CN103972418A - Organic light-emitting device and method for manufacturing same - Google Patents
Organic light-emitting device and method for manufacturing same Download PDFInfo
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- CN103972418A CN103972418A CN201310038892.XA CN201310038892A CN103972418A CN 103972418 A CN103972418 A CN 103972418A CN 201310038892 A CN201310038892 A CN 201310038892A CN 103972418 A CN103972418 A CN 103972418A
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- 238000000034 method Methods 0.000 title abstract description 3
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 239000000463 material Substances 0.000 claims abstract description 147
- 229910052751 metal Inorganic materials 0.000 claims abstract description 86
- 239000002184 metal Substances 0.000 claims abstract description 86
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 49
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 49
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000002347 injection Methods 0.000 claims abstract description 32
- 239000007924 injection Substances 0.000 claims abstract description 32
- 230000008020 evaporation Effects 0.000 claims description 103
- 238000001704 evaporation Methods 0.000 claims description 103
- 239000010949 copper Substances 0.000 claims description 76
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 72
- 229910052802 copper Inorganic materials 0.000 claims description 72
- 230000005540 biological transmission Effects 0.000 claims description 47
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 46
- 238000005401 electroluminescence Methods 0.000 claims description 44
- 238000002360 preparation method Methods 0.000 claims description 18
- 229960004643 cupric oxide Drugs 0.000 claims description 17
- 229920002554 vinyl polymer Polymers 0.000 claims description 16
- 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 claims description 14
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 13
- 239000004411 aluminium Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 12
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 12
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 claims description 11
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004305 biphenyl Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000003599 detergent Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical class N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims description 6
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 6
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 6
- 229940112669 cuprous oxide Drugs 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 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 6
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 6
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims description 6
- 229910001923 silver oxide Inorganic materials 0.000 claims description 6
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 6
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims description 6
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001259 photo etching Methods 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 230000005525 hole transport Effects 0.000 abstract description 8
- 239000005751 Copper oxide Substances 0.000 abstract 3
- 229910000431 copper oxide Inorganic materials 0.000 abstract 3
- 239000010410 layer Substances 0.000 description 270
- RAPHUPWIHDYTKU-WXUKJITCSA-N 9-ethyl-3-[(e)-2-[4-[4-[(e)-2-(9-ethylcarbazol-3-yl)ethenyl]phenyl]phenyl]ethenyl]carbazole Chemical compound C1=CC=C2C3=CC(/C=C/C4=CC=C(C=C4)C4=CC=C(C=C4)/C=C/C=4C=C5C6=CC=CC=C6N(C5=CC=4)CC)=CC=C3N(CC)C2=C1 RAPHUPWIHDYTKU-WXUKJITCSA-N 0.000 description 15
- 239000011521 glass Substances 0.000 description 14
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 14
- 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 11
- 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 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 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 7
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910021541 Vanadium(III) oxide Inorganic materials 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 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
- 230000005284 excitation Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000000075 oxide glass Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 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
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 238000007747 plating Methods 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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection 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]
- H10K50/17—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
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses an organic light-emitting device which comprises an anode, a hole injection layer, a first hole transport layer, a first light-emitting layer, a first electron transport layer, a charge generating layer, a second hole transport layer, a second light-emitting layer, a second electron transport layer, an electron injection layer and a cathode. The anode, the hole injection layer, the first hole transport layer, the first light-emitting layer, the first electron transport layer, the charge generating layer, the second hole transport layer, the second light-emitting layer, the second electron transport layer, the electron injection layer and the cathode are sequentially stacked on one another, the charge generating layer comprises a low-work-function metal doped layer, a metal oxide layer and a copper oxide doped layer, the low-work-function metal doped layer is stacked on the surface of the first electron transport layer, the metal oxide layer is formed on the surface of the low-work-function metal doped layer, the copper oxide doped layer is formed on the surface of the metal oxide layer, the low-work-function metal doped layer is made of low-work-function metal and electron transport materials which are doped in the low-work-function metal, and the copper oxide doped layer is made of copper oxides and hole transport materials which are doped in the copper oxides. The organic light-emitting device has the advantage of high light-emitting efficiency. The invention further provides a method for manufacturing the organic light-emitting 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.But the luminous efficiency of organic electroluminescence device is lower at present.
Summary of the invention
Based on this, be necessary to provide organic electroluminescence device that a kind of luminous efficiency is higher and preparation method thereof.
A kind of organic electroluminescence device, comprise the anode stacking gradually, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode, described charge generation layer comprises the low workfunction metal doped layer that is laminated in described the first electron transfer layer surface, be formed at the metal oxide layer on described low workfunction metal doped layer surface and be formed at the oxide-doped layer of the copper family on described metal oxide layer surface, the material of described low workfunction metal doped layer comprises low workfunction metal and is entrained in the electron transport material in described low workfunction metal, described in described low workfunction metal doped layer, the mass ratio of electron transport material and described low workfunction metal is 1:100 ~ 3:10, described low workfunction metal is selected from calcium, ytterbium, at least one in magnesium and barium, described electron transport material is selected from 4, 7-diphenyl-1, 10-phenanthroline, oxine aluminium, 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1, 3, 4-oxadiazoles or 2, 9-dimethyl-4, 7-biphenyl-1, at least one in 10-phenanthrolene, the material of described metal oxide layer is selected from tantalum pentoxide, at least one in niobium pentaoxide and vanadium dioxide, the material of the oxide-doped layer of described copper family comprises copper family oxide and is entrained in the hole mobile material in described copper family oxide, the mass ratio of hole mobile material described in the oxide-doped layer of described copper family and described copper family oxide is 1:200 ~ 1:5, described copper family oxide is selected from cupric oxide, at least one in silver oxide and cuprous oxide, described hole mobile material is selected from 1, 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4, 4', 4 " tri-(carbazole-9-yl) triphenylamine and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine.
In an embodiment, the thickness of described low workfunction metal doped layer is 5nm ~ 20nm therein, and the thickness of described metal oxide layer is 2nm ~ 10nm, and the thickness of the oxide-doped layer of described copper family is 1nm ~ 20nm.
Therein in an embodiment, the material of described the first luminescent layer and described the second 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.
Therein in an embodiment, the material of described the first hole transmission layer and described the second hole transmission layer is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4 " tri-(carbazole-9-yl) triphenylamine and N, N '-(1-naphthyl)-N; N '-diphenyl-4, at least one in 4 '-benzidine.
In an embodiment, the material of described the first electron transfer layer and described the second electron transfer layer is selected from 4,7-diphenyl-1 therein, 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:
Prepare hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer at anode surface successively evaporation;
Prepare low workfunction metal doped layer at described the first electron transfer layer surface evaporation, the material of described low workfunction metal doped layer comprises low workfunction metal and is entrained in the electron transport material in described low workfunction metal, described in described low workfunction metal doped layer, the mass ratio of electron transport material and described low workfunction metal is 1:100 ~ 3:10, described low workfunction metal is selected from calcium, ytterbium, at least one in magnesium and barium, described electron transport material is selected from 4, 7-diphenyl-1, 10-phenanthroline, oxine aluminium, 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1, 3, 4-oxadiazoles or 2, 9-dimethyl-4, 7-biphenyl-1, at least one in 10-phenanthrolene,
On described low workfunction metal doped layer surface, evaporation is prepared metal oxide layer, and the material of described metal oxide layer is selected from least one in tantalum pentoxide, niobium pentaoxide and vanadium dioxide;
On described metal oxide layer surface, evaporation is prepared the oxide-doped layer of copper family, the material of the oxide-doped layer of described copper family comprises copper family oxide and is entrained in the hole mobile material in described copper family oxide, the mass ratio of hole mobile material described in the oxide-doped layer of described copper family and described copper family oxide is 1:200 ~ 1:5, described copper family oxide is selected from cupric oxide, at least one in silver oxide and cuprous oxide, described hole mobile material is selected from 1, 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4, 4', 4 " tri-(carbazole-9-yl) triphenylamine and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine, and
Form the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode on the oxide-doped layer of copper family surface successively evaporation.
Therein in an embodiment, the material of described the first luminescent layer and described the second 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.
Therein in an embodiment, the material of described the first hole transmission layer and described the second hole transmission layer is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4 " tri-(carbazole-9-yl) triphenylamine and N, N '-(1-naphthyl)-N; N '-diphenyl-4, at least one in 4 '-benzidine.
In an embodiment, the thickness of described low workfunction metal doped layer is 5nm ~ 20nm therein, and the thickness of described metal oxide layer is 2nm ~ 10nm, and the thickness of the oxide-doped layer of described copper family is 1nm ~ 20nm.
Therein in an embodiment, before described anode surface forms hole injection layer, first antianode carries out pre-treatment, pre-treatment comprises: anode is carried out to photoetching treatment, be cut into needed size, adopt liquid detergent, deionized water, acetone, ethanol, the each Ultrasonic Cleaning 15min of isopropyl acetone, to remove the organic pollution of anode surface.
Above-mentioned organic electroluminescence device and preparation method thereof, charge generation layer is by low workfunction metal doped layer, the oxide-doped layer composition of metal oxide layer and copper family, low workfunction metal doped layer by electron transport material as doping object, metal is conducive to generation and the injection of electronics, object is conducive to the transmission of electronics, the material of metal oxide layer is high refractive index metal oxide, can eliminate the total reflection between interface, improve light outgoing, can avoid metal in inner infiltration simultaneously, the oxide-doped layer of copper family by hole mobile material as doping object, copper family oxide has cushioning effect, the probability of tunneled holes is increased, thereby strengthen the injection in hole, and hole mobile material can strengthen hole transport speed, improve the adhesion between charge generation layer and organic layer, charge generation layer can effectively improve the luminous efficiency of organic electroluminescence device.
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 brightness 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 anode 10, hole injection layer 20, the first hole transmission layer 32, the first luminescent layer 34, the first electron transfer layer 36, charge generation layer 40, the second hole transmission layer 52, the second luminescent layer 54, the second electron transfer layer 56, electron injecting layer 60 and the negative electrode 70 that stack gradually.
Anode 10 is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), is preferably ITO.
Hole injection layer 20 is formed at anode 10 surfaces.The material of hole injection layer 20 is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) at least one, be preferably V
2o
5.The thickness of hole injection layer 20 is 20nm ~ 80nm, is preferably 25nm.
The first hole transmission layer 32 is formed at the surface of hole injection layer 20.The material of the first hole transmission layer 32 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) and N, N '-(1-naphthyl)-N, N '-diphenyl-4; at least one in 4 '-benzidine (NPB), is preferably NPB.The thickness of the first hole transmission layer 32 is 20nm ~ 60nm, is preferably 50nm.
The first luminescent layer 34 is formed at the surface of the first hole transmission layer 32.The material of the first luminescent layer 34 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, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, at least one in 1'-biphenyl (BCzVBi) and 8-hydroxyquinoline aluminum (Alq3), is preferably BCzVBi.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 30nm.
The first electron transfer layer 36 is formed at the surface of the first luminescent layer 34.The material of the first electron transfer layer 36 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 Bphen.The thickness of the first electron transfer layer 36 is 40nm ~ 200nm, is preferably 150nm.
Charge generation layer 40 is formed at the surface of the first electron transfer layer 36.Described charge generation layer 40 comprise be laminated in the first electron transfer layer 36 surfaces low workfunction metal doped layer 42, be formed at the metal oxide layer 44 on low workfunction metal doped layer 42 surfaces and be formed at the oxide-doped layer 46 of the copper family on metal oxide layer 44 surfaces.
The material of low workfunction metal doped layer 42 comprises low workfunction metal and is entrained in the electron transport material in low workfunction metal.The work function of low workfunction metal is-2.0 ~-4.0eV, and preferred, low workfunction metal is selected from least one in calcium (Ca), ytterbium (Yb), magnesium (Mg) and barium (Ba).Electron transport material is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), oxine aluminium (Alq3), 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1,3,4-oxadiazoles (PBD) and 2,9-dimethyl-4,7-biphenyl-1, at least one in 10-phenanthrolene (BCP).In low workfunction metal doped layer 42, the mass ratio of hole mobile material and low workfunction metal is 1:100 ~ 3:10.The thickness of low workfunction metal doped layer 42 is 5nm ~ 20nm.
Metal oxide layer 44 is formed at low workfunction metal doped layer 42 surfaces.The material of metal oxide layer 44 is high refractive index metal oxide, and preferred, the material of metal oxide layer 44 is selected from tantalum pentoxide (Ta
2o
5), niobium pentaoxide (Nb
2o
5) and vanadium dioxide (VO
2).The thickness of metal oxide layer 44 is 2nm ~ 10nm.
The oxide-doped layer 46 of copper family is formed at the surface of metal oxide layer 44.The material of the oxide-doped layer 46 of copper family comprises copper family oxide and is entrained in the hole mobile material in copper family oxide.Copper family oxide is selected from cupric oxide (CuO), silver oxide (Ag
2and cuprous oxide (Cu O)
2o) at least one in, hole mobile material 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) and N, N '-(1-naphthyl)-N; N '-diphenyl-4, at least one in 4 '-benzidine (NPB).In the oxide-doped layer of copper family, the mass ratio of hole mobile material and copper family oxide is 1:200～1:5.The thickness of the oxide-doped layer 46 of copper family is 1nm ~ 20nm.
The second hole transmission layer 52 is formed at the surface of the oxide-doped layer 46 of copper family.The material of the second hole transmission layer 52 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) and N, N '-(1-naphthyl)-N, N '-diphenyl-4; at least one in 4 '-benzidine (NPB), is preferably NPB.The thickness of the second hole transmission layer 52 is 20nm ~ 60nm, is preferably 40nm.
The second luminescent layer 54 is formed at the surface of the second hole transmission layer 52.The material of the second luminescent layer 54 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, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 1'-biphenyl (BCzVBi) and 8-hydroxyquinoline aluminum (Alq
3) at least one, be preferably BCzVBi.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 30nm.
The second electron transfer layer 56 is formed at the surface of the second luminescent layer 52.The material of the second electron transfer layer 56 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 the second electron transfer layer 56 is 40nm ~ 200nm, is preferably 60nm.
Electron injecting layer 60 is formed at the second electron transfer layer 56 surfaces.The material of electron injecting layer 60 is selected from cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) and lithium fluoride (LiF) at least one, be preferably LiF.The thickness of electron injecting layer 60 is 0.5nm ~ 10nm, is preferably 0.7nm.
Negative electrode 70 is formed at electron injecting layer 60 surfaces.The material of negative electrode 70 is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au), is preferably Ag.The thickness of negative electrode 70 is 60nm ~ 300nm, is preferably 150nm.
Above-mentioned organic electroluminescence device 100, charge generation layer 40 is by low workfunction metal doped layer 42, oxide-doped layer 46 composition of metal oxide layer 44 and copper family, low workfunction metal doped layer 42 by electron transport material as doping object, metal is conducive to generation and the injection of electronics, object is conducive to the transmission of electronics, the material of metal oxide layer 44 is high refractive index metal oxide, can eliminate the total reflection between interface, improve light outgoing, can avoid metal in inner infiltration simultaneously, the oxide-doped layer of copper family 46 by hole mobile material as doping object, copper family oxide has cushioning effect, the probability of tunneled holes is increased, thereby strengthen the injection in hole, and hole mobile material can strengthen hole transport speed, improve the adhesion between charge generation layer 40 and organic layer, charge generation layer 40 can effectively improve the luminous efficiency of organic electroluminescence device.
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, prepare hole injection layer 20, the first hole transmission layer 32, the first luminescent layer 34 and the first electron transfer layer 36 at anode surface successively evaporation.
Anode 10 is indium tin oxide glass (ITO), aluminium zinc oxide glass (AZO) or indium-zinc oxide glass (IZO), is preferably ITO.
In present embodiment, before anode 10 surfaces form hole injection layer 20, first antianode 10 carries out pre-treatment, pre-treatment comprises: anode 10 is carried out to photoetching treatment, be cut into needed size, adopt liquid detergent, deionized water, acetone, ethanol, the each Ultrasonic Cleaning 15min of isopropyl acetone, to remove the organic pollution on anode 10 surfaces.
Hole injection layer 20 is formed at the surface of anode 10.Hole injection layer 20 is prepared by evaporation.The material of hole injection layer 20 is selected from molybdenum trioxide (MoO
3), tungstic acid (WO
3) and vanadic oxide (V
2o
5) at least one, be preferably V
2o
5.The thickness of hole injection layer 20 is 20nm ~ 80nm, is preferably 25nm.Evaporation is 5 × 10 at vacuum pressure
-3~ 2 × 10
-4under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
The first hole transmission layer 32 is formed at the surface of hole injection layer 20.The first hole transmission layer 32 is prepared by evaporation.The material of the first hole transmission layer 32 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) and N, N '-(1-naphthyl)-N, N '-diphenyl-4; at least one in 4 '-benzidine (NPB), is preferably NPB.The thickness of the first hole transmission layer 32 is 20nm ~ 60nm, is preferably 50nm.Evaporation is to carry out under 5 × 10-3 ~ 2 × 10-4Pa at vacuum pressure, and evaporation speed is 0.1nm/s ~ 1nm/s.
The first luminescent layer 34 is formed at the surface of the first hole transmission layer 32.The first luminescent layer 34 is prepared by evaporation.The material of the first luminescent layer 34 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, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 1'-biphenyl (BCzVBi) and 8-hydroxyquinoline aluminum (Alq
3) at least one, be preferably BCzVBi.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 30nm.Evaporation is 5 × 10 at vacuum pressure
-3~ 2 × 10
-4under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
The first electron transfer layer 36 is formed at the surface of the first luminescent layer 34.The first electron transfer layer 36 is prepared by evaporation.The material of the first electron transfer layer 36 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 Bphen.The thickness of the first electron transfer layer 36 is 40nm ~ 200nm, is preferably 150nm.Evaporation is 5 × 10 at vacuum pressure
-3~ 2 × 10
-4under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
Step S120, prepare low workfunction metal doped layer 42 at the surperficial evaporation of the first electron transfer layer 36.
The material of low workfunction metal doped layer 42 comprises low workfunction metal and is entrained in the electron transport material in low workfunction metal.The work function of low workfunction metal is-2.0 ~-4.0eV, and preferred, low workfunction metal is selected from least one in calcium (Ca), ytterbium (Yb), magnesium (Mg) and barium (Ba).Electron transport material is selected from 4,7-diphenyl-1,10-phenanthroline (Bphen), oxine aluminium (Alq3), 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1,3,4-oxadiazoles (PBD) and 2,9-dimethyl-4,7-biphenyl-1, at least one in 10-phenanthrolene (BCP).In low workfunction metal doped layer 42, the mass ratio of hole mobile material and low workfunction metal is 1:100 ~ 3:10.The thickness of low workfunction metal doped layer 42 is 5nm ~ 20nm.
Evaporation is 5 × 10 at vacuum pressure
-3~ 2 × 10
-4under Pa, carry out, low workfunction metal and hole mobile material evaporate respectively in two evaporation boats, and the evaporation speed of hole mobile material is 0.1nm/s～1nm/s, and the evaporation speed of low workfunction metal is 1nm/s ~ 10nm/s.
Step S130, prepare metal oxide layer 44 at the surperficial evaporation of low workfunction metal doped layer 42.
The material of metal oxide layer 44 is high refractive index metal oxide, and preferred, the material of metal oxide layer 44 is selected from tantalum pentoxide (Ta
2o
5), niobium pentaoxide (Nb
2o
5) and vanadium dioxide (VO
2).The thickness of metal oxide layer 44 is 2nm ~ 10nm.Evaporation is 5 × 10 at vacuum pressure
-3~ 2 × 10
-4under Pa, carry out, evaporation speed is 1nm/s ~ 10nm/s.
Step S140, prepare the oxide-doped layer of copper family 46 at the surperficial evaporation of metal oxide layer 44.
The oxide-doped layer 46 of copper family is formed at the surface of metal oxide layer 44.The material of the oxide-doped layer 46 of copper family comprises copper family oxide and is entrained in the hole mobile material in copper family oxide.Copper family oxide is selected from cupric oxide (CuO), silver oxide (Ag
2and cuprous oxide (Cu O)
2o) at least one in, hole mobile material 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) and N, N '-(1-naphthyl)-N; N '-diphenyl-4, at least one in 4 '-benzidine (NPB).In the oxide-doped layer of copper family, the mass ratio of hole mobile material and copper family oxide is 1:200～1:5.The thickness of the oxide-doped layer 46 of copper family is 1nm ~ 20nm.
Evaporation is 5 × 10 at vacuum pressure
-3~ 2 × 10
-4under Pa, carry out, copper family oxide and hole mobile material evaporate respectively in two evaporation boats, and the evaporation speed of copper family oxide is 1nm/s ~ 10nm/s, and the evaporation speed of hole mobile material is 0.1nm/s ~ 1nm/s.
Step S150, prepare the second hole transmission layer 52, the second luminescent layer 54, the second electron transfer layer 56, electron injecting layer 60 and negative electrode 70 on the oxide-doped layer of copper family 46 surface successively evaporation.
The second hole transmission layer 52 is formed at the surface of the oxide-doped layer 46 of copper family.The material of the second hole transmission layer 52 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) and N, N '-(1-naphthyl)-N, N '-diphenyl-4; at least one in 4 '-benzidine (NPB), is preferably NPB.The thickness of the second hole transmission layer 52 is 20nm ~ 60nm, is preferably 40nm.Evaporation is 5 × 10 at vacuum pressure
-3~ 2 × 10
-4under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
The second luminescent layer 54 is formed at the surface of the second hole transmission layer 52.The material of the second luminescent layer 54 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, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 1'-biphenyl (BCzVBi) and 8-hydroxyquinoline aluminum (Alq
3) at least one, be preferably BCzVBi.The thickness of luminescent layer 40 is 5nm ~ 40nm, is preferably 30nm.Evaporation is 5 × 10 at vacuum pressure
-3~ 2 × 10
-4under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
The second electron transfer layer 56 is formed at the surface of the second luminescent layer 52.The material of the second electron transfer layer 56 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 the second electron transfer layer 56 is 40nm ~ 200nm, is preferably 60nm.Evaporation is 5 × 10 at vacuum pressure
-3~ 2 × 10
-4under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
Electron injecting layer 60 is formed at the second electron transfer layer 56 surfaces.The material of electron injecting layer 60 is selected from cesium carbonate (Cs
2cO
3), cesium fluoride (CsF), nitrine caesium (CsN
3) and lithium fluoride (LiF) at least one, be preferably LiF.The thickness of electron injecting layer 60 is 0.5nm～10nm, is preferably 0.7nm.Evaporation is 5 × 10 at vacuum pressure
-3~ 2 × 10
-4under Pa, carry out, evaporation speed is 0.1nm/s～1nm/s.
Negative electrode 70 is formed at electron injecting layer 60 surfaces.The material of negative electrode 70 is selected from least one in silver (Ag), aluminium (Al), platinum (Pt) and gold (Au), is preferably Ag.The thickness of negative electrode 70 is 60nm ~ 300nm, is preferably 150nm.Evaporation is 5 × 10 at vacuum pressure
-3~ 2 × 10
-4under Pa, carry out, evaporation speed is 1nm/s ~ 10nm/s.
Above-mentioned organic electroluminescence device preparation method, technique is simple, and the luminous efficiency of the organic electroluminescence device of preparation is higher.
Below in conjunction with specific embodiment, the preparation method of organic electroluminescence device provided by the invention 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 test brightness and the colourity of Japanese Konica Minolta company.
Embodiment 1
Structure prepared by the present embodiment is ito glass/V
2o
5/ NPB/BCzVBi/Bphen/Mg:Alq
3/ Ta
2o
5the organic electroluminescence device of/CuO:NPB/NPB/BCzVBi/TPBi/LiF/Ag.
First ITO is carried out to photoetching treatment, be cut into needed size, use successively liquid detergent, deionized water, acetone, ethanol, the each ultrasonic 15min of isopropyl alcohol, the organic pollution of removal glass surface; Evaporation hole injection layer, material is V
2o
5, thickness is 25nm; Evaporation the first hole transmission layer, material is NPB, thickness is 50nm; Evaporation the first luminescent layer, material is BCzVBi, thickness is 30nm; Evaporation the first electron transfer layer, material is Bphen, thickness is 150nm; Prepare charge generation layer: formed by the oxide-doped layer of low workfunction metal doped layer, metal oxide layer and copper family.Evaporation low workfunction metal doped layer, material comprises Mg and is entrained in the Alq in Mg
3, Alq
3with the mass ratio of Mg be 1:20, thickness is 10nm; Evaporation metal oxide skin(coating), material is Ta
2o
5, thickness is 5nm; The oxide-doped layer of copper steam-plating family, material comprises CuO and is entrained in the NPB in CuO, and the mass ratio of NPB and CuO is 1:50, and thickness is 10nm; Evaporation the second hole transmission layer, material is NPB, thickness is 40nm; Evaporation the second luminescent layer, material is BCzVBi, thickness is 30nm; Evaporation the second electron transfer layer, material is TPBI, thickness is 60nm; Evaporation electron injecting layer, material is LiF, thickness is 0.7nm; Evaporation negative electrode, material is Ag, thickness is 150nm.Finally obtain needed electroluminescent device.Evaporation is 8 × 10 at vacuum pressure
-4under Pa, carry out, organic material evaporation speed is 0.5nm/s, and the evaporation speed of metallic compound is 2nm/s, and the evaporation speed of metal is 5nm/s.
Refer to Fig. 3, the structure that is depicted as preparation in embodiment 1 is ito glass/V
2o
5/ NPB/BCzVBi/Bphen/Mg:Alq
3/ Ta
2o
5the organic electroluminescence device (curve 1) of/CuO:NPB/NPB/BCzVBi/TPBi/LiF/Ag is ito glass/V with structure prepared by comparative example
2o
5the brightness of the organic electroluminescence device (curve 2) of/NPB/BCzVBi/Bphen/LiF/Ag and the relation of luminous efficiency.In the organic electroluminescence device that in organic electroluminescence device prepared by comparative example, each layer thickness is prepared with embodiment 1, each layer thickness is identical.
As seen from Figure 3, under different brightness, all large than comparative example of the luminous efficiency of embodiment 1, the maximum lumen efficiency of organic electroluminescence device prepared by embodiment 1 is 7.4lm/W, and the luminous efficiency of organic electroluminescence device prepared by comparative example is only 4.5lm/W, and the luminous efficiency of comparative example along with the increase of brightness fast-descending, this explanation, charge generation layer is by low workfunction metal doped layer, the oxide-doped layer composition of metal oxide layer and copper family, be conducive to generation and the injection of electronics, strengthen the injection in hole, strengthen hole transport speed, this charge generation layer can effectively improve the luminous efficiency of organic electroluminescence device.
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
Structure prepared by the present embodiment is AZO/V
2o
5/ NPB/ADN/Bphen/Ca:Bphen/Nb
2o
5/ Ag
2o:TAPC/TCTA/ADN/TAZ/CsN
3the organic electroluminescence device of/Pt.
First AZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface; Evaporation is prepared hole injection layer, and material is V
2o
5, thickness is 80nm; Evaporation is prepared the first hole transmission layer, and material is NPB, and thickness is 60nm; Evaporation is prepared the first luminescent layer, and material is ADN, and thickness is 5nm; Evaporation is prepared the first electron transfer layer, and material is Bphen, and thickness is 200nm; Evaporation is prepared charge generation layer: by low workfunction metal doped layer, and the oxide-doped layer composition of high refractive index metal oxide layer and copper family; Low workfunction metal doped layer, material comprises Ca and is entrained in the Bphen in Ca, and the mass ratio of Bphen and Ca is 3:10, and thickness is 5nm; The material of metal oxide layer is Nb
2o
5, thickness is 10nm; The material of the oxide-doped layer of copper family comprises Ag
2o and be entrained in Ag
2tAPC in O, TAPC and Ag
2the mass ratio of O is 1:200, and thickness is 1nm; Evaporation is prepared the second hole transmission layer, and material is TCTA, and thickness is 20nm; Evaporation is prepared the second luminescent layer, and material is ADN, and thickness is 7nm; Evaporation is prepared the second electron transfer layer, and material is TAZ, and thickness is 40nm; Evaporation is prepared electron injecting layer, and material is CsN
3, thickness is 0.5nm; Evaporation is prepared negative electrode, and material is Pt, and thickness is 60nm, finally obtains needed electroluminescent device.Evaporation is 5 × 10 at vacuum pressure
-3under Pa, carry out, organic material evaporation speed is 0.1nm/s, and the evaporation speed of metallic compound is 10nm/s, and the evaporation speed of metal is 10nm/s.
Embodiment 3
Structure prepared by the present embodiment is IZO/WO
3/ TCTA/Alq
3/ TAZ/Ba:PBD/VO
2/ Cu
2o:TCTA/TCTA/Alq
3the organic electroluminescence device of/Bphen/CsF/Al.
First IZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface; Evaporation is prepared hole injection layer, and material is WO
3, thickness is 20nm; Evaporation is prepared the first hole transmission layer, and material is TCTA, and thickness is 30nm; Evaporation is prepared the first luminescent layer, and material is Alq
3, thickness is 40nm; Evaporation is prepared the first electron transfer layer, and material is TAZ, and thickness is 200nm; Evaporation is prepared charge generation layer: by low workfunction metal doped layer, and the oxide-doped layer composition of high refractive index metal oxide layer and copper family.The material of low workfunction metal doped layer comprises Ba and is entrained in the PBD in Ba, and doping ratio is that the mass ratio of 1%(PBD and Ba is 1:100, and thickness is 20nm; The material of metal oxide layer is VO
2, thickness is 2nm; The material of the oxide-doped layer of copper family comprises Cu
2o and be entrained in Cu
2tCTA in O, TCTA and Cu
2the mass ratio of O is 1:5, and thickness is 20nm; Evaporation is prepared the second hole transmission layer, and material is TAPC, and thickness is 60nm; Evaporation is prepared the second luminescent layer, and material is Alq
3, thickness is 30nm; Evaporation is prepared the second electron transfer layer, and material is Bphen, and thickness is 40nm; Evaporation is prepared electron injecting layer, and material is CsF, and thickness is 10nm; Evaporation is prepared negative electrode, and material is Al, and thickness is 300nm, finally obtains needed electroluminescent device.Evaporation is 2 × 10 at vacuum pressure
-4under Pa, carry out, organic material evaporation speed is 1nm/s, and the evaporation speed of metallic compound is 1nm/s, and the evaporation speed of metal is 1nm/s.
Embodiment 4
Structure prepared by the present embodiment is IZO/MoO
3/ TAPC/DCJTB/Bphen/Yb:BCP/Ta
2o
5/ CuO:TCTA/TCTA/DCJTB/Bphen/Cs
2cO
3the organic electroluminescence device of/Au.
First IZO substrate of glass is used to liquid detergent successively, deionized water, ultrasonic 15min, the organic pollution of removal glass surface; Evaporation is prepared hole injection layer, and material is MoO
3, thickness is 30nm; Evaporation is prepared the first hole transmission layer, and material is TAPC, and thickness is 55nm; Evaporation is prepared the first luminescent layer, and material is DCJTB, and thickness is 5nm; Evaporation is prepared the first electron transfer layer, and material is Bphen, and thickness is 40nm; Prepare charge generation layer: by low workfunction metal doped layer, the oxide-doped layer composition of high refractive index metal oxide layer and copper family.The material of low workfunction metal doped layer comprises Yb and is entrained in the BCP in Yb, and the mass ratio of BCP and Yb is 18:100, and thickness is 15nm; The material of metal oxide layer is Ta
2o
5, thickness is 5nm; The material of the oxide-doped layer of copper family comprises CuO and is entrained in the TCTA in CuO, and the mass ratio of TCTA and CuO is 1.5:100, and thickness is 15nm; Evaporation is prepared the second hole transmission layer, and material is TCTA, and thickness is 50nm; Evaporation is prepared the second luminescent layer, and material is DCJTB, and thickness is 5nm; Evaporation is prepared the second electron transfer layer, and material is Bphen, and thickness is 100nm; Evaporation is prepared electron injecting layer, and material is Cs
2cO
3, thickness is 2nm; Evaporation is prepared negative electrode, and material is Au, and thickness is 180nm, finally obtains needed electroluminescent device.Evaporation is 5 × 10 at vacuum pressure
-4under Pa, carry out, organic material evaporation speed is 0.6nm/s, and the evaporation speed of metal compound layer is 5nm/s, and the evaporation speed of metal is 3nm/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 (10)
1. an organic electroluminescence device, it is characterized in that, comprise the anode stacking gradually, hole injection layer, the first hole transmission layer, the first luminescent layer, the first electron transfer layer, charge generation layer, the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode, described charge generation layer comprises the low workfunction metal doped layer that is laminated in described the first electron transfer layer surface, be formed at the metal oxide layer on described low workfunction metal doped layer surface and be formed at the oxide-doped layer of the copper family on described metal oxide layer surface, the material of described low workfunction metal doped layer comprises low workfunction metal and is entrained in the electron transport material in described low workfunction metal, described in described low workfunction metal doped layer, the mass ratio of electron transport material and described low workfunction metal is 1:100 ~ 3:10, described low workfunction metal is selected from calcium, ytterbium, at least one in magnesium and barium, described electron transport material is selected from 4, 7-diphenyl-1, 10-phenanthroline, oxine aluminium, 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1, 3, 4-oxadiazoles or 2, 9-dimethyl-4, 7-biphenyl-1, at least one in 10-phenanthrolene, the material of described metal oxide layer is selected from tantalum pentoxide, at least one in niobium pentaoxide and vanadium dioxide, the material of the oxide-doped layer of described copper family comprises copper family oxide and is entrained in the hole mobile material in described copper family oxide, the mass ratio of hole mobile material described in the oxide-doped layer of described copper family and described copper family oxide is 1:200 ~ 1:5, described copper family oxide is selected from cupric oxide, at least one in silver oxide and cuprous oxide, described hole mobile material is selected from 1, 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4, 4', 4 " tri-(carbazole-9-yl) triphenylamine and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine.
2. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described low workfunction metal doped layer is 5nm ~ 20nm, and the thickness of described metal oxide layer is 2nm ~ 10nm, and the thickness of the oxide-doped layer of described copper family is 1nm ~ 20nm.
3. organic electroluminescence device according to claim 1, it is characterized in that, the material of described the first luminescent layer and described the second 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.
4. organic electroluminescence device according to claim 1, it is characterized in that, the material of described the first hole transmission layer and described the second hole transmission layer is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4 " tri-(carbazole-9-yl) triphenylamine and N; N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine.
5. organic electroluminescence device according to claim 1, is characterized in that, the material of described the first electron transfer layer and described the second 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:
Prepare hole injection layer, the first hole transmission layer, the first luminescent layer and the first electron transfer layer at anode surface successively evaporation;
Prepare low workfunction metal doped layer at described the first electron transfer layer surface evaporation, the material of described low workfunction metal doped layer comprises low workfunction metal and is entrained in the electron transport material in described low workfunction metal, described in described low workfunction metal doped layer, the mass ratio of electron transport material and described low workfunction metal is 1:100 ~ 3:10, described low workfunction metal is selected from calcium, ytterbium, at least one in magnesium and barium, described electron transport material is selected from 4, 7-diphenyl-1, 10-phenanthroline, oxine aluminium, 2-(4'-2-methyl-2-phenylpropane base)-5-(4'-xenyl)-1, 3, 4-oxadiazoles or 2, 9-dimethyl-4, 7-biphenyl-1, at least one in 10-phenanthrolene,
On described low workfunction metal doped layer surface, evaporation is prepared metal oxide layer, and the material of described metal oxide layer is selected from least one in tantalum pentoxide, niobium pentaoxide and vanadium dioxide;
On described metal oxide layer surface, evaporation is prepared the oxide-doped layer of copper family, the material of the oxide-doped layer of described copper family comprises copper family oxide and is entrained in the hole mobile material in described copper family oxide, the mass ratio of hole mobile material described in the oxide-doped layer of described copper family and described copper family oxide is 1:200 ~ 1:5, described copper family oxide is selected from cupric oxide, at least one in silver oxide and cuprous oxide, described hole mobile material is selected from 1, 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4, 4', 4 " tri-(carbazole-9-yl) triphenylamine and N, N '-(1-naphthyl)-N, N '-diphenyl-4, at least one in 4 '-benzidine, and
Form the second hole transmission layer, the second luminescent layer, the second electron transfer layer, electron injecting layer and negative electrode on the oxide-doped layer of copper family surface successively evaporation.
7. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that: the material of described the first luminescent layer and described the second 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.
8. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that: the material of described the first hole transmission layer and described the second hole transmission layer is selected from 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane, 4,4', 4 " tri-(carbazole-9-yl) triphenylamine and N, N '-(1-naphthyl)-N; N '-diphenyl-4, at least one in 4 '-benzidine.
9. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that: the thickness of described low workfunction metal doped layer is 5nm ~ 20nm, the thickness of described metal oxide layer is 2nm ~ 10nm, and the thickness of the oxide-doped layer of described copper family is 1nm ~ 20nm.
10. the preparation method of organic electroluminescence device according to claim 6, it is characterized in that: before described anode surface forms hole injection layer, first antianode carries out pre-treatment, pre-treatment comprises: anode is carried out to photoetching treatment, be cut into needed size, adopt liquid detergent, deionized water, acetone, ethanol, the each Ultrasonic Cleaning 15min of isopropyl acetone, to remove the organic pollution of anode surface.
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