CN104009169A - Organic electroluminescent device and preparation method - Google Patents
Organic electroluminescent device and preparation method Download PDFInfo
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- CN104009169A CN104009169A CN201310059723.4A CN201310059723A CN104009169A CN 104009169 A CN104009169 A CN 104009169A CN 201310059723 A CN201310059723 A CN 201310059723A CN 104009169 A CN104009169 A CN 104009169A
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- hafnium
- organic electroluminescence
- electroluminescence device
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 58
- 239000011521 glass Substances 0.000 claims abstract description 53
- 239000000758 substrate Substances 0.000 claims abstract description 42
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 25
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 25
- 238000002347 injection Methods 0.000 claims abstract description 23
- 239000007924 injection Substances 0.000 claims abstract description 23
- 229910000449 hafnium oxide Inorganic materials 0.000 claims abstract description 7
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 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 abstract description 7
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims abstract description 7
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims description 53
- 230000008020 evaporation Effects 0.000 claims description 53
- 238000005401 electroluminescence Methods 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 26
- 229910052735 hafnium Inorganic materials 0.000 claims description 25
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 25
- 230000005540 biological transmission Effects 0.000 claims description 22
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 22
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 20
- 238000005566 electron beam evaporation Methods 0.000 claims description 14
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 14
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 14
- 238000007747 plating Methods 0.000 claims description 14
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- LRTTZMZPZHBOPO-UHFFFAOYSA-N [B].[B].[Hf] Chemical compound [B].[B].[Hf] LRTTZMZPZHBOPO-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 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 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
- 239000004305 biphenyl Substances 0.000 claims description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 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
- 230000001133 acceleration Effects 0.000 claims description 3
- -1 anode Substances 0.000 claims description 2
- 150000002363 hafnium compounds Chemical class 0.000 abstract 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 abstract 2
- MELCCCHYSRGEEL-UHFFFAOYSA-N hafnium diboride Chemical compound [Hf]1B=B1 MELCCCHYSRGEEL-UHFFFAOYSA-N 0.000 abstract 1
- 230000005525 hole transport Effects 0.000 abstract 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 118
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 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 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 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 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000000605 extraction Methods 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
- 239000010405 anode material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 239000010955 niobium Substances 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005516 engineering process Methods 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000012360 testing method Methods 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
- 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
- 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
- 239000002245 particle Substances 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
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/854—Arrangements for extracting light from the devices comprising scattering means
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Optics & Photonics (AREA)
- Manufacturing & Machinery (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
An organic electroluminescent device comprises a scattering layer, a glass substrate, an anode, a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer, an electron injection layer and a cathode which are successively laminated. The scattering layer contains a hafnium compound and metal oxides doped in the hafnium compound, wherein mass of the metal oxides accounts for 10wt%-50wt% of mass of the hafnium compound; the material of the hafnium compound is selected from at least one of hafnium oxide and hafnium diboride; and the metal oxides are selected from at least one of tantalum pentoxide, niobium pentoxide and vanadium pentoxide. 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 scattering layer stacking gradually, substrate of glass, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described scattering layer comprises the compound of hafnium and is doped to the metal oxide in the compound of hafnium, wherein, the mass percent that described metal oxide accounts for the compound of described hafnium is 10%～50%, the material of the compound of described hafnium is selected from least one in hafnium oxide and hafnium boride, described metal oxide is selected from tantalum pentoxide, at least one in niobium pentaoxide and vanadic oxide.
The thickness of described scattering layer is 50nm ~ 500nm.
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.
The material of described electron injecting layer is selected from least one of cesium carbonate, cesium fluoride, nitrine caesium and lithium fluoride.
A preparation method for organic electroluminescence device, comprises the following steps:
Front in substrate of glass adopts electron beam evaporation plating scattering layer, described scattering layer comprises the compound of hafnium and is doped to the metal oxide in the compound of hafnium, wherein, the mass percent that described metal oxide accounts for the compound of described hafnium is 10%～50%, the material of the compound of described hafnium is selected from least one in hafnium oxide and hafnium boride, described metal oxide is selected from least one in tantalum pentoxide, niobium pentaoxide and vanadic oxide, adopt magnetron sputtering mode to prepare anode at the reverse side of described substrate of glass, 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 scattering layer is 50nm ~ 500nm.
Described evaporation is 5 × 10 at vacuum pressure
-5pa ~ 2 × 10
-3under Pa, carry out, evaporation speed is 0.1nm/s ~ 10nm/s.
Described electron beam evaporation plating is 5 × 10 at vacuum pressure
-5pa ~ 2 × 10
-3under Pa, carry out, energy density is 10W/cm
2～l00W/cm
2.
Described magnetron sputtering is 5 × 10 at vacuum pressure
-5pa ~ 2 × 10
-3under Pa, carry out, acceleration pressure is 300V～800V, and magnetic field is 50G～200G, and power density is 1W/cm
2~ 40W/cm
2.
Above-mentioned organic electroluminescence device and preparation method thereof, by preparing scattering layer at glass substrate reverse side, this scattering layer can scatter out the light in glass of high refractive index, light is effectively reflected, can make most of light directly see through, be applicable to evaporation preparation, good film-forming property, 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 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 scattering layer 10., substrate of glass 20, anode 30, hole injection layer 40, 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 and N-LASF44.
Prepare scattering layer 10 in the front of substrate of glass 20, described scattering layer 10 comprises the compound of hafnium and is doped to the metal oxide in the compound of hafnium, wherein, the mass percent that described metal oxide accounts for the compound of described hafnium is 10%～50%, the material of the compound of described hafnium is selected from least one in hafnium oxide and hafnium boride, and described metal oxide is selected from least one in tantalum pentoxide, niobium pentaoxide and vanadic oxide.
The thickness of scattering layer 10 is 50nm～500nm.
Anode 30 is formed at the reverse side of substrate of glass 20.Anode 30 anodes comprise at least one in indium tin oxide (ITO), aluminium zinc oxide (AZO) and indium-zinc oxide (IZO).
The thickness of described anode 30 is 80nm ~ 300nm.
The exiting surface of substrate of glass 20 is positive, and one side on the other side is the reverse side of substrate of glass 20.
Hole injection layer 40 is formed at the surface of anode 30.The material of hole injection layer 40 is selected from molybdenum trioxide (MoO
3).Also can adopt tungstic acid (WO
3) and vanadic oxide (V
2o
5) at least one, the thickness of hole injection layer 40 is 20nm～80nm.
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) and 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, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 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, by preparing scattering layer 10 at glass substrate 20 reverse side, this scattering layer 10 can scatter out the light in glass of high refractive index, light is effectively reflected, can make most of light directly see through, be applicable to evaporation preparation, good film-forming property, 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 electron beam evaporation plating to prepare scattering layer 10 in the front of substrate of glass 20.
Described scattering layer 10 comprises the compound of hafnium and is doped to the metal oxide in the compound of hafnium, wherein, the mass percent that described metal oxide accounts for the compound of described hafnium is 10%～50%, the material of the compound of described hafnium is selected from least one in hafnium oxide and hafnium boride, and described metal oxide is selected from least one in tantalum pentoxide, niobium pentaoxide and vanadic oxide.
The thickness of scattering layer 10 is 50nm～500nm.
Electron beam evaporation plating is 5 × 10 at vacuum pressure
-5pa ~ 2 × 10
-3under Pa, carry out, energy density is 10W/cm
2～l00W/cm
2.
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 and N-LASF44.
Step S120, adopt magnetron sputtering mode to prepare anode at the reverse side of described substrate of glass 20.
Anode 30 anodes comprise at least one in indium tin oxide (ITO), aluminium zinc oxide (AZO) and indium-zinc oxide (IZO).
The thickness of described anode 30 is 80nm ~ 30nm.
Magnetron sputtering is 5 × 10 at vacuum pressure
-5pa ~ 2 × 10
-3under Pa, carry out, acceleration pressure is 300V～800V, and magnetic field is 50G～200G, and power density is 1W/cm
2~ 40W/cm
2.
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 S130, on the surface of anode 30, evaporation forms hole injection layer 40, hole transmission layer 50, luminescent layer 60, electron transfer layer 70, electron injecting layer 80 and negative electrode 90 successively.
Hole injection layer 40 is formed at the surface of anode 30.The material of hole injection layer 40 is selected from molybdenum trioxide (MoO
3).Also can adopt tungstic acid (WO
3) and vanadic oxide (V
2o
5) at least one, the thickness of hole injection layer 40 is 20nm～80nm.Evaporation is 5 × 10 at vacuum pressure
-5pa ~ 2 × 10
-3under Pa, carry out, evaporation speed is 0.1nm/s ~ 1nm/s.
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) and 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, two (the 9-ethyl-3-carbazole vinyl)-1 of 4'-, 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
It is Ta that the present embodiment is prepared structure
2o
5: HfO
2/ substrate of glass/ITO/MoO
3the organic electroluminescence device of/TAPC/BCzVBi/TPBi/LiF/Al.
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 electron beam evaporation plating mode to prepare scattering layer in the front of substrate of glass, the material of scattering layer is Ta
2o
5and HfO
2, wherein, Ta
2o
5account for HfO
2mass percent be 15%, the condition of electron beam evaporation plating is that vacuum pressure is 8 × 10
-4pa, energy density is 25W/cm
2, adopt the mode of magnetron sputtering to prepare anode at substrate of glass reverse side, anode material is ITO, adopting the condition of magnetron sputtering is that vacuum pressure is 8 × 10
-4pa, accelerating voltage is 400V, and magnetic field is 100G, and power density is 200W/cm
2, then prepare hole injection layer at anode surface successively evaporation: selected materials is MoO
3, the thickness of hole injection layer is 30nm, hole transmission layer: selected materials is TAPC, and the thickness of hole transmission layer is 45nm, and evaporation is prepared luminescent layer: selected materials is BCzVBi, 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 LiF, and thickness is 0.7nm; Evaporation is prepared negative electrode, and material is Al, 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 Ta
2o
5: HfO
2/ substrate of glass/ITO/MoO
3the organic electroluminescence device (curve 1) of/TAPC/BCzVBi/TPBi/LiF/Al with structure prepared by comparative example is: ito glass/MoO
3the luminous efficiency of the organic electroluminescence device (curve 2) of/TCTA/BCzVBi/TPBi/LiF/Al and the relation of brightness.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 3.9lm/W, and that comparative example is only 2.8lm/W, and the luminous efficiency of comparative example along with the increase of brightness fast-descending, this explanation, the compound of employing hafnium and VB family oxide adulterate and prepare scattering layer, high index of refraction can effectively reflect light, the light that makes to be fetched in glass carries out maximum scattering, and can make the particle between rete pile up tightr, 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
It is Nb that the present embodiment is prepared structure
2o
5: HfB
2/ substrate of glass/AZO/V
2o
5the organic electroluminescence device of/TCTA/ADN/Bphen/CsF/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 electron beam evaporation plating mode to prepare scattering layer in the front of substrate of glass, the material of scattering layer is Nb
2o
5and HfB
2, wherein, Nb
2o
5account for HfB
2mass percent be 50%, the condition of electron beam evaporation plating is that vacuum pressure is 2 × 10
-3pa, energy density is 100W/cm
2, adopt the mode of magnetron sputtering to prepare anode at substrate of glass reverse side, anode material is AZO, adopting the condition of magnetron sputtering is that vacuum pressure is 2 × 10
-3pa, accelerating voltage is 300V, magnetic field is 200G,, power density is 40W/cm
2, then prepare hole injection layer at anode surface successively evaporation: selected materials is V
2o
5, the thickness of hole injection layer is 20nm, hole transmission layer: selected materials is TCTA, and the thickness of hole transmission layer is 40nm, and evaporation is prepared luminescent layer: selected materials is ADN, 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 CsF, 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
It is V that the present embodiment is prepared structure
2o
5: HfO
2/ substrate of glass/IZO/WO
3/ TCTA/DCJTB/TPBi/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 electron beam evaporation plating mode to prepare scattering layer in the front of substrate of glass, the material of scattering layer is V
2o
5and HfO
2, wherein, V
2o
5account for HfO
2mass percent be 10%, the condition of electron beam evaporation plating is that vacuum pressure is 5 × 10
-5pa, energy density is 10W/cm
2, adopt the mode of magnetron sputtering to prepare anode at substrate of glass reverse side, anode material is IZO, adopting the condition of magnetron sputtering is that vacuum pressure is 5 × 10
-5pa, accelerating voltage is 800V, and magnetic field is 50G, and power density is 1W/cm
2, then prepare hole injection layer at anode surface successively evaporation: selected materials is WO
3, the thickness of hole injection layer is 80nm, hole transmission layer: selected materials is TCTA, and the thickness of hole transmission layer is 80nm, and evaporation is prepared luminescent layer: selected materials is DCJTB, thickness is 10nm; Evaporation is prepared electron transfer layer, and material is TPBi, 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 10nm/s.
Embodiment 4
It is Ta that the present embodiment is prepared structure
2o
5: HfO
2/ substrate of glass/AZO/WO
3/ NPB/Alq
3/ TAZ/CsN
3the organic electroluminescence device of/Ag.
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 electron beam evaporation plating mode to prepare scattering layer in the front of substrate of glass, the material of scattering layer is Ta
2o
5and HfO
2, wherein, Ta
2o
5account for HfO
2mass percent be 30%, the condition of electron beam evaporation plating is that vacuum pressure is 2 × 10
-4pa, energy density is 50W/cm
2, adopt the mode of magnetron sputtering to prepare anode at substrate of glass reverse side, anode material is AZO, adopting the condition of magnetron sputtering is that vacuum pressure is 2 × 10
-4pa, accelerating voltage is 500V, and magnetic field is 80G, and power density is 25W/cm
2, then prepare hole injection layer at anode surface successively evaporation: selected materials is WO
3, the thickness of hole injection layer is 50nm, hole transmission layer: selected materials is NPB, and the thickness of hole transmission layer is 45nm, and evaporation is prepared luminescent layer: selected materials is Alq
3, thickness is 40nm; Evaporation is prepared electron transfer layer, and material is /TAZ that thickness is 80nm; Evaporation is prepared electron injecting layer, material is CsN
3, thickness is 3nm; Evaporation is prepared negative electrode, and material is Ag, 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 (10)
1. an organic electroluminescence device, it is characterized in that, comprise the scattering layer stacking gradually, substrate of glass, anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described scattering layer comprises the compound of hafnium and is doped to the metal oxide in the compound of hafnium, wherein, the mass percent that described metal oxide accounts for the compound of described hafnium is 10%～50%, the material of the compound of described hafnium is selected from least one in hafnium oxide and hafnium boride, described metal oxide is selected from tantalum pentoxide, at least one in niobium pentaoxide and vanadic oxide.
2. organic electroluminescence device according to claim 1, is characterized in that, the thickness of described scattering layer is 50nm ~ 500nm.
3. 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.
4. 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.
5. organic electroluminescence device according to claim 1, is characterized in that, the material of described electron injecting layer is selected from least one of cesium carbonate, cesium fluoride, nitrine caesium and lithium fluoride.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
Front in substrate of glass adopts electron beam evaporation plating scattering layer, described scattering layer comprises the compound of hafnium and is doped to the metal oxide in the compound of hafnium, wherein, the mass percent that described metal oxide accounts for the compound of described hafnium is 10%～50%, the material of the compound of described hafnium is selected from least one in hafnium oxide and hafnium boride, described metal oxide is selected from least one in tantalum pentoxide, niobium pentaoxide and vanadic oxide, adopt magnetron sputtering mode to prepare anode at the reverse side of described substrate of glass, and
Prepare hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode at described anode surface successively evaporation.
7. the preparation method of organic electroluminescence device according to claim 6, is characterized in that: the thickness of described scattering layer is 50nm ~ 500nm.
8. 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.
9. the preparation method of organic electroluminescence device according to claim 6, is characterized in that: described electron beam evaporation plating is 5 × 10 at vacuum pressure
-5pa ~ 2 × 10
-3under Pa, carry out, energy density is 10W/cm
2～l00W/cm
2.
10. the preparation method of organic electroluminescence device according to claim 6, is characterized in that, described magnetron sputtering is 5 × 10 at vacuum pressure
-5pa ~ 2 × 10
-3under Pa, carry out, acceleration pressure is 300V～800V, and magnetic field is 50G～200G, and power density is 1W/cm
2~ 40W/cm
2.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1656626A (en) * | 2002-03-29 | 2005-08-17 | 通用电气公司 | Mechanically flexible organic electroluminescent device with directional light emission |
| US20090128019A1 (en) * | 2002-09-11 | 2009-05-21 | General Electric Company | Diffusion barrier coatings having graded compositions and devices incorporating the same |
| CN102569667A (en) * | 2011-01-31 | 2012-07-11 | 南京第壹有机光电有限公司 | Electroluminescent device with high efficiency luminescence |
-
2013
- 2013-02-26 CN CN201310059723.4A patent/CN104009169A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1656626A (en) * | 2002-03-29 | 2005-08-17 | 通用电气公司 | Mechanically flexible organic electroluminescent device with directional light emission |
| US20090128019A1 (en) * | 2002-09-11 | 2009-05-21 | General Electric Company | Diffusion barrier coatings having graded compositions and devices incorporating the same |
| CN102569667A (en) * | 2011-01-31 | 2012-07-11 | 南京第壹有机光电有限公司 | Electroluminescent device with high efficiency luminescence |
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Application publication date: 20140827 |