounts for 1 wt%-10wt% of mass of the first metal layer. Luminous efficiency of the above organic electroluminescent device is high. The invention also provides a preparation method of the organic electroluminescent device.
Description
Technical field
The present invention relates to a kind of organic electroluminescence device and preparation method thereof.
Background technology
The principle of luminosity of organic electroluminescence device is based under the effect of extra electric field, and electronics is injected into organic lowest unocccupied molecular orbital (LUMO) from negative electrode, and hole is injected into organic highest occupied molecular orbital (HOMO) from anode.Electronics and hole meet at luminescent layer, compound, form exciton, exciton moves under electric field action, and energy is passed to luminescent material, and excitation electron is from ground state transition to excitation state, excited energy, by Radiation-induced deactivation, produces photon, discharges luminous energy.
In traditional luminescent device, the light of device inside only has 18% left and right can be transmitted into outside to go, and other part can consume in device outside with other forms, (as the specific refractivity between glass and ITO, glass refraction is that 1.5, ITO is 1.8 between interface, refractive index poor, light arrives glass from ITO, will there is total reflection), caused the loss of total reflection, thereby it is lower to cause entirety to go out optical property.
Summary of the invention
Based on this, be necessary to provide organic electroluminescence device that a kind of light extraction efficiency is higher and preparation method thereof.
A kind of organic electroluminescence device, comprise the substrate of glass stacking gradually, anode, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described anode is by the first lanthanide oxide layer stacking gradually, metal level and the second lanthanide oxide layer composition, wherein, described the first lanthanide oxide and the second lanthanide oxide are selected from titanium dioxide praseodymium, praseodymium sesquioxide, at least one in three ytterbium oxides and samarium oxide, described metal level comprises the first metal layer and is entrained in the second metal level composition in described the first metal layer, wherein, the first metal layer is selected from silver, aluminium, at least one in platinum and gold, described the second metal level is that work function is-metal of 4.0eV ~-2.0eV, the mass percent that the second metal level accounts for described the first metal layer is 1%～10%.
The thickness of described the first lanthanide oxide layer is 0.5nm ~ 2nm, and the thickness of metal level is 5nm～30nm, and the thickness of the second lanthanide oxide layer is 1nm ~ 10nm.
The material of described the second metal level be selected from in magnesium, calcium, caesium and ytterbium at least one.
The material of described luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl and oxine aluminium.
The material of described electron transfer layer is selected from 4,7-diphenyl-1,10-phenanthroline, 1,2, at least one in 4-triazole derivative and N-aryl benzimidazole.
A preparation method for organic electroluminescence device, comprises the following steps:
At the back side of substrate of glass evaporation anode, anode comprises the first lanthanide oxide layer stacking gradually, metal level and the second lanthanide oxide layer, wherein, described the first lanthanide oxide and the second lanthanide oxide are selected from titanium dioxide praseodymium, praseodymium sesquioxide, at least one in three ytterbium oxides and samarium oxide, described metal level comprises the first metal layer and is entrained in the second metal level composition in described the first metal layer, wherein, the first metal layer is selected from silver, aluminium, at least one in platinum and gold, described the second metal level is that work function is-metal of 4.0eV ~-2.0eV, the mass percent that the second metal level accounts for described the first metal layer is 1%～10%, and
On the surface of described anode, evaporation is prepared hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively.
The thickness of described the first lanthanide oxide layer is 0.5nm ~ 2nm, and the thickness of metal level is 5nm～30nm, and the thickness of the second lanthanide oxide layer is 1nm ~ 10nm.
The material of described the second metal level be selected from in magnesium, calcium, caesium and ytterbium at least one.
Described evaporation is 5 × 10 at vacuum pressure
-5pa ~ 2 × 10
-3under Pa, carry out, evaporation speed is 0.1nm/s ~ 10nm/s.
Above-mentioned organic electroluminescence device and preparation method thereof, eliminate the total reflection between glass and anode by build up anode in preparation, make glass surface leveling, be conducive to the connection between rete, improve the conductivity of device, and work function is lower, reduces interface potential barrier, improve hole injectability, this structure can improve the light extraction efficiency of organic electroluminescence device greatly.
Brief description of the drawings
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode;
Fig. 2 is the preparation method's of the organic electroluminescence device of an execution mode flow chart;
Fig. 3 is current density and the luminous efficiency graph of a relation of the organic electroluminescence device prepared of embodiment 1.
Embodiment
Below in conjunction with the drawings and specific embodiments, organic electroluminescence device and preparation method thereof is further illustrated.
Refer to Fig. 1, the organic electroluminescence device 100 of an execution mode comprises the substrate of glass 20, anode 30, hole transmission layer 50, luminescent layer 60, electron transfer layer 70, electron injecting layer 80 and the negative electrode 90 that stack gradually.
The glass that substrate of glass 20 is 1.8 ~ 2.2 for refractive index, in 400nm transmitance higher than 90%.Substrate of glass 20 is preferably the glass that the trade mark is N-LAF36, N-LASF31A, N-LASF41A or N-LASF44.
Anode 30 is formed at the surface of substrate of glass 20.Anode 30 is by the first lanthanide oxide layer 301 stacking gradually, metal level 302 and the second lanthanide oxide layer 303 form, wherein, described the first lanthanide oxide 301 and the second lanthanide oxide 303 are selected from titanium dioxide praseodymium, praseodymium sesquioxide, at least one in three ytterbium oxides and samarium oxide, described metal level 302 comprises the first metal layer and is entrained in the second metal level composition in described the first metal layer, wherein, the first metal layer is selected from silver, aluminium, at least one in platinum and gold, described the second metal level is that work function is-metal of 4.0eV ~-2.0eV, the mass percent that the second metal level accounts for described the first metal layer is 1%～10%.
The thickness of the first lanthanide oxide layer 301 is 0.5nm ~ 2nm, and the thickness of metal level 302 is 5nm～30nm, and the thickness of the second lanthanide oxide layer 303 is 1nm ~ 10nm.
The material of the second metal level be selected from in magnesium, calcium, caesium and ytterbium at least one.
Hole transmission layer 50 is formed at the surface of anode 30.The material of hole transmission layer 50 is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), N; N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine (NPB).The thickness of hole transmission layer 50 is 40-80nm.
Luminescent layer 60 is formed at the surface of hole transmission layer 50.The material of luminescent layer 60 is selected from 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--β-naphthylene anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq
3) at least one, be preferably Alq
3.The thickness of luminescent layer 60 is 5nm ~ 40nm, is preferably 20nm.
Electron transfer layer 70 is formed at the surface of luminescent layer 60.The material of electron transfer layer 70 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and at least one in 4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TPBI.The thickness of electron transfer layer 70 is 40nm ~ 250nm, is preferably 150nm.
Electron injecting layer 80 is formed at the surface of electron transfer layer 70.The material of electron injecting layer 80 is selected from cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) and lithium fluoride (LiF) at least one, be preferably CsF.The thickness of electron injecting layer 80 is 0.5nm ~ 10nm, is preferably 1.5nm.
Negative electrode 90 is formed at the surface of electron injecting layer 80.The material of negative electrode 90 is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au), is preferably Al.The thickness of negative electrode 90 is 80nm ~ 250nm, is preferably 150nm.
Above-mentioned organic electroluminescence device 100, build up anode 30 by preparation and eliminate the total reflection between glass and anode, make glass surface leveling, be conducive to the connection between rete, improve the conductivity of device, and work function is lower, reduces interface potential barrier, improve hole injectability, this structure can improve the light extraction efficiency of organic electroluminescence device greatly.
Be appreciated that other functional layers also can be set in this organic electroluminescence device 100 as required.
Please refer to Fig. 2, the preparation method of the organic electroluminescence device 100 of an embodiment, it comprises the following steps:
Step S110, adopt evaporation to prepare anode 30 at the back side of substrate of glass 20.
The glass that substrate of glass 20 is 1.8 ~ 2.2 for refractive index, in 400nm transmitance higher than 90%.Substrate of glass 20 is preferably the glass that the trade mark is N-LAF36, N-LASF31A, N-LASF41A or N-LASF44.
Anode 30 is by the first lanthanide oxide layer stacking gradually, metal level and the second lanthanide oxide layer composition, wherein, described the first lanthanide oxide and the second lanthanide oxide are selected from titanium dioxide praseodymium, praseodymium sesquioxide, at least one in three ytterbium oxides and samarium oxide, described metal level comprises the first metal layer and is entrained in the second metal level composition in described the first metal layer, wherein, the first metal layer is selected from silver, aluminium, at least one in platinum and gold, described the second metal level is that work function is-metal of 4.0eV ~-2.0eV, the mass percent that the second metal level accounts for described the first metal layer is 1%～10%.
The thickness of described the first lanthanide oxide layer is 0.5nm ~ 2nm, and the thickness of metal level is 5nm～30nm, and the thickness of the second lanthanide oxide layer is 1nm ~ 10nm.
The material of described the second metal level be selected from in magnesium, calcium, caesium and ytterbium at least one.
Described evaporation is 5 × 10 at vacuum pressure
-5pa ~ 2 × 10
-3under Pa, carry out, evaporation speed is 0.1nm/s ~ 10nm/s.
In present embodiment, substrate of glass 20 is placed in isopropyl alcohol and soaks 1 hour ~ 5 hours after using before use distilled water, alcohol flushing totally.
Step S120, on the surface of anode 30, evaporation forms hole transmission layer 50, luminescent layer 60, electron transfer layer 70, electron injecting layer 80 and negative electrode 90 successively.
Hole transmission layer 50 is formed at the surface of hole injection layer 40.The material of hole transmission layer 50 is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane (TAPC), 4,4 ', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA), N; N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine (NPB).The thickness of hole transmission layer 50 is 40-80nm.Evaporation is 5 × 10 at vacuum pressure
-5pa ~ 2 × 10
-3under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.Luminescent layer 60 is formed at the surface of hole transmission layer 50.The material of luminescent layer 60 is selected from 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--β-naphthylene anthracene (ADN), 4,4 '-bis-(9-ethyl-3-carbazole vinyl)-1,1 '-biphenyl (BCzVBi) and oxine aluminium (Alq
3) at least one, be preferably Alq
3.The thickness of luminescent layer 60 is 5nm ~ 40nm, is preferably 20nm.Evaporation is 5 × 10 at vacuum pressure
-5pa ~ 2 × 10
-3under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
Electron transfer layer 70 is formed at the surface of luminescent layer 60.The material of electron transfer layer 70 is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), 1,2, and at least one in 4-triazole derivative (as TAZ) and N-aryl benzimidazole (TPBI), is preferably TPBI.The thickness of electron transfer layer 70 is 40nm ~ 250nm, is preferably 150nm.Evaporation is 5 × 10 at vacuum pressure
-5pa ~ 2 × 10
-3under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
Electron injecting layer 80 is formed at the surface of electron transfer layer 70.The material of electron injecting layer 80 is selected from cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) and lithium fluoride (LiF) at least one, be preferably CsF.The thickness of electron injecting layer 80 is 0.5nm ~ 10nm, is preferably 1.5nm.Evaporation is 5 × 10 at vacuum pressure
-5pa ~ 2 × 10
-3under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
Negative electrode 90 is formed at the surface of electron injecting layer 80.The material of negative electrode 90 is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au), is preferably Ag.The thickness of negative electrode 90 is 80nm ~ 250nm, is preferably 150nm.Evaporation is 5 × 10 at vacuum pressure
-5pa ~ 2 × 10
-3under Pa, carry out, evaporation speed is 1nm/s ~ 10nm/s.
Above-mentioned organic electroluminescence device preparation method, preparation technology is simple; The light extraction efficiency of the organic electroluminescence device of preparation is higher.
Below in conjunction with specific embodiment, the preparation method of organic electroluminescence device is elaborated.
The preparation used of the embodiment of the present invention and comparative example and tester are: high vacuum coating system (scientific instrument development center, Shenyang Co., Ltd), the USB4000 fiber spectrometer testing electroluminescent spectrum of U.S. marine optics Ocean Optics, the Keithley2400 test electric property of Keithley company of the U.S., CS-100A colorimeter measuring current density and the colourity of Japanese Konica Minolta company.
Embodiment 1
The present embodiment is prepared structure
2: Mg:Ag:PrO
2//TCTA/Alq
3the organic electroluminescence device of/TPBi/CsF/Ag.
Substrate of glass is N-LASF44, distilled water for substrate of glass, alcohol flushing is clean after, be placed in isopropyl alcohol and soak an evening.Adopt the mode of evaporation to prepare anode at glass basic surface, first evaporation one deck PrO
2, thickness is 1nm, then evaporated metal layer again, and metal level is the doping metals layer of Mg and Ag, and wherein to account for the mass percent of Ag be 5% to Mg, and the thickness of metal level is 10nm, then at surperficial evaporation one deck PrO of metal level
2, thickness is 2nm, then build up anode surface successively evaporation prepare hole transmission layer: selected materials is TCTA, and the thickness of hole transmission layer is 45nm, and evaporation is prepared luminescent layer: selected materials is Alq
3, thickness is 20nm; Evaporation is prepared electron transfer layer, and material is TPBi, and thickness is 150nm; Evaporation is prepared electron injecting layer, material is CsF, and thickness is 1.5nm; Evaporation is prepared negative electrode, and material is Ag, and thickness is 150nm; Finally obtain needed electroluminescent device.Operating pressure prepared by evaporation is 8 × 10
-4pa, the evaporation speed of organic material is 0.2nm/s, the evaporation speed of metal and metal oxide materials is 2nm/s.
Refer to Fig. 3, the structure that is depicted as preparation in embodiment 1 is/substrate of glass/PrO
2: Mg:Ag:PrO
2//TCTA/Alq
3the organic electroluminescence device (curve 1) of/TPBi/CsF/Ag with structure prepared by comparative example is: ito glass/MoO
3/ TCTA/Alq
3the luminous efficiency of the organic electroluminescence device (curve 2) of/TPBi/CsF/Ag and the relation of current density.Step and each layer thickness that comparative example is prepared with organic electroluminescence devices are all identical with embodiment 1.
From scheming, can see, all large than comparative example of the luminous efficiency of embodiment 1, the luminous efficiency of embodiment 1 is 13.2m/W, and that comparative example is only 2.2lm/W, and the luminous efficiency of comparative example along with the increase of current density fast-descending, this explanation, stacked structures is done to make glass surface leveling, is conducive to the connection between rete, improves the conductivity of device, can reduce interface potential barrier, improve hole injectability.The final light extraction efficiency that improves device, this structure can improve the light extraction efficiency of organic electroluminescence device greatly.
The luminous efficiency of the organic electroluminescence device that below prepared by each embodiment is all similar with embodiment 1, and each organic electroluminescence device also has similar luminous efficiency, repeats no more below.
Embodiment 2
The present embodiment is prepared structure
2o
3ca:Al:Yb
2o
3the organic electroluminescence device of/TAPC/ADN/Bphen/LiF/Pt.
Substrate of glass is N-LAF36, distilled water for substrate of glass, alcohol flushing is clean after, be placed in isopropyl alcohol and soak an evening; Adopt the mode of evaporation to prepare anode at glass basic surface, first evaporation one deck Pr
2o
3, thickness is 2nm, then evaporated metal layer again, and metal level is the doping metals layer of Ca and Al, and wherein to account for the mass percent of Al be 1% to Ca, and the thickness of metal level is 20nm, then at surperficial evaporation one deck Yb of metal level
2o
3, thickness is 2nm, then build up anode surface successively evaporation prepare hole transmission layer: selected materials is TAPC, and the thickness of hole transmission layer is 40nm, and evaporation is prepared luminescent layer: selected materials is ADN, and thickness is 8nm; Evaporation is prepared electron transfer layer, and material is Bphen, and thickness is 65nm; Evaporation is prepared electron injecting layer, material is LiF, and thickness is 0.5nm; Evaporation is prepared negative electrode, and material is Pt, and thickness is 80nm; Finally obtain needed electroluminescent device.Operating pressure prepared by evaporation is 2 × 10
-3pa, the evaporation speed of organic material is 1nm/s, the evaporation speed of metal and metal oxide materials is 10nm/s.
Embodiment 3
The present embodiment is prepared structure
2o
3: Cs:Pt:Pr
2o
3/ NPB/DCJTB/TAZ/Cs
2cO
3the organic electroluminescence device of/Au.
Substrate of glass is N-LASF31A, distilled water for substrate of glass, alcohol flushing is clean after, be placed in isopropyl alcohol and soak an evening; Adopt the mode of evaporation to prepare anode at glass basic surface, first evaporation one deck Yb
2o
3, thickness is 0.5nm, then evaporated metal layer again, and metal level is the doping metals layer of Cs and Pt, and wherein to account for the mass percent of Pt be 5% to Cs, and the thickness of metal level is 5nm, then at surperficial evaporation one deck Pr of metal level
2o
3, thickness is 1nm, then build up anode surface successively evaporation prepare hole transmission layer: selected materials is NPB, and the thickness of hole transmission layer is 80nm, and evaporation is prepared luminescent layer: selected materials is DCJTB, and thickness is 10nm; Evaporation is prepared electron transfer layer, and material is TAZ, and thickness is 200nm; Evaporation is prepared electron injecting layer, material is Cs
2cO
3, thickness is 10nm; Evaporation is prepared negative electrode, and material is Au, and thickness is 100nm; Finally obtain needed electroluminescent device.Operating pressure prepared by evaporation is 5 × 10
-5pa, the evaporation speed of organic material is 0.1nm/s, the evaporation speed of metal and metal oxide materials is 1nm/s.
Embodiment 4
It is substrate of glass/Sm that the present embodiment is prepared structure
2o
3yb:Au:Sm
2o
3/ TCTA/BCzVBi/TPBi/CsN
3the organic electroluminescence device of/Al.
Substrate of glass is N-LASF41A, distilled water for substrate of glass, alcohol flushing is clean after, be placed in isopropyl alcohol and soak an evening; Adopt the mode of evaporation to prepare anode at glass basic surface, first evaporation one deck Sm
2o
3, thickness is 1.5nm, then evaporated metal layer again, and metal level is the doping metals layer of Yb and Au, and wherein to account for the mass percent of Au be 7% to Yb, and the thickness of metal level is 30nm, then at surperficial evaporation one deck Sm of metal level
2o
3, thickness is 10nm, then build up anode surface successively evaporation prepare hole transmission layer: selected materials is TCTA, and the thickness of hole transmission layer is 45nm, and evaporation is prepared luminescent layer: selected materials is BCzVBi, and thickness is 40nm; Evaporation is prepared electron transfer layer, and material is TPBi, and thickness is 80nm; Evaporation is prepared electron injecting layer, material is CsN
3, thickness is 3nm; Evaporation is prepared negative electrode, and material is Al, and thickness is 250nm; Finally obtain needed electroluminescent device.Operating pressure prepared by evaporation is 2 × 10
-4pa, the evaporation speed of organic material is 0.5nm/s, the evaporation speed of metal and metal oxide materials is 6nm/s.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (9)
1. an organic electroluminescence device, it is characterized in that, comprise the substrate of glass stacking gradually, anode, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described anode is by the first lanthanide oxide layer stacking gradually, metal level and the second lanthanide oxide layer composition, wherein, described the first lanthanide oxide and the second lanthanide oxide are selected from titanium dioxide praseodymium, praseodymium sesquioxide, at least one in three ytterbium oxides and samarium oxide, described metal level comprises the first metal layer and is entrained in the second metal level composition in described the first metal layer, wherein, the first metal layer is selected from silver, aluminium, at least one in platinum and gold, described the second metal level is that work function is-metal of 4.0eV ~-2.0eV, the mass percent that the second metal level accounts for described the first metal layer is 1%～10%.
2. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described the first lanthanide oxide layer is 0.5nm ~ 2nm, and the thickness of metal level is 5nm～30nm, and the thickness of the second lanthanide oxide layer is 1nm ~ 10nm.
3. organic electroluminescence device according to claim 1, is characterized in that, the material of described the second metal level be selected from in magnesium, calcium, caesium and ytterbium at least one.
4. organic electroluminescence device according to claim 1, it is characterized in that, the material of described luminescent layer is selected from 4-(dintrile methyl)-2-butyl-6-(1,1,7,7-tetramethyl Lip river of a specified duration pyridine-9-vinyl)-4H-pyrans, 9,10-bis--β-naphthylene anthracene, 4, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl and oxine aluminium.
5. organic electroluminescence device according to claim 1, is characterized in that, the material of described electron transfer layer is selected from 4,7-diphenyl-1,10-phenanthroline, 1,2, at least one in 4-triazole derivative and N-aryl benzimidazole.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
At the back side of substrate of glass evaporation anode, described anode is the first lanthanide oxide layer stacking gradually, metal level and the second lanthanide oxide layer, wherein, described the first lanthanide oxide and the second lanthanide oxide are selected from titanium dioxide praseodymium, praseodymium sesquioxide, at least one in three ytterbium oxides and samarium oxide, described metal level comprises the first metal layer and is entrained in the second metal level composition in described the first metal layer, wherein, the first metal layer is selected from silver, aluminium, at least one in platinum and gold, described the second metal level is that work function is-metal of 4.0eV ~-2.0eV, the mass percent that the second metal level accounts for described the first metal layer is 1%～10%, and
On the surface of described anode, evaporation is prepared hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode successively.
7. the preparation method of organic electroluminescence device according to claim 6, is characterized in that: the thickness of described the first lanthanide oxide layer is 0.5nm ~ 2nm, and the thickness of metal level is 5nm～30nm, and the thickness of the second lanthanide oxide layer is 1nm ~ 10nm.
8. the preparation method of organic electroluminescence device according to claim 6, is characterized in that: the material of described the second metal level be selected from in magnesium, calcium, caesium and ytterbium at least one.
9. the preparation method of organic electroluminescence device according to claim 6, is characterized in that: described evaporation is 5 × 10 at vacuum pressure
-5pa ~ 2 × 10
-3under Pa, carry out, evaporation speed is 0.1nm/s ~ 10nm/s.
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Application publication date: 20140827 |