CN104518117A - Organic light emitting diode device and preparation method thereof - Google Patents
Organic light emitting diode device and preparation method thereof Download PDFInfo
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- CN104518117A CN104518117A CN201310455345.1A CN201310455345A CN104518117A CN 104518117 A CN104518117 A CN 104518117A CN 201310455345 A CN201310455345 A CN 201310455345A CN 104518117 A CN104518117 A CN 104518117A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 66
- 239000010410 layer Substances 0.000 claims abstract description 378
- 239000000463 material Substances 0.000 claims abstract description 123
- 239000002131 composite material Substances 0.000 claims abstract description 81
- 229910052751 metal Inorganic materials 0.000 claims abstract description 64
- 239000002184 metal Substances 0.000 claims abstract description 64
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 42
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 239000002346 layers by function Substances 0.000 claims abstract description 31
- 229910001316 Ag alloy Inorganic materials 0.000 claims abstract description 9
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 9
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001704 evaporation Methods 0.000 claims description 69
- 230000008020 evaporation Effects 0.000 claims description 69
- 150000002736 metal compounds Chemical class 0.000 claims description 62
- 229910000765 intermetallic Inorganic materials 0.000 claims description 49
- 238000005401 electroluminescence Methods 0.000 claims description 44
- 238000002347 injection Methods 0.000 claims description 35
- 239000007924 injection Substances 0.000 claims description 35
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 30
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 26
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 238000007738 vacuum evaporation Methods 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 21
- 239000002585 base Substances 0.000 claims description 20
- 230000005540 biological transmission Effects 0.000 claims description 20
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 18
- 239000004411 aluminium Substances 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- HSEVUSRQUCWDNF-UHFFFAOYSA-N NCC=1C=C(C=CC1)N(C1=CC=C(C=C1)C1=CC=C(N(C2=CC=CC=C2)C2=CC(=CC=C2)CN)C=C1)C1=CC=CC=C1 Chemical compound NCC=1C=C(C=CC1)N(C1=CC=C(C=C1)C1=CC=C(N(C2=CC=CC=C2)C2=CC(=CC=C2)CN)C=C1)C1=CC=CC=C1 HSEVUSRQUCWDNF-UHFFFAOYSA-N 0.000 claims description 13
- 239000011787 zinc oxide Substances 0.000 claims description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 12
- 235000010290 biphenyl Nutrition 0.000 claims description 12
- 239000004305 biphenyl Substances 0.000 claims description 12
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 12
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052741 iridium Inorganic materials 0.000 claims description 10
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims description 9
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 9
- 159000000002 lithium salts Chemical class 0.000 claims description 9
- NBYLBWHHTUWMER-UHFFFAOYSA-N 2-Methylquinolin-8-ol Chemical compound C1=CC=C(O)C2=NC(C)=CC=C21 NBYLBWHHTUWMER-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 8
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical class C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 claims description 6
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 claims description 5
- 150000005360 2-phenylpyridines Chemical class 0.000 claims description 5
- UNRQTHVKJQUDDF-UHFFFAOYSA-N acetylpyruvic acid Chemical compound CC(=O)CC(=O)C(O)=O UNRQTHVKJQUDDF-UHFFFAOYSA-N 0.000 claims description 5
- RTRAMYYYHJZWQK-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=CC=N1 RTRAMYYYHJZWQK-UHFFFAOYSA-N 0.000 claims description 5
- 150000003222 pyridines Chemical class 0.000 claims description 5
- VOIVTTPPKHORBL-UHFFFAOYSA-N 1-naphthalen-1-ylanthracene Chemical compound C1=CC=C2C(C=3C4=CC5=CC=CC=C5C=C4C=CC=3)=CC=CC2=C1 VOIVTTPPKHORBL-UHFFFAOYSA-N 0.000 claims description 4
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 claims description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 4
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 abstract description 8
- 239000000956 alloy Substances 0.000 abstract description 8
- 238000000605 extraction Methods 0.000 abstract description 3
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 abstract 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 abstract 1
- 239000010409 thin film Substances 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 description 24
- 239000011521 glass Substances 0.000 description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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 9
- 238000007598 dipping method Methods 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 8
- IWZZBBJTIUYDPZ-DVACKJPTSA-N (z)-4-hydroxypent-3-en-2-one;iridium;2-phenylpyridine Chemical compound [Ir].C\C(O)=C\C(C)=O.[C-]1=CC=CC=C1C1=CC=CC=N1.[C-]1=CC=CC=C1C1=CC=CC=N1 IWZZBBJTIUYDPZ-DVACKJPTSA-N 0.000 description 6
- 238000001994 activation Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 239000003599 detergent Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 5
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 4
- MWMNLUGPPZOPJQ-UHFFFAOYSA-N 4-(4-aminophenyl)-3-naphthalen-1-ylaniline Chemical class C1=CC(N)=CC=C1C1=CC=C(N)C=C1C1=CC=CC2=CC=CC=C12 MWMNLUGPPZOPJQ-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 4
- YERGTYJYQCLVDM-UHFFFAOYSA-N iridium(3+);2-(4-methylphenyl)pyridine Chemical compound [Ir+3].C1=CC(C)=CC=C1C1=CC=CC=N1.C1=CC(C)=CC=C1C1=CC=CC=N1.C1=CC(C)=CC=C1C1=CC=CC=N1 YERGTYJYQCLVDM-UHFFFAOYSA-N 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 229910007857 Li-Al Inorganic materials 0.000 description 2
- 229910008447 Li—Al Inorganic materials 0.000 description 2
- QHODXIVESWMRGP-UHFFFAOYSA-N NCC=1C=C(C=CC1)C1=C(C=CC(=C1)NC1=CC=CC=C1)C1=CC=C(NC2=CC=CC=C2)C=C1 Chemical compound NCC=1C=C(C=CC1)C1=C(C=CC(=C1)NC1=CC=CC=C1)C1=CC=C(NC2=CC=CC=C2)C=C1 QHODXIVESWMRGP-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 3-aminomethyl phenyl Chemical group 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/82—Cathodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/82—Cathodes
- H10K50/822—Cathodes characterised by their shape
-
- 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
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides an organic light emitting diode device. The organic light emitting diode device includes a transparent electric conduction anode substrate as well as a light-emitting functional layer and a cathode which are sequentially stacked on the transparent electric conduction anode substrate, wherein the cathode includes a cathode layer and a second cathode layer which are stacked sequentially; the first cathode layer comprises a plurality of strip-shaped oxide/metal/oxide composite layers which are arranged on the light-emitting functional layer at intervals; the second cathode layer comprises a metal oxide layer, an alloy layer and an electric conduction oxide thin film layer which are stacked sequentially, wherein the metal oxide layer is made of at least two kinds of materials selected from Nb2O5, V2O5 and Ta2O5, and the alloy layer is made of magnesium-silver alloy or lithium-aluminum alloy. The organic light emitting diode device can be adopted as a transparent product when not being lit; and when the organic light emitting diode device works normally, the light extraction contrast of the anode and cathode is (15 to 20):1. The invention also provides a preparation method of the organic light emitting diode device.
Description
Technical field
The present invention relates to organic electroluminescence device, be specifically related to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescent (Organic Light Emission Diode), hereinafter referred to as OLED, there is the characteristics such as brightness is high, material selection range is wide, driving voltage is low, all solidstate active illuminating, have high definition, wide viewing angle simultaneously, and the advantage such as fast response time, be a kind of Display Technique and light source of great potential, meet the development trend of information age mobile communication and information displaying, and the requirement of green lighting technique, be the focal point of current lot of domestic and foreign researcher.
Transparent organic electroluminescent device (TOLED) is the one of OLED, and when powering up, anode and negative electrode two sides all can utilizing emitted lights for it, and become the characteristic of transparence when not powering up, and open a special applications direction in display field.But in some practical application, need organic electroluminescence devices becomes transparence characteristic when not powering up, and two sides all high-efficiency bight-dippings are not needed when powering up, anode and negative electrode bright dipping keep suitable contrast, under such circumstances, the transparent organic electroluminescent device of existing two sides high-efficiency bight-dipping will cause larger light loss.
Summary of the invention
In view of this, the invention provides a kind of organic electroluminescence device and preparation method thereof.By preparing the negative electrode of composite construction, and the first cathode layer being arranged to striped stride distribution, finally acquired and not can be used as opaque products when lighting, and anode and negative electrode going out the organic electroluminescence device that optical contrast ratio is 15 ~ 20:1 when normal work.
On the one hand, the invention provides a kind of organic electroluminescence device, comprise transparent conductive anode substrate and be cascading light emitting functional layer on described transparent conductive anode substrate and negative electrode, described negative electrode comprises be cascading the first cathode layer in described light emitting functional layer and the second cathode layer;
Described first cathode layer comprises multiple metallic compound/metal/metal compound composite bed be arranged in striped stride in described light emitting functional layer, described metallic compound/metal/metal compound composite bed is three-decker, and the material of described three-decker consists of MoO
3/ Al/MoO
3, ZnS/Ag/ZnS, ITO/Pt/ITO, ITO/Au/ITO, ITO/Ag/ITO or ZnO/Cu/ZnO;
Described second cathode layer comprises the metal oxide layer, alloy-layer and the conductive oxide film layer that are cascading on described first cathode layer; The material of described metal oxide layer is Nb
2o
5, V
2o
5and Ta
2o
5in at least two kinds, the material of described alloy-layer is magnesium-silver alloy or lithium-aluminium alloy, and the material of described conductive oxide film layer is indium tin oxide, aluminium zinc oxide or indium-zinc oxide.
Negative electrode is arranged to above-mentioned composite construction by the present invention, device transparent shape when not lighting can be made, be that striped stride is arranged in light emitting functional layer by metallic compound/metal/metal compound composite bed, when device is lighted, can make the part light outgoing of cathode plane, and another part light is reflected back toward device inside, thus reduces unnecessary light loss, obtain suitable anode cathode and go out optical contrast ratio, when normal work, anode and negative electrode go out optical contrast ratio to this device is 15 ~ 20:1.Metallic compound/metal/metal compound composite bed is a kind of manufacture method of semitransparent cathode, and take into account light transmission and conductivity, intermetallic metal plays main electric action, and the metallic compound on both sides is to being injected with certain help.Arranging of metal oxide layer, alloy-layer and conductive oxide film layer can increase electron injection, wherein, and the Nb of metal oxide layer
2o
5, V
2o
5and Ta
2o
5have scattering process, therefore metal oxide layer can be used as inscattering layer enhancing light extraction efficiency, and alloy-layer work content is low, and chemical stability is good, improves electron injection ability; Form phase local area High-Field between conductive oxide film layer with the first cathode layer, add the electron tunneling of negative electrode to organic luminescence function layer.Organic electroluminescence device anode surface of the present invention adopts and exceeds finish matter, cathode plane is provided with translucent first cathode layer that striped stride is arranged, light emission rate is relatively poor, the first cathode layer can produce reflection to light, thus decrease the bright dipping of cathode plane, what change anode and negative electrode goes out optical contrast ratio.When normal work, anode and negative electrode go out optical contrast ratio to organic electroluminescence device of the present invention is 15 ~ 20:1.
"/" in metallic compound of the present invention/metal/metal compound composite bed represents interface between layers.
The present invention second cathode layer is arranged on the first cathode layer and refers to, the second cathode layer is arranged on the metallic compound/metal/metal compound composite bed in described light emitting functional layer and is not metallized the surface of compound/metal/metal compound composite bed covering.
Preferably, the width of described metallic compound/metal/metal compound composite bed is 100 μm ~ 150 μm.
Preferably, the distance between adjacent two described metallic compounds/metal/metal compound composite bed is 100 μm ~ 150 μm.
Preferably, in the three-decker of described metallic compound/metal/metal compound composite bed, the thickness of metal compound layer is 30nm ~ 50nm, and the thickness of metal level is 10nm ~ 30nm.
Preferably, the thickness of described metal oxide layer is 30nm ~ 50nm.
Preferably, described Nb
2o
5, V
2o
5and Ta
2o
5mole dosage in metal oxide layer is equal.
Preferably, the thickness of described alloy-layer is 10nm ~ 20nm.
Preferably, the magnesium of described magnesium-silver alloy, silver-colored mass ratio are 8 ~ 13:1, and in described lithium-aluminium alloy, the mass fraction of lithium is 0.5 ~ 1%.More preferably, the magnesium of described magnesium-silver alloy, silver-colored mass ratio are 10:1, and in described lithium-aluminium alloy, the mass fraction of lithium is 0.6%.
Preferably, the thickness of described conductive oxide film layer is 20nm ~ 40nm.
Preferably, described transparent conductive anode substrate is ito glass substrate, AZO glass substrate or IZO glass substrate.
Preferably, described light emitting functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that are cascading on described transparent conductive anode substrate.
Preferably, the material of described hole injection layer comprises hole mobile material and is entrained in the hole-injecting material in described hole mobile material, and the doping mass fraction of described hole-injecting material is 25% ~ 35%; Described hole-injecting material is MoO
3, WO
3, V
2o
5and ReO
3in at least one, described hole mobile material is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) and 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] one in cyclohexane (TAPC), the thickness of hole injection layer is 10nm ~ 15nm.
Preferably, the material of described hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) and 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] one in cyclohexane (TAPC), thickness is 30 ~ 50nm.
Preferably, the material of described luminescent layer comprises green glow material of main part and green glow guest materials, and the doping mass fraction of described green glow guest materials is 2% ~ 10%, and the thickness of luminescent layer is 10nm ~ 30nm.
Preferably, described green glow material of main part is 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), 9,9'-(1,3-phenyl) two-9H-carbazoles (mCP), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD), 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC) or two (1-naphthyl) anthracene (ADN) of 9,10-; Described green glow guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy)
3), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy)
2(acac)) or three [2-(p-methylphenyl) pyridines] close iridium (Ir (mppy)
3).
Preferably, the material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq
3), 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ) and 1,3, one in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI), thickness is 10nm ~ 60nm.
Preferably, the material of described electron injecting layer comprises electron transport material and is entrained in the alkali metal sulfates in described electron transport material, and lithium salts or cesium salt, the doping mass fraction of described alkali metal sulfates is 6% ~ 25%, and the doping mass fraction of described lithium salts or cesium salt is 25% ~ 35%; Described alkali metal sulfates is Li
2sO
4, Na
2sO
4, K
2sO
4, Rb
2sO
4and Cs
2sO
4in any one, described lithium salts is LiF, LiN
3and Li
3any one in N, described cesium salt is CsF, CsN
3and Cs
3any one in N, described electron transport material is 4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq
3), 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, the one in 2,4-triazole (TAZ) and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI); The thickness of described electron injecting layer is 15nm ~ 45nm.
On the other hand, the invention provides a kind of preparation method of organic electroluminescence device, comprise the following steps:
Adopt the mode of vacuum evaporation to prepare light emitting functional layer on transparent conductive anode substrate, vacuum degree is 1 × 10
-5~ 1 × 10
-3pa;
Prepare negative electrode on described light emitting functional layer surface again, obtain organic electroluminescence device; Described negative electrode comprises the first cathode layer and the second cathode layer; Described first cathode layer comprises multiple metallic compound/metal/metal compound composite bed be arranged in striped stride in described light emitting functional layer; Described second cathode layer comprises metal oxide layer, alloy-layer and conductive oxide film layer; Particularly:
One mask plate is provided, described mask plate is covered described light emitting functional layer surface, then adopt the mode of vacuum evaporation at the multiple metallic compound/metal/metal compound composite bed arranged in striped stride of described light emitting functional layer surface preparation, vacuum degree is 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate
described metallic compound/metal/metal compound composite bed is three-decker, and the material of described three-decker consists of MoO
3/ Al/MoO
3, ZnS/Ag/ZnS, ITO/Pt/ITO, ITO/Au/ITO, ITO/Ag/ITO or ZnO/Cu/ZnO;
Then the mode of magnetron sputtering is adopted to prepare metal oxide layer on described first cathode layer; Adopt the mode of vacuum evaporation to prepare alloy-layer again on described metal oxide layer, vacuum degree is 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate
the mode of magnetron sputtering is finally adopted to prepare conductive oxide film layer on described alloy-layer; Background vacuum in above-mentioned magnetron sputtering process is 1 × 10
-5~ 1 × 10
-3pa, accelerating voltage is 300 ~ 800V, and magnetic field is 50 ~ 200G, and power density is 10 ~ 40W/cm
2; The material of described metal oxide layer is Nb
2o
5, V
2o
5and Ta
2o
5in at least two kinds, the material of described alloy-layer is magnesium-silver alloy or lithium-aluminium alloy, and the material of described conductive oxide film layer is indium tin oxide, aluminium zinc oxide or indium-zinc oxide.
Preferably, the width of described metallic compound/metal/metal compound composite bed is 100 μm ~ 150 μm.
Preferably, the distance between adjacent two described metallic compounds/metal/metal compound composite bed is 100 μm ~ 150 μm.
Preferably, in the three-decker of described metallic compound/metal/metal compound composite bed, the thickness of described metal compound layer is 30nm ~ 50nm, and the thickness of described metal level is 10nm ~ 30nm.
Preferably, the thickness of described metal oxide layer is 30nm ~ 50nm.
Preferably, described Nb
2o
5, V
2o
5and Ta
2o
5mole dosage in metal oxide layer is equal.
Preferably, the thickness of described alloy-layer is 10nm ~ 20nm.
Preferably, the magnesium of described magnesium-silver alloy, silver-colored mass ratio are 8 ~ 13:1, and in described lithium-aluminium alloy, the mass fraction of lithium is 0.5 ~ 1%.More preferably, the magnesium of described magnesium-silver alloy, silver-colored mass ratio are 10:1, and in described lithium-aluminium alloy, the mass fraction of lithium is 0.6%.
Preferably, the thickness of described conductive oxide film layer is 20nm ~ 40nm.
Preferably, described transparent conductive anode substrate is ito glass substrate, AZO glass substrate or IZO glass substrate.
Preferably, described light emitting functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that are cascading on described transparent conductive anode substrate.
Preferably, the material of described hole injection layer comprises hole mobile material and is entrained in the hole-injecting material in described hole mobile material, and the doping mass fraction of described hole-injecting material is 25% ~ 35%; Described hole-injecting material is MoO
3, WO
3, V
2o
5and ReO
3in at least one, described hole mobile material is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) and 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] one in cyclohexane (TAPC), the thickness of hole injection layer is 10nm ~ 15nm.In preparation process, vacuum degree is 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate
Preferably, the material of described hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) and 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] one in cyclohexane (TAPC), thickness is 30 ~ 50nm.In preparation process, vacuum degree is 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate
Preferably, the material of described luminescent layer comprises green glow material of main part and green glow guest materials, and the doping mass fraction of described green glow guest materials is 2% ~ 10%, and the thickness of luminescent layer is 10nm ~ 30nm; In preparation process, vacuum degree is 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate
Preferably, described green glow material of main part is 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), 9,9'-(1,3-phenyl) two-9H-carbazoles (mCP), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD), 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane (TAPC) or two (1-naphthyl) anthracene (ADN) of 9,10-; Described green glow guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy)
3), acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy)
2(acac)) or three [2-(p-methylphenyl) pyridines] close iridium (Ir (mppy)
3).
Preferably, the material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq
3), 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ) and 1,3, one in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI), thickness is 10nm ~ 60nm; In preparation process, vacuum degree is 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate
Preferably, the material of described electron injecting layer comprises electron transport material and is entrained in the alkali metal sulfates in described electron transport material, and lithium salts or cesium salt, the doping mass fraction of described alkali metal sulfates is 6% ~ 25%, and the doping mass fraction of described lithium salts or cesium salt is 25% ~ 35%; Described alkali metal sulfates is Li
2sO
4, Na
2sO
4, K
2sO
4, Rb
2sO
4and Cs
2sO
4in any one, described lithium salts is LiF, LiN
3and Li
3any one in N, described cesium salt is CsF, CsN
3and Cs
3any one in N, described electron transport material is 4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq
3), 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, the one in 2,4-triazole (TAZ) and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI); The thickness of described electron injecting layer is 15nm ~ 45nm; In preparation process, vacuum degree is 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate
The invention provides a kind of organic electroluminescence device and preparation method thereof and there is following beneficial effect:
(1) organic electroluminescence device provided by the invention, negative electrode is composite construction, comprise the first cathode layer and the second cathode layer, first cathode layer comprises multiple metallic compound/metal/metal compound composite bed arranged in striped stride, and the second cathode layer comprises metal oxide layer, alloy-layer and conductive oxide film layer; This device can as opaque products when not lighting, and when normal work, anode and negative electrode go out optical contrast ratio is 15 ~ 20:1;
(2) preparation technology of organic electroluminescence device of the present invention is simple, and easy large area preparation, is suitable for industrialization and uses on a large scale.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device that the embodiment of the present invention 1 obtains;
Fig. 2 be the metallic compound/metal/metal compound composite bed of the embodiment of the present invention 1 organic electroluminescence device schematic diagram is set.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
A preparation method for organic electroluminescence device, comprises the following steps:
(1) transparent ito glass substrate is carried out successively liquid detergent cleaning, washed with de-ionized water, acetone cleaning, ethanol purge, all clean with supersonic wave cleaning machine, each washing 5 minutes, repeats 3 times respectively, and then by oven for drying; And surface activation process is carried out to the ito glass after cleaning, to increase the oxygen content on ITO surface, improve the work function on ITO surface; ITO thickness 150nm;
(2) adopt the mode of vacuum thermal resistance evaporation in ito glass substrate surface preparation light emitting functional layer, comprise hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively; Particularly:
The preparation of hole injection layer: by MoO
3be doped into N, as hole injection layer material in N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), MoO
3doping mass fraction be 30%, the thickness of hole injection layer is 12.5nm, vacuum degree 1 × 10
-5pa, evaporation rate
The preparation of hole transmission layer: adopt N, N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), thickness is 40nm, and vacuum degree is 1 × 10
-5pa, evaporation rate is
The preparation of luminescent layer: adopt 4,4 ', 4 ' '-three (carbazole-9-base) triphenylamine (TCTA) to be material of main part; Three (2-phenylpyridines) are adopted to close iridium (Ir (ppy)
3) be green glow guest materials, Ir (ppy)
3doping mass fraction is 6%, thickness 20nm; Vacuum degree is 1 × 10
-5pa, evaporation rate is
The preparation of electron transfer layer: adopt electron transport material 4,7-diphenyl-1,10-phenanthroline (Bphen), vacuum degree 1 × 10
-5pa, evaporation rate
evaporation thickness 35nm;
The preparation of electron injecting layer: adopt LiF and Li
2sO
4be doped to the composite material formed in electron transport material 4,7-diphenyl-1,10-phenanthroline (Bphen), Li
2sO
4doping mass fraction is 15%, LiF doping mass fraction is 30%, and evaporation thickness is 35nm, and vacuum degree is 1 × 10
-5pa, evaporation rate is
(3) on electron injecting layer, prepare negative electrode, obtain organic electroluminescence device; Negative electrode comprises the first cathode layer and the second cathode layer that stack gradually; First cathode layer comprises multiple metallic compound/metal/metal compound composite bed be arranged in striped stride on electron injecting layer; Second cathode layer comprises metal oxide layer, alloy-layer and conductive oxide film layer;
Particularly: a mask plate is first provided, mask plate is covered electron injecting layer surface, adopt the mode of vacuum evaporation at the multiple metallic compound/metal/metal compound composite bed arranged in striped stride of electron injecting layer surface preparation, be specially MoO
3/ Al/MoO
3, namely first preparing a layer thickness is the MoO of 50nm
3layer, then at MoO
3the Al layer that a layer thickness is 30nm prepared by layer, then on Al layer, prepare the MoO that a layer thickness is 50nm
3layer, the width of metallic compound/metal/metal compound composite bed is 100 μm, and the spacing of adjacent two metallic compounds/metal/metal compound composite bed is 100 μm, and the vacuum degree of Vacuum Evaporation Process is 1 × 10
-5pa, evaporation rate
Then metal oxide layer is prepared on the surface adopting the mode of magnetron sputtering on metallic compound/metal/metal compound composite bed and electron injecting layer not to cover composite bed, and material is Nb
2o
5and V
2o
5with the composite material that mol ratio 1:1 is formed, thickness is 40nm, and the background vacuum in magnetron sputtering process is 1 × 10
-4pa, accelerating voltage is 300V, and magnetic field is 50G, and power density is 10W/cm
2;
Adopt the mode of vacuum evaporation to prepare alloy-layer again on metal oxide layer, material is Mg:Ag(mass ratio 10:1) alloy, thickness is 15nm, and vacuum degree is 1 × 10
-4pa, evaporation rate
Finally adopt the mode of magnetron sputtering to prepare conductive oxide film layer over the alloyed layer, material is IZO, thickness 30nm, and the background vacuum in magnetron sputtering process is 1 × 10
-4pa, accelerating voltage is 300V, and magnetic field is 50G, and power density is 10W/cm
2.
Fig. 1 is the structural representation of the organic electroluminescence device that the embodiment of the present invention 1 obtains.As shown in Figure 1, the present embodiment organic electroluminescence device, comprises transparent conductive anode substrate 10, light emitting functional layer 20 and negative electrode 30 successively.Described negative electrode 30 comprises the first cathode layer 31 and the second cathode layer 32, first cathode layer 31 thickness is 200nm.The alloy-layer 322 that second cathode layer 32 comprises metal oxide layer 321 that a layer thickness is 40nm, a layer thickness is 15nm and a layer thickness are the conductive oxide film layer 323 of 30nm.
Fig. 2 be the first cathode layer of the embodiment of the present invention 1 organic electroluminescence device schematic diagram is set.First cathode layer 31 comprises multiple metallic compound/metal/metal compound composite bed 311 be arranged in striped stride in light emitting functional layer 20, the width of metallic compound/metal/metal compound composite bed 311 is 100 μm, and the spacing of adjacent two metallic compounds/metal/metal compound composite bed 311 is 100 μm.
Embodiment 2
A preparation method for organic electroluminescence device, comprises the following steps:
(1) transparent ito glass substrate is carried out successively liquid detergent cleaning, washed with de-ionized water, acetone cleaning, ethanol purge, all clean with supersonic wave cleaning machine, each washing 5 minutes, repeats 3 times respectively, and then by oven for drying; And surface activation process is carried out to the ito glass after cleaning, to increase the oxygen content on ITO surface, improve the work function on ITO surface; ITO thickness 120nm;
(2) adopt the mode of vacuum thermal resistance evaporation in ito glass substrate surface preparation light emitting functional layer, comprise hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively; Particularly:
The preparation of hole injection layer: by WO
3as hole injection layer material in '-three (carbazole-9-base) triphenylamine (TCTA) that is doped into 4,4 ', 4 ', WO
3doping mass fraction be 25%, the thickness of hole injection layer is 10nm, vacuum degree 5 × 10
-5pa, evaporation rate
The preparation of hole transmission layer: adopt 4,4 ', 4 ' '-three (carbazole-9-base) triphenylamine (TCTA), thickness is 30nm, and vacuum degree is 5 × 10
-5pa, evaporation rate is
The preparation of luminescent layer: adopt 9,9 '-(1,3-phenyl) two-9H-carbazole (mCP) to be material of main part; Adopt acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy)
2(acac)) be green glow guest materials, Ir (ppy)
2(acac) mass fraction that adulterates is 2%, thickness 10nm; Vacuum degree is 5 × 10
-5pa, evaporation rate is
The preparation of electron transfer layer: adopt electron transport material 4,7-diphenyl-1,10-Phen (BCP), vacuum degree 5 × 10
-5pa, evaporation rate
evaporation thickness 10nm;
The preparation of electron injecting layer: adopt LiN
3and Na
2sO
4be doped to the composite material formed in electron transport material 4,7-diphenyl-1,10-Phen (BCP), Na
2sO
4doping mass fraction is 25%, LiN
3doping mass fraction is 25%, and evaporation thickness is 45nm, and vacuum degree is 5 × 10
-5pa, evaporation rate is
(3) on electron injecting layer, prepare negative electrode, obtain organic electroluminescence device; Negative electrode comprises the first cathode layer and the second cathode layer that stack gradually; First cathode layer comprises multiple metallic compound/metal/metal compound composite bed be arranged in striped stride on electron injecting layer; Second cathode layer comprises metal oxide layer, alloy-layer and conductive oxide film layer;
Particularly: a mask plate is first provided, mask plate is covered electron injecting layer surface, adopt the mode of vacuum evaporation at the multiple metallic compound/metal/metal compound composite bed arranged in striped stride of electron injecting layer surface preparation, be specially ZnS/Ag/ZnS, namely the ZnS layer that a layer thickness is 40nm is first prepared, the Ag layer that a layer thickness is 20nm is prepared again on ZnS layer, then on Al layer, prepare the ZnS layer that a layer thickness is 40nm, the width of metallic compound/metal/metal compound composite bed is 120 μm, the spacing of adjacent two metallic compounds/metal/metal compound composite bed is 120 μm, the vacuum degree of Vacuum Evaporation Process is 1 × 10
-5pa, evaporation rate
Then metal oxide layer is prepared on the surface adopting the mode of magnetron sputtering on metallic compound/metal/metal compound composite bed and electron injecting layer not to cover composite bed, and material is Ta
2o
5and V
2o
5with the composite material that mol ratio 1:1 is formed, thickness is 30nm, and the background vacuum in magnetron sputtering process is 1 × 10
-5pa, accelerating voltage is 800V, and magnetic field is 200G, and power density is 40W/cm
2;
Adopt the mode of vacuum evaporation to prepare alloy-layer again on metal oxide layer, material is Mg:Ag(mass ratio 10:1) alloy, thickness is 20nm, and vacuum degree is 1 × 10
-5paPa, evaporation rate
Finally adopt the mode of magnetron sputtering to prepare conductive oxide film layer over the alloyed layer, material is ITO, thickness 20nm, and the background vacuum in magnetron sputtering process is 1 × 10
-5pa, accelerating voltage is 800V, and magnetic field is 200G, and power density is 40W/cm
2.
Embodiment 3
A preparation method for organic electroluminescence device, comprises the following steps:
(1) transparent ito glass substrate is carried out successively liquid detergent cleaning, washed with de-ionized water, acetone cleaning, ethanol purge, all clean with supersonic wave cleaning machine, each washing 5 minutes, repeats 3 times respectively, and then by oven for drying; And surface activation process is carried out to the ito glass after cleaning, to increase the oxygen content on ITO surface, improve the work function on ITO surface; ITO thickness 100nm;
(2) adopt the mode of vacuum thermal resistance evaporation in ito glass substrate surface preparation light emitting functional layer, comprise hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively; Particularly:
The preparation of hole injection layer: by V
2o
5be doped into 4, as hole injection layer material in 4 '-two (9-carbazole) biphenyl (CBP), V
2o
5doping mass fraction be 35%, the thickness of hole injection layer is 15nm, vacuum degree 5 × 10
-5pa, evaporation rate
The preparation of hole transmission layer: adopt 4,4 '-two (9-carbazole) biphenyl (CBP), thickness is 50nm, and vacuum degree is 5 × 10
-5pa, evaporation rate is
The preparation of luminescent layer: adopt 4,4 '-two (9-carbazole) biphenyl (CBP) to be material of main part; Three [2-(p-methylphenyl) pyridines] are adopted to close iridium (Ir (mppy)
3) be green glow guest materials, Ir (mppy)
3doping mass fraction is 10%, thickness 30nm; Vacuum degree is 5 × 10
-5pa, evaporation rate is
The preparation of electron transfer layer: adopt electron transport material 4-biphenyl phenolic group-two (2-methyl-oxine) to close aluminium (Balq), vacuum degree 5 × 10
-5pa, evaporation rate
evaporation thickness 60nm;
The preparation of electron injecting layer: adopt Li
3n and K
2sO
4be doped to electron transport material 4-biphenyl phenolic group-two (2-methyl-oxine) and close the composite material formed in aluminium (Balq), K
2sO
4doping mass fraction is 6%, Li
3n doping mass fraction is 35%, and evaporation thickness is 15nm, and vacuum degree is 5 × 10
-5pa, evaporation rate is
(3) on electron injecting layer, prepare negative electrode, obtain organic electroluminescence device; Negative electrode comprises the first cathode layer and the second cathode layer that stack gradually; First cathode layer comprises multiple metallic compound/metal/metal compound composite bed be arranged in striped stride on electron injecting layer; Second cathode layer comprises metal oxide layer, alloy-layer and conductive oxide film layer;
Particularly: a mask plate is first provided, mask plate is covered electron injecting layer surface, adopt the mode of vacuum evaporation at the multiple metallic compound/metal/metal compound composite bed arranged in striped stride of electron injecting layer surface preparation, be specially ITO/Pt/ITO, namely first preparing a layer thickness is the ITO layer of 35nm, prepare the Pt layer that a layer thickness is 15nm on the ito layer again, then on Pt layer, the ITO layer that a layer thickness is 35nm is prepared, the width of metallic compound/metal/metal compound composite bed is 110 μm, the spacing of adjacent two metallic compounds/metal/metal compound composite bed is 110 μm, the vacuum degree of Vacuum Evaporation Process is 1 × 10
-5pa, evaporation rate
Then metal oxide layer is prepared on the surface adopting the mode of magnetron sputtering on metallic compound/metal/metal compound composite bed and electron injecting layer not to cover composite bed, and material is Nb
2o
5, Ta
2o
5with the composite material that mol ratio 1:1 is formed, thickness is 50nm, and the background vacuum in magnetron sputtering process is 1 × 10
-3pa, accelerating voltage is 600V, and magnetic field is 100G, and power density is 20W/cm
2;
Adopt the mode of vacuum evaporation to prepare alloy-layer again on metal oxide layer, material is the mass fraction 0.6% of Li-Al(Li) alloy, thickness is 10nm, and vacuum degree is 1 × 10
-3pa, evaporation rate
Finally adopt the mode of magnetron sputtering to prepare conductive oxide film layer over the alloyed layer, material is AZO, thickness 40nm, and the background vacuum in magnetron sputtering process is 1 × 10
-3pa, accelerating voltage is 600V, and magnetic field is 100G, and power density is 20W/cm
2.
Embodiment 4
A preparation method for organic electroluminescence device, comprises the following steps:
(1) transparent ito glass substrate is carried out successively liquid detergent cleaning, washed with de-ionized water, acetone cleaning, ethanol purge, all clean with supersonic wave cleaning machine, each washing 5 minutes, repeats 3 times respectively, and then by oven for drying; And surface activation process is carried out to the ito glass after cleaning, to increase the oxygen content on ITO surface, improve the work function on ITO surface; ITO thickness 100nm;
(2) adopt the mode of vacuum thermal resistance evaporation in ito glass substrate surface preparation light emitting functional layer, comprise hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively; Particularly:
The preparation of hole injection layer: by ReO
3be doped into N, N '-two (3-aminomethyl phenyl)-N, N ' in-diphenyl-4,4 '-benzidine (TPD) as hole injection layer material, ReO
3doping mass fraction be 30%, the thickness of hole injection layer is 13nm, vacuum degree 5 × 10
-5pa, evaporation rate
The preparation of hole transmission layer: adopt N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine (TPD), thickness is 40nm, and vacuum degree is 5 × 10
-5pa, evaporation rate is
The preparation of luminescent layer: adopt N, N '-two (3-aminomethyl phenyl)-N, N '-diphenyl-4,4 '-benzidine (TPD) to be material of main part; Three (2-phenylpyridines) are adopted to close iridium (Ir (ppy)
3) be green glow guest materials, Ir (mppy)
3doping mass fraction is 5%, thickness 20nm; Vacuum degree is 5 × 10
-5pa, evaporation rate is
The preparation of electron transfer layer: adopt electron transport material oxine aluminium (Alq
3), vacuum degree 5 × 10
-5pa, evaporation rate
evaporation thickness 30nm;
The preparation of electron injecting layer: adopt CsF and Rb
2sO
4be doped to electron transport material oxine aluminium (Alq
3) the middle composite material formed, Rb
2sO
4doping mass fraction is 10%, CsF doping mass fraction is 30%, and evaporation thickness is 30nm, and vacuum degree is 5 × 10
-5pa, evaporation rate is
(3) on electron injecting layer, prepare negative electrode, obtain organic electroluminescence device; Negative electrode comprises the first cathode layer and the second cathode layer that stack gradually; First cathode layer comprises multiple metallic compound/metal/metal compound composite bed be arranged in striped stride on electron injecting layer; Second cathode layer comprises metal oxide layer, alloy-layer and conductive oxide film layer;
Particularly: a mask plate is first provided, mask plate is covered electron injecting layer surface, adopt the mode of vacuum evaporation at the multiple metallic compound/metal/metal compound composite bed arranged in striped stride of electron injecting layer surface preparation, be specially ITO/Au/ITO, namely first preparing a layer thickness is the ITO layer of 30nm, prepare the Au layer that a layer thickness is 10nm on the ito layer again, then on Au layer, the ITO layer that a layer thickness is 30nm is prepared, the width of metallic compound/metal/metal compound composite bed is 150 μm, the spacing of adjacent two metallic compounds/metal/metal compound composite bed is 150 μm, the vacuum degree of Vacuum Evaporation Process is 1 × 10
-4pa, evaporation rate
Then metal oxide layer is prepared on the surface adopting the mode of magnetron sputtering on metallic compound/metal/metal compound composite bed and electron injecting layer not to cover composite bed, and material is Nb
2o
5, V
2o
5, Ta
2o
5with the composite material that mol ratio 1:1:1 is formed, thickness is 40nm, and the background vacuum in magnetron sputtering process is 1 × 10
-5pa, accelerating voltage is 400V, and magnetic field is 100G, and power density is 30W/cm
2;
Adopt the mode of vacuum evaporation to prepare alloy-layer again on metal oxide layer, material is Mg:Ag(mass ratio 10:1) alloy, thickness is 10nm, and vacuum degree is 1 × 10
-5pa, evaporation rate
Finally adopt the mode of magnetron sputtering to prepare conductive oxide film layer over the alloyed layer, material is IZO, thickness 20nm, and the background vacuum in magnetron sputtering process is 1 × 10
-5pa, accelerating voltage is 400V, and magnetic field is 100G, and power density is 30W/cm
2.
Embodiment 5
A preparation method for organic electroluminescence device, comprises the following steps:
(1) transparent ito glass substrate is carried out successively liquid detergent cleaning, washed with de-ionized water, acetone cleaning, ethanol purge, all clean with supersonic wave cleaning machine, each washing 5 minutes, repeats 3 times respectively, and then by oven for drying; And surface activation process is carried out to the ito glass after cleaning, to increase the oxygen content on ITO surface, improve the work function on ITO surface; ITO thickness 100nm;
(2) adopt the mode of vacuum thermal resistance evaporation in ito glass substrate surface preparation light emitting functional layer, comprise hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively; Particularly:
The preparation of hole injection layer: by MoO
3be doped into as hole injection layer material in 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane (TAPC), MoO
3doping mass fraction be 25%, the thickness of hole injection layer is 10nm, vacuum degree 5 × 10
-5pa, evaporation rate
The preparation of hole transmission layer: adopt 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane (TAPC), thickness is 40nm, and vacuum degree is 5 × 10
-5pa, evaporation rate is
The preparation of luminescent layer: adopt 1,1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane (TAPC) to be material of main part; Adopt acetopyruvic acid two (2-phenylpyridine) iridium (Ir (ppy)
2(acac)) be green glow guest materials, Ir (ppy)
2(acac) mass fraction that adulterates is 7%, thickness 20nm; Vacuum degree is 5 × 10
-5pa, evaporation rate is
The preparation of electron transfer layer: adopt electron transport material 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), vacuum degree 5 × 10
-5pa, evaporation rate
evaporation thickness 50nm;
The preparation of electron injecting layer: adopt CsN
3and Cs
2sO
4be doped to electron transport material 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, the composite material formed in 2,4-triazole (TAZ), Cs
2sO
4doping mass fraction is 10%, CsN
3doping mass fraction is 30%, and evaporation thickness is 30nm, and vacuum degree is 5 × 10
-5pa, evaporation rate is
(3) on electron injecting layer, prepare negative electrode, obtain organic electroluminescence device; Negative electrode comprises the first cathode layer and the second cathode layer that stack gradually; First cathode layer comprises multiple metallic compound/metal/metal compound composite bed be arranged in striped stride on electron injecting layer; Second cathode layer comprises metal oxide layer, alloy-layer and conductive oxide film layer;
Particularly: a mask plate is first provided, mask plate is covered electron injecting layer surface, adopt the mode of vacuum evaporation at the multiple metallic compound/metal/metal compound composite bed arranged in striped stride of electron injecting layer surface preparation, be specially ITO/Ag/ITO, namely first preparing a layer thickness is the ITO layer of 35nm, prepare the Ag layer that a layer thickness is 20nm on the ito layer again, then on Ag layer, the ITO layer that a layer thickness is 35nm is prepared, the width of metallic compound/metal/metal compound composite bed is 120 μm, the spacing of adjacent two metallic compounds/metal/metal compound composite bed is 120 μm, the vacuum degree of Vacuum Evaporation Process is 1 × 10
-4pa, evaporation rate
Then metal oxide layer is prepared on the surface adopting the mode of magnetron sputtering on metallic compound/metal/metal compound composite bed and electron injecting layer not to cover composite bed, and material is Nb
2o
5, V
2o
5with the composite material that mol ratio 1:1 is formed, thickness is 35nm, and the background vacuum in magnetron sputtering process is 1 × 10
-5pa, accelerating voltage is 400V, and magnetic field is 100G, and power density is 30W/cm
2;
Adopt the mode of vacuum evaporation to prepare alloy-layer again on metal oxide layer, material is Mg:Ag(mass ratio 10:1) alloy, thickness is 16nm, and vacuum degree is 1 × 10
-5pa, evaporation rate
Finally adopt the mode of magnetron sputtering to prepare conductive oxide film layer over the alloyed layer, material is ITO, thickness 30nm, and the background vacuum in magnetron sputtering process is 1 × 10
-5pa, accelerating voltage is 400V, and magnetic field is 100G, and power density is 30W/cm
2.
Embodiment 6
A preparation method for organic electroluminescence device, comprises the following steps:
(1) transparent ito glass substrate is carried out successively liquid detergent cleaning, washed with de-ionized water, acetone cleaning, ethanol purge, all clean with supersonic wave cleaning machine, each washing 5 minutes, repeats 3 times respectively, and then by oven for drying; And surface activation process is carried out to the ito glass after cleaning, to increase the oxygen content on ITO surface, improve the work function on ITO surface; ITO thickness 100nm;
(2) adopt the mode of vacuum thermal resistance evaporation in ito glass substrate surface preparation light emitting functional layer, comprise hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer successively; Particularly:
The preparation of hole injection layer: by WO
3be doped into N, as hole injection layer material in N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), V
2o
5doping mass fraction be 30%, the thickness of hole injection layer is 12nm, vacuum degree 1 × 10
-3pa, evaporation rate
The preparation of hole transmission layer: adopt N, N '-diphenyl-N, N '-two (1-naphthyl)-1,1 '-biphenyl-4,4 '-diamines (NPB), thickness is 50nm, and vacuum degree is 1 × 10
-3pa, evaporation rate is
The preparation of luminescent layer: adopt 9,10-two (1-naphthyl) anthracene (AND) to be material of main part; Three [2-(p-methylphenyl) pyridines] are adopted to close iridium (Ir (mppy)
3) be green glow guest materials, Ir (mppy)
3doping mass fraction is 6%, thickness 20nm; Vacuum degree is 1 × 10
-3pa, evaporation rate is
The preparation of electron transfer layer: adopt electron transport material 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI), vacuum degree 1 × 10
-3pa a, evaporation rate
evaporation thickness 60nm;
The preparation of electron injecting layer: adopt Cs
3n and Cs
2sO
4be doped to the composite material formed in electron transport material 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI), Cs
2sO
4doping mass fraction is 10%, Cs
3n doping mass fraction is 30%, and evaporation thickness is 30nm, and vacuum degree is 1 × 10
-3pa, evaporation rate is
(3) on electron injecting layer, prepare negative electrode, obtain organic electroluminescence device; Negative electrode comprises the first cathode layer and the second cathode layer that stack gradually; First cathode layer comprises multiple metallic compound/metal/metal compound composite bed be arranged in striped stride on electron injecting layer; Second cathode layer comprises metal oxide layer, alloy-layer and conductive oxide film layer;
Particularly: a mask plate is first provided, mask plate is covered electron injecting layer surface, adopt the mode of vacuum evaporation at the multiple metallic compound/metal/metal compound composite bed arranged in striped stride of electron injecting layer surface preparation, be specially ZnO/Cu/ZnO, namely first preparing a layer thickness is the ZnO layer of 35nm, the Cu layer that a layer thickness is 20nm is prepared again in ZnO layer, then on Cu layer, the ZnO layer that a layer thickness is 35nm is prepared, the width of metallic compound/metal/metal compound composite bed is 130 μm, the spacing of adjacent two metallic compounds/metal/metal compound composite bed is 130 μm, the vacuum degree of Vacuum Evaporation Process is 1 × 10
-3pa, evaporation rate
Then metal oxide layer is prepared on the surface adopting the mode of magnetron sputtering on metallic compound/metal/metal compound composite bed and electron injecting layer not to cover composite bed, and material is V
2o
5, Ta
2o
5with the composite material that mol ratio 1:1 is formed, thickness is 40nm, and the background vacuum in magnetron sputtering process is 1 × 10
-5pa, accelerating voltage is 600V, and magnetic field is 100G, and power density is 20W/cm
2;
Adopt the mode of vacuum evaporation to prepare alloy-layer again on metal oxide layer, material is the mass fraction 0.6% of Li-Al(Li) alloy, thickness is 15nm, and vacuum degree is 1 × 10
-5pa, evaporation rate
Finally adopt the mode of magnetron sputtering to prepare conductive oxide film layer over the alloyed layer, material is AZO, thickness 30nm, and the background vacuum in magnetron sputtering process is 1 × 10
-5pa, accelerating voltage is 600V, and magnetic field is 100G, and power density is 20W/cm
2.
Effect example
Test of the present invention and Preparation equipment 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 of Keithley company of the U.S. tests electric property, the CS-100A colorimeter test brightness of Japanese Konica Minolta company and colourity.
By the organic electroluminescence device obtained by the embodiment of the present invention 1 ~ 6 at 1000cd/m
2carry out luminous efficiency test under brightness, test result is as shown in table 1:
Table 1
As can be seen from the data of table 1, organic electroluminescence device provided by the invention, anode surface bright dipping is many, cathode plane bright dipping is few, this exceeds finish matter because anode surface adopts, and bright dipping is many, and light extraction efficiency is higher, cathode plane is provided with translucent first cathode layer that striped stride is arranged, first cathode layer can produce reflection to light, thus decreases the bright dipping of cathode plane, and the second cathode layer can carry out transmission to light, thus cathode plane light emission rate is relatively poor, bright dipping is less.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. an organic electroluminescence device, the light emitting functional layer comprising transparent conductive anode substrate and be cascading on described transparent conductive anode substrate and negative electrode, it is characterized in that, described negative electrode comprises be cascading the first cathode layer in described light emitting functional layer and the second cathode layer;
Described first cathode layer comprises multiple metallic compound/metal/metal compound composite bed be arranged in striped stride in described light emitting functional layer, described metallic compound/metal/metal compound composite bed is three-decker, and the material of described three-decker consists of MoO
3/ Al/MoO
3, ZnS/Ag/ZnS, ITO/Pt/ITO, ITO/Au/ITO, ITO/Ag/ITO or ZnO/Cu/ZnO;
Described second cathode layer comprises the metal oxide layer, alloy-layer and the conductive oxide film layer that are cascading on described first cathode layer; The material of described metal oxide layer is Nb
2o
5, V
2o
5and Ta
2o
5in at least two kinds, the material of described alloy-layer is magnesium-silver alloy or lithium-aluminium alloy, and the material of described conductive oxide film layer is indium tin oxide, aluminium zinc oxide or indium-zinc oxide.
2. organic electroluminescence device as claimed in claim 1, it is characterized in that, the width of described metallic compound/metal/metal compound composite bed is 100 μm ~ 150 μm, and the distance between adjacent two described metallic compounds/metal/metal compound composite bed is 100 μm ~ 150 μm.
3. organic electroluminescence device as claimed in claim 1, it is characterized in that, in the three-decker of described metallic compound/metal/metal compound composite bed, the thickness of metal compound layer is 30nm ~ 50nm, and the thickness of metal level is 10nm ~ 30nm.
4. organic electroluminescence device as claimed in claim 1, it is characterized in that, the thickness of described metal oxide layer is 30nm ~ 50nm, and the thickness of described alloy-layer is 10nm ~ 20nm, and the thickness of described conductive oxide film layer is 20nm ~ 40nm.
5. organic electroluminescence device as claimed in claim 1, it is characterized in that, described light emitting functional layer comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that are cascading on described transparent conductive anode substrate.
6. organic electroluminescence device as claimed in claim 5, it is characterized in that, the material of described hole injection layer comprises hole mobile material and is entrained in the hole-injecting material in described hole mobile material, and the doping mass fraction of described hole-injecting material is 25% ~ 35%; Described hole-injecting material is MoO
3, WO
3, V
2o
5and ReO
3in at least one, described hole mobile material is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-base) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine and 1,1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] one in cyclohexane, the thickness of hole injection layer is 10nm ~ 15nm.
7. organic electroluminescence device as claimed in claim 5, it is characterized in that, the material of described hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-base) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine and 1, one in 1-bis-[4-[N, N '-two (p-tolyl) are amino] phenyl] cyclohexane, thickness is 30 ~ 50nm; The material of described electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1, and 2,4-triazole and 1, one in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene, thickness is 10nm ~ 60nm.
8. organic electroluminescence device as claimed in claim 5, it is characterized in that, the material of described luminescent layer comprises green glow material of main part and green glow guest materials, the doping mass fraction of described green glow guest materials is 2% ~ 10%, described green glow material of main part is 4, 4', 4''-tri-(carbazole-9-base) triphenylamine, 9, 9'-(1, 3-phenyl) two-9H-carbazoles, 4, 4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4, 4'-benzidine, 1, 1-bis-[4-[N, N '-two (p-tolyl) is amino] phenyl] cyclohexane or 9, two (1-naphthyl) anthracene of 10-, described green glow guest materials is that three (2-phenylpyridines) close iridium, acetopyruvic acid two (2-phenylpyridine) iridium or three [2-(p-methylphenyl) pyridines] and close iridium, the thickness of described luminescent layer is 10nm ~ 30nm.
9. organic electroluminescence device as claimed in claim 5, it is characterized in that, the material of described electron injecting layer comprises electron transport material and is entrained in the alkali metal sulfates in described electron transport material, and lithium salts or cesium salt, the doping mass fraction of described alkali metal sulfates is 6% ~ 25%, and the doping mass fraction of described lithium salts or cesium salt is 25% ~ 35%; Described alkali metal sulfates is Li
2sO
4, Na
2sO
4, K
2sO
4, Rb
2sO
4and Cs
2sO
4in any one, described lithium salts is LiF, LiN
3and Li
3any one in N, described cesium salt is CsF, CsN
3and Cs
3any one in N, described electron transport material is 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phens, 4-biphenyl phenolic group-two (2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-base)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2, one in 4-triazole, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene; The thickness of described electron injecting layer is 15nm ~ 45nm.
10. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
Adopt the mode of vacuum evaporation to prepare light emitting functional layer on transparent conductive anode substrate, vacuum degree is 1 × 10
-5~ 1 × 10
-3pa;
Prepare negative electrode on described light emitting functional layer surface again, obtain organic electroluminescence device; Described negative electrode comprises the first cathode layer and the second cathode layer; Described first cathode layer comprises multiple metallic compound/metal/metal compound composite bed be arranged in striped stride in described light emitting functional layer; Described second cathode layer comprises metal oxide layer, alloy-layer and conductive oxide film layer; Particularly:
One mask plate is provided, described mask plate is covered described light emitting functional layer surface, then adopt the mode of vacuum evaporation at the multiple metallic compound/metal/metal compound composite bed arranged in striped stride of described light emitting functional layer surface preparation, vacuum degree is 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate
described metallic compound/metal/metal compound composite bed is three-decker, and the material of described three-decker consists of MoO
3/ Al/MoO
3, ZnS/Ag/ZnS, ITO/Pt/ITO, ITO/Au/ITO, ITO/Ag/ITO or ZnO/Cu/ZnO;
Then the mode of magnetron sputtering is adopted to prepare metal oxide layer on described first cathode layer; Adopt the mode of vacuum evaporation to prepare alloy-layer again on described metal oxide layer, vacuum degree is 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate
the mode of magnetron sputtering is finally adopted to prepare conductive oxide film layer on described alloy-layer; Background vacuum in above-mentioned magnetron sputtering process is 1 × 10
-5~ 1 × 10
-3pa, accelerating voltage is 300 ~ 800V, and magnetic field is 50 ~ 200G, and power density is 10 ~ 40W/cm
2; The material of described metal oxide layer is Nb
2o
5, V
2o
5and Ta
2o
5in at least two kinds, the material of described alloy-layer is magnesium-silver alloy or lithium-aluminium alloy, and the material of described conductive oxide film layer is indium tin oxide, aluminium zinc oxide or indium-zinc oxide.
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| CN107017350A (en) * | 2015-10-28 | 2017-08-04 | 三星显示有限公司 | Organic illuminating element |
| CN107785494A (en) * | 2016-08-24 | 2018-03-09 | 乐金显示有限公司 | Organic light-emitting display device |
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| CN113078271A (en) * | 2020-01-03 | 2021-07-06 | 上海和辉光电有限公司 | Organic electroluminescent device and display device |
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