CN104183765A - Organic light emitting diode and preparation method thereof - Google Patents
Organic light emitting diode and preparation method thereof Download PDFInfo
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- CN104183765A CN104183765A CN201310193553.9A CN201310193553A CN104183765A CN 104183765 A CN104183765 A CN 104183765A CN 201310193553 A CN201310193553 A CN 201310193553A CN 104183765 A CN104183765 A CN 104183765A
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- phenyl
- carbazole
- diphenyl
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- 238000002360 preparation method Methods 0.000 title abstract description 91
- 239000002131 composite material Substances 0.000 claims abstract description 50
- 239000011521 glass Substances 0.000 claims abstract description 30
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims description 297
- 238000001704 evaporation Methods 0.000 claims description 154
- 230000008020 evaporation Effects 0.000 claims description 154
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 94
- 229910052741 iridium Inorganic materials 0.000 claims description 63
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 63
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 54
- 230000003667 anti-reflective effect Effects 0.000 claims description 52
- 238000004020 luminiscence type Methods 0.000 claims description 46
- 238000002347 injection Methods 0.000 claims description 45
- 239000007924 injection Substances 0.000 claims description 45
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 37
- 230000005540 biological transmission Effects 0.000 claims description 35
- 239000004305 biphenyl Substances 0.000 claims description 33
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 27
- 235000010290 biphenyl Nutrition 0.000 claims description 27
- 238000005401 electroluminescence Methods 0.000 claims description 27
- 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 25
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 24
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 24
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 24
- 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 24
- 229910000577 Silicon-germanium Inorganic materials 0.000 claims description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 19
- 239000004411 aluminium Substances 0.000 claims description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 claims description 15
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 15
- 229920002635 polyurethane Polymers 0.000 claims description 15
- 239000004814 polyurethane Substances 0.000 claims description 15
- ZVFQEOPUXVPSLB-UHFFFAOYSA-N 3-(4-tert-butylphenyl)-4-phenyl-5-(4-phenylphenyl)-1,2,4-triazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C(N1C=2C=CC=CC=2)=NN=C1C1=CC=C(C=2C=CC=CC=2)C=C1 ZVFQEOPUXVPSLB-UHFFFAOYSA-N 0.000 claims description 13
- VOIVTTPPKHORBL-UHFFFAOYSA-N 1-naphthalen-1-ylanthracene Chemical class C1=CC=C2C(C=3C4=CC5=CC=CC=C5C=C4C=CC=3)=CC=CC2=C1 VOIVTTPPKHORBL-UHFFFAOYSA-N 0.000 claims description 12
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 12
- 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 11
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- -1 4, 6-difluorophenyl Chemical group 0.000 claims description 7
- 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 7
- LPCWDYWZIWDTCV-UHFFFAOYSA-N 1-phenylisoquinoline Chemical compound C1=CC=CC=C1C1=NC=CC2=CC=CC=C12 LPCWDYWZIWDTCV-UHFFFAOYSA-N 0.000 claims description 6
- 150000005360 2-phenylpyridines Chemical class 0.000 claims description 6
- IYVKASORLNOINI-UHFFFAOYSA-N 9-(3-pyridin-2-ylphenyl)carbazole Chemical class N1=CC=CC=C1C1=CC=CC(N2C3=CC=CC=C3C3=CC=CC=C32)=C1 IYVKASORLNOINI-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 6
- UNRQTHVKJQUDDF-UHFFFAOYSA-N acetylpyruvic acid Chemical compound CC(=O)CC(=O)C(O)=O UNRQTHVKJQUDDF-UHFFFAOYSA-N 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- RTRAMYYYHJZWQK-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=CC=N1 RTRAMYYYHJZWQK-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910052950 sphalerite Inorganic materials 0.000 claims description 5
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 5
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 3
- KZULYCPTNSEXTR-UHFFFAOYSA-N 2-(2,4-difluorophenyl)pyridine 2-[5-(trifluoromethyl)-1H-1,2,4-triazol-3-yl]pyridine Chemical compound FC(C1=NNC(=N1)C1=NC=CC=C1)(F)F.FC1=CC=C(C(=C1)F)C1=NC=CC=C1 KZULYCPTNSEXTR-UHFFFAOYSA-N 0.000 claims description 3
- FHGGUWFGLZJGDB-UHFFFAOYSA-N C1=CC=CC=C1.C1(=CC=CC=C1)[Si](C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1=CC=CC=C1.C1(=CC=CC=C1)[Si](C1=CC=CC=C1)C1=CC=CC=C1 FHGGUWFGLZJGDB-UHFFFAOYSA-N 0.000 claims description 3
- MJHALVMQSVRHLU-UHFFFAOYSA-N N1=C(C=CC=C1)C1=NN=NN1.FC1=CC=C(C(=C1)F)C1=NC=CC=C1 Chemical compound N1=C(C=CC=C1)C1=NN=NN1.FC1=CC=C(C(=C1)F)C1=NC=CC=C1 MJHALVMQSVRHLU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000002985 plastic film Substances 0.000 description 18
- 229920006255 plastic film Polymers 0.000 description 18
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 13
- 229920003023 plastic Polymers 0.000 description 13
- 239000004033 plastic Substances 0.000 description 13
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 10
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 10
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 10
- 238000007738 vacuum evaporation Methods 0.000 description 10
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 238000000059 patterning Methods 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- XJHCXCQVJFPJIK-UHFFFAOYSA-M cesium fluoride Substances [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 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 5
- 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 4
- 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
- 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
- 238000005286 illumination Methods 0.000 description 3
- CECAIMUJVYQLKA-UHFFFAOYSA-N iridium 1-phenylisoquinoline Chemical compound [Ir].C1=CC=CC=C1C1=NC=CC2=CC=CC=C12.C1=CC=CC=C1C1=NC=CC2=CC=CC=C12.C1=CC=CC=C1C1=NC=CC2=CC=CC=C12 CECAIMUJVYQLKA-UHFFFAOYSA-N 0.000 description 3
- 229910016460 CzSi Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WIHKEPSYODOQJR-UHFFFAOYSA-N [9-(4-tert-butylphenyl)-6-triphenylsilylcarbazol-3-yl]-triphenylsilane Chemical compound C1=CC(C(C)(C)C)=CC=C1N1C2=CC=C([Si](C=3C=CC=CC=3)(C=3C=CC=CC=3)C=3C=CC=CC=3)C=C2C2=CC([Si](C=3C=CC=CC=3)(C=3C=CC=CC=3)C=3C=CC=CC=3)=CC=C21 WIHKEPSYODOQJR-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- DETFWTCLAIIJRZ-UHFFFAOYSA-N triphenyl-(4-triphenylsilylphenyl)silane Chemical compound C1=CC=CC=C1[Si](C=1C=CC(=CC=1)[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 DETFWTCLAIIJRZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- YSZJKUDBYALHQE-UHFFFAOYSA-N rhenium trioxide Chemical compound O=[Re](=O)=O YSZJKUDBYALHQE-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
- H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
-
- 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
- H10K50/86—Arrangements for improving contrast, e.g. preventing reflection of ambient light
-
- 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
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
-
- 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
- H10K85/10—Organic polymers or oligomers
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to an organic light emitting diode comprising an anti-reflection composite layer, a substrate, an anode layer, a short circuit reducing layer, a first organic light-emitting function layer, a charge generation layer, a second organic light-emitting function layer and a cathode layer which are stacked in sequence. The anti-reflection composite layer comprises a white glass plate and anti-reflection films arranged at the two sides of the white glass plate. The substrate is arranged on one of the anti-reflection films and a light-outgoing gap is arranged between the substrate and the anti-reflection film. According to the organic light emitting diode, through arranging the anti-reflection film under the light-outgoing surface, and arranging the short circuit reducing layer on the anode layer, the light-outgoing efficiency of the whole device is greatly improved. A preparation method is easy, low in equipment requirement, and can be widely popularized and applied. Besides, the invention further relates to the preparation method of the organic light emitting diode.
Description
Technical field
The present invention relates to electroluminescent technology field, especially relate to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) has advantages of that some are unique: (1) OLED belongs to diffused area source, does not need by extra light-conducting system, to obtain large-area white light source as light-emitting diode (LED); (2) due to the diversity of luminous organic material, OLED illumination is the light of design color as required, no matter be little Molecule OLEDs at present, or polymer organic LED (PLED) has all obtained and has comprised white-light spectrum at the light of interior all colours; (3) OLED can make on as glass, pottery, metal or plastic or other material at multiple substrate, thereby freer while making to design lighting source; (4) adopt the mode of making OLED demonstration to make OLED illumination panel, can in illumination, show information; (5) OLED also can be used as controlled look in illuminator, allows user to regulate light atmosphere according to individual demand.Yet traditional not high problem of OLED ubiquity light extraction efficiency.
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.
An organic electroluminescence device, comprises the antireflection composite bed, substrate, anode layer, short reduction layer, the first organic luminescence function layer, charge generation layer, the second organic luminescence function layer and the cathode layer that are cascading; Wherein, the anti-reflective film that described antireflection composite bed comprises white glass plate and is positioned at described white glass plate both sides, described substrate be located at wherein on an anti-reflective film and and this anti-reflective film between be provided with bright dipping space; The material of described short reduction layer is SiGe(SiGe) and In
2o
3(indium sesquioxide), ZnS(zinc sulphide), SnO
2(tin ash) or SiO
2(silicon dioxide); Described the first organic luminescence function layer is included in the first hole injection layer, the first hole transmission layer, the first red light luminescent layer, the first green luminescence layer, blue light-emitting and the first electron transfer layer being cascading on described short reduction layer; Described the second organic luminescence function layer is included in the second hole injection layer, the second hole transmission layer, the second red light luminescent layer, the second green luminescence layer, the second electron transfer layer and the electron injecting layer being cascading on described charge generation layer, and described cathode layer is located on described electron injecting layer.
In an embodiment, the material of described anti-reflective film is SiGe(SiGe therein), thickness is 10～20nm.
In an embodiment, the material of described substrate is polyurethane therein, described substrate near a side of described antireflection composite bed be provided with a plurality of be uniformly distributed and with the integrated projection of described substrate.
In an embodiment, described projection is square therein, and thickness is 5～20 μ m, spacing 5～20 μ m between adjacent protrusion.
In an embodiment, described anode layer is the ITO(tin indium oxide of thickness 100nm therein) layer.
In an embodiment, the material of described the first hole injection layer is MoO therein
3(molybdenum trioxide), WO
3(tungstic acid), V
2o
5(vanadic oxide) or ReO
3(rhenium trioxide) is entrained in N according to 25～35% doping mass ratio, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 4,4'-bis-(9-carbazole) biphenyl (CBP), N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine (TPD) or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] the middle composite material forming of cyclohexane (TAPC);
The material of described the first hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane;
The material of described the first red light luminescent layer is that two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanediones) close iridium (Ir (MDQ)
2(acac)), two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III) (PQIr), two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III) ((fbi)
2ir (acac)), two [2-(2-fluorophenyl)-1,3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) closes iridium (III) ((F-BT)
2ir (acac)), two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) (Ir (btp)
2(acac)) or three (1-phenyl-isoquinolin) close iridium) (Ir (piq)
3) according to 0.5～2% doping mass ratio, be entrained in 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA), 9,9'-(1,3-phenyl) two-9H-carbazole (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 '-bis-(p-tolyl) amino] phenyl] two (1-naphthyl) anthracenes of cyclohexane (TAPC) or 9,10-) composite material that forms in (ADN);
The material of described the first green luminescence layer 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 (III) (Ir (mppy)
3) according to 2～10% doping mass ratio, be entrained in 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 9,9'-(1,3-phenyl) two-9H-carbazole, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine, 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] composite material that forms in two (1-naphthyl) anthracenes of cyclohexane or 9,10-;
The material of described blue light-emitting comprises Blue-light emitting host material, blue light guest materials and charge generating material, described Blue-light emitting host material is 4, 4'-bis-(9-carbazole) biphenyl, 9, 9'-(1, 3-phenyl) two-9H-carbazole, 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles (CzSi) of 6-, 2, two (3-(9H-carbazole-9-yl) phenyl) pyridines (26DCzPPY) of 6-, 3, two (3-(9H-carbazole-9-yl) phenyl) pyridines (35DCzPPY) or 1 of 5-, two (triphenyl silicon) benzene (UGH2) of 4--, described blue light guest materials is two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic), two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium (FIr6), three (2-(4', the fluoro-5 '-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium (FCNIr), two (4, 6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1, 2, 4-triazole) close iridium (FIrtaz) or two (4, 6-difluorophenyl pyridine) (5-(pyridine-2-yl)-tetrazolium) closes iridium) (FIrN4), described charge generating material is MoO
3, V
2o
5, WO
3or ReO
3, the mass ratio of described Blue-light emitting host material, described blue light guest materials and described charge generating material is 1:5～20:5～10,
The material of described the first electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen), 4,7-diphenyl-1,10-Phen (BCP), 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium (BAlq), oxine aluminium (Alq
3), 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole (TAZ) or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI).
In an embodiment, the material of described charge generation layer is MoO therein
3, V
2o
5, WO
3or ReO
3, thickness is 5～30nm.
In an embodiment, the material of described the second hole injection layer is MoO therein
3, WO
3, V
2o
5or ReO
3doping mass ratio according to 25～35% is entrained in N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] composite material that forms in cyclohexane;
The material of described the second hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane;
The material of described the second red light luminescent layer is two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium, two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III), two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III), two [2-(2-fluorophenyl)-1, 3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III), two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) or three (1-phenyl-isoquinolin) and close iridium) doping mass ratio according to 0.5～2% is entrained in 4, 4', 4''-tri-(carbazole-9-yl) triphenylamine, 9, 9'-(1, 3-phenyl) two-9H-carbazole, 4, 4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4, 4'-benzidine, 1, 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane or 9, two (1-naphthyl) anthracenes of 10-) composite material forming in,
The material of described the second green luminescence layer is that three (2-phenylpyridines) close iridium, acetopyruvic acid two (2-phenylpyridine) iridium or three [2-(p-methylphenyl) pyridine] and close iridium (III) and be entrained in 4 according to 2～10% doping mass ratio, 4', 4''-tri-(carbazole-9-yl) triphenylamine, 9,9'-(1,3-phenyl) two-9H-carbazole, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine, 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] composite material that forms in two (1-naphthyl) anthracenes of cyclohexane or 9,10-;
The material of described the second electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene;
The material of described electron injecting layer is Cs
2cO
3(cesium carbonate), CsF(cesium fluoride), CsN
3(cesium trinitride), Li
2cO
3(lithium carbonate), LiF(lithium fluoride) or Li
2o(lithia) according to 25～35% doping mass ratio, be entrained in 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole or 1, the composite material forming in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene.
In an embodiment, the material of described cathode layer is Ag, Al or Au therein, and thickness is 50～200nm.
A manufacture method for organic electroluminescence device, comprises the steps:
In the both sides of white glass plate, magnetron sputtering is prepared anti-reflective film respectively, obtain the antireflection composite bed that contains two-layer anti-reflective film, simultaneously in a side deposits conductive material of substrate, make anode layer, then by the folded anti-reflective film that is located at a side in described antireflection composite bed of the opposite side of described substrate and and this anti-reflective film between be provided with bright dipping space;
Adopt the mode of magnetron sputtering, on described anode layer, prepare short reduction layer, material selection SiGe and the In of magnetron sputtering
2o
3, ZnS, SnO
2or SiO
2according to the composite material of mass ratio 1:1;
On described short reduction layer, prepare successively the first hole injection layer, the first hole transmission layer, the first red light luminescent layer, the first green luminescence layer, blue light-emitting and the first electron transfer layer;
On described the first electron transfer layer, evaporation is prepared charge generation layer, and the material of described charge generation layer is MoO
3, V
2o
5, WO
3or ReO
3;
On described charge generation layer, prepare successively the second hole injection layer, the second hole transmission layer, the second red light luminescent layer, the second green luminescence layer, the second electron transfer layer and electron injecting layer;
On described electron injecting layer, evaporation is prepared cathode layer, obtains described organic electroluminescence device.
Above-mentioned organic electroluminescence device by under exiting surface, anti-reflective film being set, and arranges short reduction layer on anode layer, and the light extraction efficiency of whole device improves greatly.And above-mentioned manufacture method is easy, low for equipment requirements, can wide popularization and application.
Accompanying drawing explanation
Fig. 1 is the structural representation of the organic electroluminescence device of an execution mode.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments organic electroluminescence device and preparation method thereof is described in further detail below.
As shown in Figure 1, the organic electroluminescence device 100 of an execution mode comprises antireflection composite bed 110, substrate 120, anode layer 130, short reduction layer 140, the first organic luminescence function layer 150, charge generation layer 160, the second organic luminescence function layer 170 and the cathode layer 180 being cascading.
The anti-reflective film 114 that antireflection composite bed 110 comprises white glass plate 112 and is positioned at white glass plate 112 both sides.The material of anti-reflective film 114 is SiGe, and thickness is 10～20nm.
Substrate 120 be located at wherein on an anti-reflective film 114 and and this anti-reflective film 114 between be provided with bright dipping space.The material of substrate 120 is polyurethane.Substrate 120 near a side of antireflection composite bed 114 be provided with a plurality of be uniformly distributed and with substrate 120 integrated protruding 122.In the present embodiment, projection 122 is square, and thickness is 5～20 μ m, spacing 5～20 μ m between adjacent protrusion 122.Substrate 120 is provided with folded being located on antireflection composite bed 110 of a side of projection 122, thereby between the two, forms gap, and light can penetrate from this gap, and meanwhile, due to the existence of anti-reflective film 114, light extraction efficiency significantly improves.
Anode layer 130 is for covering the ITO layer of the thickness 100nm in substrate 120.
The material of short reduction layer 140 is the composite material that bi-material forms according to mass ratio 1:1, and wherein a kind of material is SiGe, and another kind is In
2o
3, ZnS, SnO
2or SiO
2.The thickness of short reduction layer 140 is 4～10nm.
The first organic luminescence function layer 150 is included in the first hole injection layer 151, the first hole transmission layer 152, the first red light luminescent layer 153, the first green luminescence layer 154, blue light-emitting 155 and the first electron transfer layer 156 being cascading on short reduction layer 140.
The material of the first hole injection layer 151 is the MoO for adulterating
3, WO
3, V
2o
5or ReO
3doping mass ratio according to 25～35% is entrained in N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] composite material that forms in the material of main part such as cyclohexane.Wherein, doping quality than data representation for the material that adulterates and the mass ratio of material of main part, below in like manner.The thickness of the first hole injection layer 151 is 10～15nm.
The material of the first hole transmission layer 152 is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane.The thickness of the first hole transmission layer 152 is 30～50nm.
The material of the first red light luminescent layer 153 is two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium, two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III), two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III), two [2-(2-fluorophenyl)-1, 3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III), two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) or three (1-phenyl-isoquinolin) and close iridium) doping mass ratio according to 0.5～2% is entrained in 4, 4', 4''-tri-(carbazole-9-yl) triphenylamine, 9, 9'-(1, 3-phenyl) two-9H-carbazole, 4, 4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4, 4'-benzidine, 1, 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane or 9, two (1-naphthyl) anthracenes of 10-) composite material forming in.The thickness of the first red light luminescent layer 153 is 10～30nm.
The material of the first green luminescence layer 154 is that three (2-phenylpyridines) close iridium, acetopyruvic acid two (2-phenylpyridine) iridium or three [2-(p-methylphenyl) pyridine] and close iridium (III) and be entrained in 4 according to 2～10% doping mass ratio, 4', 4''-tri-(carbazole-9-yl) triphenylamine, 9,9'-(1,3-phenyl) two-9H-carbazole, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine, 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] composite material that forms in two (1-naphthyl) anthracenes of cyclohexane or 9,10-.The thickness of the first green luminescence layer 154 is 10～30nm.
The material of blue light-emitting 155 comprises Blue-light emitting host material, blue light guest materials and charge generating material, Blue-light emitting host material is 4, 4'-bis-(9-carbazole) biphenyl, 9, 9'-(1, 3-phenyl) two-9H-carbazole, 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles of 6-, 2, two (3-(9H-carbazole-9-yl) phenyl) pyridines of 6-, 3, two (3-(9H-carbazole-9-yl) phenyl) pyridines or 1 of 5-, two (triphenyl silicon) benzene of 4--, blue light guest materials is two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium, three (2-(4', the fluoro-5 '-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium, two (4, 6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1, 2, 4-triazole) close iridium or two (4, 6-difluorophenyl pyridine) (5-(pyridine-2-yl)-tetrazolium) closes iridium), charge generating material is MoO
3, V
2o
5, WO
3or ReO
3, the mass ratio of Blue-light emitting host material, blue light guest materials and charge generating material is 1:5～20:5～10.The thickness of blue light-emitting 155 is 5～15nm.
The material of the first electron transfer layer 156 is 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene.The thickness of the first electron transfer layer 156 is 10～60nm.
The material of charge generation layer 160 is MoO
3, V
2o
5, WO
3or ReO
3, thickness is 5～30nm.
The second organic luminescence function layer 170 is included in the second hole injection layer 171, the second hole transmission layer 172, the second red light luminescent layer 173, the second green luminescence layer 174, the second electron transfer layer 175 and the electron injecting layer 176 being cascading on charge generation layer 160.
The material of the second hole injection layer 171 is MoO
3, WO
3, V
2o
5or ReO
3doping mass ratio according to 25～35% is entrained in N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] composite material that forms in cyclohexane.The thickness of the second hole transmission layer 171 is 10～15nm.
The material of the second hole transmission layer 172 is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane.The thickness of the second hole transmission layer 172 is 30～50nm.
The material of the second red light luminescent layer 173 is two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium, two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III), two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III), two [2-(2-fluorophenyl)-1, 3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III), two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) or three (1-phenyl-isoquinolin) and close iridium) doping mass ratio according to 0.5～2% is entrained in 4, 4', 4''-tri-(carbazole-9-yl) triphenylamine, 9, 9'-(1, 3-phenyl) two-9H-carbazole, 4, 4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4, 4'-benzidine, 1, 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane or 9, two (1-naphthyl) anthracenes of 10-) composite material forming in.The thickness of the second red light luminescent layer 173 is 10～30nm.
The material of the second green luminescence layer 174 is that three (2-phenylpyridines) close iridium, acetopyruvic acid two (2-phenylpyridine) iridium or three [2-(p-methylphenyl) pyridine] and close iridium (III) and be entrained in 4 according to 2～10% doping mass ratio, 4', 4''-tri-(carbazole-9-yl) triphenylamine, 9,9'-(1,3-phenyl) two-9H-carbazole, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine, 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] composite material that forms in two (1-naphthyl) anthracenes of cyclohexane or 9,10-.The thickness of the second green luminescence layer is 10～30nm.
The material of the second electron transfer layer 175 is 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene.The thickness of the second electron transfer layer 175 is 10～60nm.
The material of electron injecting layer 176 is Cs
2cO
3, CsF, CsN
3, Li
2cO
3, LiF or Li
2o is entrained in 4 according to 25～35% doping mass ratio, 7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole or 1, the composite material forming in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene.The thickness of electron injecting layer 176 is 20～40nm.
Cathode layer 180 is located on electron injecting layer 176.The material of cathode layer 180 is Ag, Al or Au, and thickness is 50～200nm.
This organic electroluminescence device 100 is by anti-reflective film 114 is set under exiting surface, and short reduction layer 140 is set on anode layer 130, and the light extraction efficiency of whole device 100 improves greatly.
In addition, present embodiment also provides a kind of manufacture method of organic electroluminescence device, comprises the steps:
Step 1: magnetron sputtering is prepared anti-reflective film respectively in the both sides of white glass plate, obtain the antireflection composite bed that contains two-layer anti-reflective film, simultaneously in a side deposits conductive material of substrate, make anode layer, then by the folded anti-reflective film that is located at a side in antireflection composite bed of the opposite side of substrate and and this anti-reflective film between be provided with bright dipping space.
In the present embodiment, the opposite side that is also included in substrate carries out micro-pattern textureization to be made, and substrate is dried and is processed to remove the step of water and air as far as possible at vacuum state.Wherein, micro-pattern textureization is made and is specifically adopted square tool, at the opposite side of substrate, produces and has a plurality of equally distributed square projections.The thickness of square projection is 5～20 μ m, spacing 5～20 μ m between adjacent protrusion.
Step 2: adopt the mode of magnetron sputtering, on anode layer, prepare short reduction layer, the composite material that the material selection bi-material of magnetron sputtering forms according to mass ratio 1:1, wherein a kind of material is SiGe, another kind of material is In
2o
3, ZnS, SnO
2or SiO
2.
Step 3: prepare successively the first hole injection layer, the first hole transmission layer, the first red light luminescent layer, the first green luminescence layer, blue light-emitting and the first electron transfer layer on short reduction layer.
The making of the first hole injection layer, the first hole transmission layer, the first red light luminescent layer, the first green luminescence layer, blue light-emitting and the first electron transfer layer mainly adopts the mode of vacuum evaporation.
Step 4: charge generation layer is prepared in vacuum evaporation on the first electron transfer layer, the material of charge generation layer is MoO
3, V
2o
5, WO
3or ReO
3.
Step 5: prepare successively the second hole injection layer, the second hole transmission layer, the second red light luminescent layer, the second green luminescence layer, the second electron transfer layer and electron injecting layer on charge generation layer.
The making of the second hole injection layer, the second hole transmission layer, the second red light luminescent layer, the second green luminescence layer, the second electron transfer layer and electron injecting layer mainly adopts the mode of vacuum evaporation.
Step 6: cathode layer is prepared in vacuum evaporation on electron injecting layer, obtains organic electroluminescence device.
Above-mentioned manufacture method is easy, low for equipment requirements, can wide popularization and application.
Be below specific embodiment part:
Embodiment 1:
A) choose there is high refractive index transparent polyurethane plastic as high refractive index layer.First the transparent ito anode of thickness 100nm is deposited on to the surface of polyurethane plastic, adopt square tool to carry out micro-pattern texture making on another surface of plastic film, on another surface of plastic film, making thickness is 5 μ m, and spacing is a plurality of equally distributed square projection of 5 μ m.
Choose a white glass plate, adopt the mode of vacuum sputtering at white glass plate two sides difference sputter one deck anti-reflective film, the material of anti-reflective film is SiGe, and base vacuum degree is 1 * 10
-5pa, thickness 20nm.
The side that plastic film is had to square projection is on the anti-reflective film of white glass plate one side, and micro-patterning texture structure has been connected on anti-reflective film, has produced space between the two.By the structure obtaining vacuumize 15min at 80 ℃, reduce remaining water and gas.
The making of short reduction layer: adopt the mode of magnetron sputtering to make short reduction layer on ito anode layer, short reduction layer material is SiGe and In
2o
3according to the composite material of mass ratio 1:1, base vacuum degree is 1 * 10
-5pa, thickness 10nm.
Adopt the mode of vacuum evaporation to be prepared as follows each layer:
B) preparation of the first hole injection layer: by MoO
3be doped in NPB as the first hole injection layer, doping content 30wt%(" wt " and represent mass concentration, below in like manner), thickness 12.5nm, vacuum degree 5 * 10
-5pa, evaporation rate
C) preparation of the first hole transmission layer: material adopts NPB, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 40nm.
D) preparation of the first red light luminescent layer: material of main part adopts TCTA, red guest material adopts Ir (MDQ)
2(acac); Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 20nm, the mass ratio of red guest material and material of main part is 1:100.
E) preparation of the first green luminescence layer: material of main part adopts TCTA, green guest material adopts Ir (ppy)
3; Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 20nm, the mass ratio of green guest material and material of main part is 6:100.
F) preparation of blue light-emitting: material of main part adopts CBP, blue guest material to adopt FIrpic, charge generating material to adopt MoO
3; Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 10nm, the mass ratio of material of main part, blue guest material and charge generating material is 100:12.5:7.5.
G) preparation of the first electron transfer layer: electron transport material is Bphen, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 35nm.
H) preparation of charge generation layer: adopt bipolarity charge generation layer MoO
3, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 17.5nm.
I) preparation of the second hole injection layer: by MoO
3be doped in NPB as the second hole injection layer doping content 30wt%, thickness 12.5nm, vacuum degree 5 * 10
-5pa, evaporation rate
J) preparation of the second hole transmission layer: material adopts NPB; Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 40nm.
K) preparation of the second red light luminescent layer: material of main part adopts TCTA, red guest material to adopt Ir (MDQ)
2(acac); Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 20nm, the mass ratio of red guest material and material of main part is 1:100.
L) preparation of the second green luminescence layer: material of main part adopts TCTA, green guest material to adopt Ir (ppy)
3; Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 20nm, the mass ratio of green guest material and material of main part is 6:100.
M) preparation of the second electron transfer layer: material is Bphen, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 35nm.
N) preparation of electron injecting layer: adopt that N-shaped is material doped to be entered in electron transport material to form electron injecting layer, N-shaped material is Cs
2cO
3, electron transport material adopts Bphen, the doping content 30wt% of N-shaped material in electron transport material, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 30nm.
O) preparation of cathode layer: metallic cathode adopts silver (Ag), and thickness is 125nm, vacuum degree 5 * 10
-5pa, evaporation rate
Embodiment 2:
A) choose there is high refractive index transparent polyurethane plastic as high refractive index layer.First the transparent ito anode of thickness 100nm is deposited on to the surface of polyurethane plastic, adopt square tool to carry out micro-pattern texture making on another surface of plastic film, on another surface of plastic film, making thickness is 10 μ m, and spacing is a plurality of equally distributed square projection of 10 μ m.
Choose a white glass plate, adopt the mode of vacuum sputtering at white glass plate two sides difference sputter one deck anti-reflective film, the material of anti-reflective film is SiGe, and base vacuum degree is 1 * 10
-5pa, thickness 20nm.
The side that plastic film is had to square projection is on the anti-reflective film of white glass plate one side, and micro-patterning texture structure has been connected on anti-reflective film, has produced space between the two.By the structure obtaining vacuumize 15min at 80 ℃, reduce remaining water and gas.
The making of short reduction layer: adopt the mode of magnetron sputtering to make short reduction layer on ito anode layer, the material selection SiGe of short reduction layer and ZnS are according to the composite material of mass ratio 1:1, and base vacuum degree is 1 * 10
-5pa, thickness 10nm.
Adopt the mode of vacuum evaporation to be prepared as follows each layer:
B) preparation of the first hole injection layer: by WO
3be doped in TCTA as the first hole injection layer doping content 25wt%, thickness 10nm, vacuum degree 5 * 10
-5pa, evaporation rate
C) preparation of the first hole transmission layer: material adopts TCTA, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 30nm.
D) preparation of the first red light luminescent layer: material of main part adopts mCP, red guest material adopts PQIr; Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 10nm, the mass ratio of red guest material and material of main part is 0.5:100.
E) preparation of the first green luminescence layer: material of main part adopts mCP, green guest material adopts Ir (ppy)
2(acac); Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 10nm, the mass ratio of green guest material and material of main part is 2:100.
F) preparation of blue light-emitting: material of main part adopts mCP, blue guest material to adopt Fir6, charge generating material to adopt V
2o
5; Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 5nm, the mass ratio of material of main part, blue guest material and charge generating material is 100:5:5.
G) preparation of the first electron transfer layer: electron transport material is BCP, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 10nm.
H) preparation of charge generation layer: adopt bipolarity charge generation layer V
2o
5, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 5nm.
I) preparation of the second hole injection layer: by WO
3be doped in TCTA as the second hole injection layer doping content 25wt%, thickness 10nm, vacuum degree 5 * 10
-5pa, evaporation rate
J) preparation of the second hole transmission layer: material adopts TCTA; Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 30nm.
K) preparation of the second red light luminescent layer: material of main part adopts mCP, red guest material to adopt PQIr; Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 10nm, the mass ratio of red guest material and material of main part is 0.5:100.
L) preparation of the second green luminescence layer: material of main part adopts mCP, green guest material to adopt Ir (ppy)
3(acac); Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 10nm, the mass ratio of green guest material and material of main part is 2:100.
M) preparation of the second electron transfer layer: material is BCP, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 10nm.
N) preparation of electron injecting layer: adopt that N-shaped is material doped to be entered in electron transport material to form electron injecting layer, N-shaped material is CsF, and electron transport material adopts BCP, the doping content 25wt% of N-shaped material in electron transport material, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 20nm.
O) preparation of cathode layer: metallic cathode adopts silver (Al), and thickness is 50nm, vacuum degree 5 * 10
-5pa, evaporation rate
Embodiment 3:
A) choose there is high refractive index transparent polyurethane plastic as high refractive index layer.First the transparent ito anode of thickness 100nm is deposited on to the surface of polyurethane plastic, adopt square tool to carry out micro-pattern texture making on another surface of plastic film, on another surface of plastic film, making thickness is 15 μ m, and spacing is a plurality of equally distributed square projection of 15 μ m.
Choose a white glass plate, adopt the mode of vacuum sputtering at white glass plate two sides difference sputter one deck anti-reflective film, the material of anti-reflective film is SiGe, and base vacuum degree is 1 * 10
-5pa, thickness 20nm.
The side that plastic film is had to square projection is on the anti-reflective film of white glass plate one side, and micro-patterning texture structure has been connected on anti-reflective film, has produced space between the two.By the structure obtaining vacuumize 15min at 80 ℃, reduce remaining water and gas.
The making of short reduction layer: adopt the mode of magnetron sputtering to make short reduction layer on ito anode layer, material selection SiGe and the SnO of short reduction layer
2according to the composite material of mass ratio 1:1, base vacuum degree is 1 * 10
-5pa, thickness 10nm.
Adopt the mode of vacuum evaporation to be prepared as follows each layer:
B) preparation of the first hole injection layer: by V
2o
5be doped in CBP as the first hole injection layer doping content 35wt%, thickness 15nm, vacuum degree 5 * 10
-5pa, evaporation rate
C) preparation of the first hole transmission layer: material adopts CBP, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 50nm.
D) preparation of the first red light luminescent layer: material of main part adopts CBP, red guest material adopts (fbi)
2ir (acac); Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 30nm, the mass ratio of red guest material and material of main part is 2:100.
E) preparation of the first green luminescence layer: material of main part adopts CBP, green guest material adopts Ir (mppy)
3; Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 30nm, the mass ratio of green guest material and material of main part is 10:100.
F) preparation of blue light-emitting: material of main part adopts CzSi, blue guest material to adopt FCNIr, charge generating material to adopt WO
3; Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 15nm, the mass ratio of material of main part, blue guest material and charge generating material is 100:20:10.
G) preparation of the first electron transfer layer: electron transport material is BAlq, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 60nm.
H) preparation of charge generation layer: adopt bipolarity charge generation layer WO
3, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 30nm.
I) preparation of the second hole injection layer: by V
2o
5be doped in CBP as the second hole injection layer doping content 35wt%, thickness 15nm, vacuum degree 5 * 10
-5pa, evaporation rate
J) preparation of the second hole transmission layer: material adopts CBP; Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 50nm.
K) preparation of the second red light luminescent layer: material of main part adopts CBP, red guest material adopts (fbi)
2ir (acac); Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 30nm, the mass ratio of red guest material and material of main part is 2:100.
L) preparation of the second green luminescence layer: material of main part adopts CBP, green guest material adopts Ir (mppy)
3; Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 30nm, the mass ratio of green guest material and material of main part is 10:100.
M) preparation of the second electron transfer layer: material is BAlq, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 60nm.
N) preparation of electron injecting layer: adopt that N-shaped is material doped to be entered in electron transport material to form electron injecting layer, N-shaped material is CsN
3, electron transport material adopts BAlq, the doping content 35wt% of N-shaped material in electron transport material, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 40nm.
O) preparation of cathode layer: metallic cathode adopts silver (Au), and thickness is 200nm, vacuum degree 5 * 10
-5pa, evaporation rate
Embodiment 4:
A) choose there is high refractive index transparent polyurethane plastic as high refractive index layer.First the transparent ito anode of thickness 100nm is deposited on to the surface of polyurethane plastic, adopt square tool to carry out micro-pattern texture making on another surface of plastic film, on another surface of plastic film, making thickness is 20 μ m, and spacing is a plurality of equally distributed square projection of 20 μ m.
Choose a white glass plate, adopt the mode of vacuum sputtering at white glass plate two sides difference sputter one deck anti-reflective film, the material of anti-reflective film is SiGe, and base vacuum degree is 1 * 10
-4pa, thickness 15nm.
The side that plastic film is had to square projection is on the anti-reflective film of white glass plate one side, and micro-patterning texture structure has been connected on anti-reflective film, has produced space between the two.By the structure obtaining vacuumize 15min at 80 ℃, reduce remaining water and gas.
The making of short reduction layer: adopt the mode of magnetron sputtering to make short reduction layer on ito anode layer, material selection SiGe and the SiO of short reduction layer
2according to the composite material of mass ratio 1:1, base vacuum degree is 1 * 10
-4pa, thickness 6nm.
Adopt the mode of vacuum evaporation to be prepared as follows each layer:
B) preparation of the first hole injection layer: by ReO
3be doped in TPD as the first hole injection layer doping content 30wt%, thickness 13nm, vacuum degree 5 * 10
-5pa, evaporation rate
C) preparation of the first hole transmission layer: material adopts TPD, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 40nm.
D) preparation of the first red light luminescent layer: material of main part adopts TPD, red guest material adopts (F-BT)
2ir (acac); Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 20nm, the mass ratio of red guest material and material of main part is 1:100.
E) preparation of the first green luminescence layer: material of main part adopts TPD, green guest material adopts Ir (ppy)
3; Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 20nm, the mass ratio of green guest material and material of main part is 5:100.
F) preparation of blue light-emitting: material of main part adopts 26DCzPPY, blue guest material to adopt FIrtaz, charge generating material to adopt ReO
3; Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 10nm, the mass ratio of material of main part, blue guest material and charge generating material is 100:12:7.
G) preparation of the first electron transfer layer: electron transport material is Alq
3, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 40nm.
H) preparation of charge generation layer: adopt bipolarity charge generation layer ReO
3, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 20nm.
I) preparation of the second hole injection layer: by ReO
3be doped in TPD as the second hole injection layer doping content 30wt%, thickness 12nm, vacuum degree 5 * 10
-5pa, evaporation rate
J) preparation of the second hole transmission layer: material adopts TPD, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 40nm.
K) preparation of the second red light luminescent layer: material of main part adopts TPD, red guest material adopts (F-BT)
2ir (acac); Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 20nm, the mass ratio of red guest material and material of main part is 1:100.
L) preparation of the second green luminescence layer: material of main part adopts TPD, green guest material adopts Ir (ppy)
3; Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 20nm, the mass ratio of green guest material and material of main part is 5:100.
M) preparation of the second electron transfer layer: electron transport material is Alq
3, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 30nm.
N) preparation of electron injecting layer: adopt that N-shaped is material doped to be entered in electron transport material to form electron injecting layer, N-shaped material is Li
2cO
3, electron transport material adopts Alq
3, the doping content 30wt% of N-shaped material in electron transport material, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 30nm.
O) preparation of cathode layer: metallic cathode adopts silver (Ag), and thickness is 100nm, vacuum degree 5 * 10
-5pa, evaporation rate
Embodiment 5:
A) choose there is high refractive index transparent polyurethane plastic as high refractive index layer.First the transparent ito anode of thickness 100nm is deposited on to the surface of polyurethane plastic, adopt square tool to carry out micro-pattern texture making on another surface of plastic film, on another surface of plastic film, making thickness is 11 μ m, and spacing is a plurality of equally distributed square projection of 11 μ m.
Choose a white glass plate, adopt the mode of vacuum sputtering at white glass plate two sides difference sputter one deck anti-reflective film, the material of anti-reflective film is SiGe, and base vacuum degree is 1 * 10
-5pa, thickness 15nm.
The side that plastic film is had to square projection is on the anti-reflective film of white glass plate one side, and micro-patterning texture structure has been connected on anti-reflective film, has produced space between the two.By the structure obtaining vacuumize 15min at 80 ℃, reduce remaining water and gas.
The making of short reduction layer: adopt the mode of magnetron sputtering to make short reduction layer on ito anode layer, material selection SiGe and the In of short reduction layer
2o
3according to the composite material of mass ratio 1:1, base vacuum degree is 1 * 10
-4pa, thickness 6nm.
Adopt the mode of vacuum evaporation to be prepared as follows each layer:
B) preparation of the first hole injection layer: by MoO
3be doped in TAPC as the first hole injection layer doping content 25wt%, thickness 10nm, vacuum degree 5 * 10
-5pa, evaporation rate
C) preparation of the first hole transmission layer: material adopts TAPC, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 40nm.
D) preparation of the first red light luminescent layer: material of main part adopts TAPC, red guest material adopts Ir (btp)
2(acac); Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 20nm, the mass ratio of red guest material and material of main part is 1:100.
E) preparation of the first green luminescence layer: material of main part adopts TAPC, green guest material adopts Ir (ppy)
2(acac); Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 20nm, the mass ratio of green guest material and material of main part is 7:100.
F) preparation of blue light-emitting: material of main part adopts 35DCzPPY, blue guest material to adopt FIrN4, charge generating material to adopt MoO
3; Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 10nm, the mass ratio of material of main part, blue guest material and charge generating material is 100:12:7.
G) preparation of the first electron transfer layer: electron transport material is TAZ, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 40nm.
H) preparation of charge generation layer: adopt bipolarity charge generation layer MoO
3, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 20nm.
I) preparation of the second hole injection layer: by MoO
3be doped in TAPC as the second hole injection layer doping content 28wt%, thickness 13nm, vacuum degree 5 * 10
-5pa, evaporation rate
J) preparation of the second hole transmission layer: material adopts TAPC, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 40nm.
K) preparation of the second red light luminescent layer: material of main part adopts TAPC, red guest material adopts Ir (btp)
2(acac); Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 20nm, the mass ratio of red guest material and material of main part is 1:100.
L) preparation of the second green luminescence layer: material of main part adopts TAPC, green guest material adopts Ir (ppy)
2(acac); Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 20nm, the mass ratio of green guest material and material of main part is 7:100.
M) preparation of the second electron transfer layer: electron transport material is TAZ, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 50nm.
N) preparation of electron injecting layer: adopt that N-shaped is material doped to be entered in electron transport material to form electron injecting layer, N-shaped material is LiF, and electron transport material adopts TAZ, the doping content 30wt% of N-shaped material in electron transport material, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 30nm.
O) preparation of cathode layer: metallic cathode adopts silver (Al), and thickness is 100nm, vacuum degree 5 * 10
-5pa, evaporation rate
Embodiment 6:
A) choose there is high refractive index transparent polyurethane plastic as high refractive index layer.First the transparent ito anode of thickness 100nm is deposited on to the surface of polyurethane plastic, adopt square tool to carry out micro-pattern texture making on another surface of plastic film, on another surface of plastic film, making thickness is 18 μ m, and spacing is a plurality of equally distributed square projection of 18 μ m.
Choose a white glass plate, adopt the mode of vacuum sputtering at white glass plate two sides difference sputter one deck anti-reflective film, the material of anti-reflective film is SiGe, and base vacuum degree is 1 * 10
-3pa, thickness 10nm.
The side that plastic film is had to square projection is on the anti-reflective film of white glass plate one side, and micro-patterning texture structure has been connected on anti-reflective film, has produced space between the two.By the structure obtaining vacuumize 15min at 80 ℃, reduce remaining water and gas.
The making of short reduction layer: adopt the mode of magnetron sputtering to make short reduction layer on ito anode layer, the material selection SiGe of short reduction layer and ZnS are according to the composite material of mass ratio 1:1, and base vacuum degree is 1 * 10
-3pa, thickness 4nm.
Adopt the mode of vacuum evaporation to be prepared as follows each layer:
B) preparation of the first hole injection layer: by WO
3be doped in NPB as the first hole injection layer doping content 30wt%, thickness 12nm, vacuum degree 5 * 10
-5pa, evaporation rate
C) preparation of the first hole transmission layer: material adopts NPB, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 40nm.
D) preparation of the first red light luminescent layer: material of main part adopts ADN, red guest material adopts Ir (piq)
3; Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 20nm, the mass ratio of red guest material and material of main part is 1:100.
E) preparation of the first green luminescence layer: material of main part adopts ADN, green guest material adopts Ir (mppy)
3; Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 20nm, the mass ratio of green guest material and material of main part is 6:100.
F) preparation of blue light-emitting: material of main part adopts UGH2, blue guest material to adopt FIrpic, charge generating material to adopt V
2o
5; Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 10nm, the mass ratio of material of main part, blue guest material and charge generating material is 100:12:7.
G) preparation of the first electron transfer layer: electron transport material is TPBI, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 40nm.
H) preparation of charge generation layer: adopt bipolarity charge generation layer V
2o
5, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 20nm.
I) preparation of the second hole injection layer: by WO
3be doped in NPB as the second hole injection layer doping content 30wt%, thickness 12nm, vacuum degree 5 * 10
-5pa, evaporation rate
J) preparation of the second hole transmission layer: material adopts NPB, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 40nm.
K) preparation of the second red light luminescent layer: material of main part adopts ADN, red guest material adopts Ir (piq)
3; Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 20nm, the mass ratio of red guest material and material of main part is 1:100.
L) preparation of the second green luminescence layer: material of main part adopts ADN, green guest material adopts Ir (mppy)
3; Vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 20nm, the mass ratio of green guest material and material of main part is 6:100.
M) preparation of the second electron transfer layer: electron transport material is TPBI, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 30nm.
N) preparation of electron injecting layer: adopt that N-shaped is material doped to be entered in electron transport material to form electron injecting layer, N-shaped material is Li
2o, electron transport material adopts TPBI, the doping content 30wt% of N-shaped material in electron transport material, vacuum degree 5 * 10
-5pa, evaporation rate
evaporation thickness 30nm.
O) preparation of cathode layer: metallic cathode adopts silver (Al), and thickness is 100nm, vacuum degree 5 * 10
-5pa, evaporation rate
Table 2 is the luminous efficiency test result of the organic electroluminescence device of embodiment 1-6 making, specific as follows:
Table 2
As can be seen from Table 2, the organic electroluminescence device that embodiment 1-6 makes is owing to adopting anti-reflective film and short reduction layer, and the luminous efficiency of whole device significantly improves.
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, is characterized in that, comprises the antireflection composite bed, substrate, anode layer, short reduction layer, the first organic luminescence function layer, charge generation layer, the second organic luminescence function layer and the cathode layer that are cascading; Wherein, the anti-reflective film that described antireflection composite bed comprises white glass plate and is positioned at described white glass plate both sides, described substrate be located at wherein on an anti-reflective film and and this anti-reflective film between be provided with bright dipping space; The material of described short reduction layer is SiGe and In
2o
3, ZnS, SnO
2or SiO
2according to the composite material of mass ratio 1:1; Described the first organic luminescence function layer is included in the first hole injection layer, the first hole transmission layer, the first red light luminescent layer, the first green luminescence layer, blue light-emitting and the first electron transfer layer being cascading on described short reduction layer; Described the second organic luminescence function layer is included in the second hole injection layer, the second hole transmission layer, the second red light luminescent layer, the second green luminescence layer, the second electron transfer layer and the electron injecting layer being cascading on described charge generation layer, and described cathode layer is located on described electron injecting layer.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, the material of described anti-reflective film is SiGe, and thickness is 10～20nm.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, the material of described substrate is polyurethane, described substrate near a side of described antireflection composite bed be provided with a plurality of be uniformly distributed and with the integrated projection of described substrate.
4. organic electroluminescence device as claimed in claim 3, is characterized in that, described projection is square, and thickness is 5～20 μ m, spacing 5～20 μ m between adjacent protrusion.
5. organic electroluminescence device as claimed in claim 1, is characterized in that, described anode layer is the ITO layer of thickness 100nm.
6. organic electroluminescence device as claimed in claim 1, is characterized in that, the material of described the first hole injection layer is MoO
3, WO
3, V
2o
5or ReO
3doping mass ratio according to 25～35% is entrained in N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] composite material that forms in cyclohexane;
The material of described the first hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane;
The material of described the first red light luminescent layer is two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium, two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III), two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III), two [2-(2-fluorophenyl)-1, 3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III), two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) or three (1-phenyl-isoquinolin) and close iridium) doping mass ratio according to 0.5～2% is entrained in 4, 4', 4''-tri-(carbazole-9-yl) triphenylamine, 9, 9'-(1, 3-phenyl) two-9H-carbazole, 4, 4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4, 4'-benzidine, 1, 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane or 9, two (1-naphthyl) anthracenes of 10-) composite material forming in,
The material of described the first green luminescence layer is that three (2-phenylpyridines) close iridium, acetopyruvic acid two (2-phenylpyridine) iridium or three [2-(p-methylphenyl) pyridine] and close iridium (III) and be entrained in 4 according to 2～10% doping mass ratio, 4', 4''-tri-(carbazole-9-yl) triphenylamine, 9,9'-(1,3-phenyl) two-9H-carbazole, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine, 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] composite material that forms in two (1-naphthyl) anthracenes of cyclohexane or 9,10-;
The material of described blue light-emitting comprises Blue-light emitting host material, blue light guest materials and charge generating material, described Blue-light emitting host material is 4, 4'-bis-(9-carbazole) biphenyl, 9, 9'-(1, 3-phenyl) two-9H-carbazole, 9-(4-2-methyl-2-phenylpropane base)-3, two (triphenyl the silicon)-9H-carbazoles of 6-, 2, two (3-(9H-carbazole-9-yl) phenyl) pyridines of 6-, 3, two (3-(9H-carbazole-9-yl) phenyl) pyridines or 1 of 5-, two (triphenyl silicon) benzene of 4--, described blue light guest materials is two (4, 6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, two (4, 6-difluorophenyl pyridine)-tetra-(1-pyrazolyl) boric acid closes iridium, three (2-(4', the fluoro-5 '-cyano group of 6'-bis-) phenylpyridine-N, C2') close iridium, two (4, 6-difluorophenyl pyridine)-(3-(trifluoromethyl)-5-(pyridine-2-yl)-1, 2, 4-triazole) close iridium or two (4, 6-difluorophenyl pyridine) (5-(pyridine-2-yl)-tetrazolium) closes iridium), described charge generating material is MoO
3, V
2o
5, WO
3or ReO
3, the mass ratio of described Blue-light emitting host material, described blue light guest materials and described charge generating material is 1:5～20:5～10,
The material of described the first electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene.
7. organic electroluminescence device as claimed in claim 1, is characterized in that, the material of described charge generation layer is MoO
3, V
2o
5, WO
3or ReO
3, thickness is 5～30nm.
8. organic electroluminescence device as claimed in claim 1, is characterized in that, the material of described the second hole injection layer is MoO
3, WO
3, V
2o
5or ReO
3doping mass ratio according to 25～35% is entrained in N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] composite material that forms in cyclohexane;
The material of described the second hole transmission layer is N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines, 4,4', 4''-tri-(carbazole-9-yl) triphenylamine, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine or 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane;
The material of described the second red light luminescent layer is two (2-methyl-diphenyl [f, h] quinoxaline) (acetylacetone,2,4-pentanedione) close iridium, two [2-phenylchinoline base)-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III), two [N-isopropyl-2-(4-fluorophenyl) benzimidazole] (acetylacetone,2,4-pentanediones) close iridium (III), two [2-(2-fluorophenyl)-1, 3-benzothiazole-N, C2] (acetylacetone,2,4-pentanedione) close iridium (III), two (2-benzothiophene-2-base-pyridine) (acetylacetone,2,4-pentanediones) close iridium (III) or three (1-phenyl-isoquinolin) and close iridium) doping mass ratio according to 0.5～2% is entrained in 4, 4', 4''-tri-(carbazole-9-yl) triphenylamine, 9, 9'-(1, 3-phenyl) two-9H-carbazole, 4, 4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4, 4'-benzidine, 1, 1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] cyclohexane or 9, two (1-naphthyl) anthracenes of 10-) composite material forming in,
The material of described the second green luminescence layer is that three (2-phenylpyridines) close iridium, acetopyruvic acid two (2-phenylpyridine) iridium or three [2-(p-methylphenyl) pyridine] and close iridium (III) and be entrained in 4 according to 2～10% doping mass ratio, 4', 4''-tri-(carbazole-9-yl) triphenylamine, 9,9'-(1,3-phenyl) two-9H-carbazole, 4,4'-bis-(9-carbazole) biphenyl, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-4,4'-benzidine, 1,1-bis-[4-[N, N '-bis-(p-tolyl) amino] phenyl] composite material that forms in two (1-naphthyl) anthracenes of cyclohexane or 9,10-;
The material of described the second electron transfer layer is 4,7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole or 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene;
The material of described electron injecting layer is Cs
2cO
3, CsF, CsN
3, Li
2cO
3, LiF or Li
2o is entrained in 4 according to 25～35% doping mass ratio, 7-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-Phen, 4-biphenyl phenolic group-bis-(2-methyl-oxine) close aluminium, oxine aluminium, 3-(biphenyl-4-yl)-5-(4-tert-butyl-phenyl)-4-phenyl-4H-1,2,4-triazole or 1, the composite material forming in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene.
9. organic electroluminescence device as claimed in claim 1, is characterized in that, the material of described cathode layer is Ag, Al or Au, and thickness is 50～200nm.
10. a manufacture method for organic electroluminescence device, is characterized in that, comprises the steps:
In the both sides of white glass plate, magnetron sputtering is prepared anti-reflective film respectively, obtain the antireflection composite bed that contains two-layer anti-reflective film, simultaneously in a side deposits conductive material of substrate, make anode layer, then by the folded anti-reflective film that is located at a side in described antireflection composite bed of the opposite side of described substrate and and this anti-reflective film between be provided with bright dipping space;
Adopt the mode of magnetron sputtering, on described anode layer, prepare short reduction layer, material selection SiGe and the In of magnetron sputtering
2o
3, ZnS, SnO
2or SiO
2according to the composite material of mass ratio 1:1;
On described short reduction layer, prepare successively the first hole injection layer, the first hole transmission layer, the first red light luminescent layer, the first green luminescence layer, blue light-emitting and the first electron transfer layer;
On described the first electron transfer layer, evaporation is prepared charge generation layer, and the material of described charge generation layer is MoO
3, V
2o
5, WO
3or ReO
3;
On described charge generation layer, prepare successively the second hole injection layer, the second hole transmission layer, the second red light luminescent layer, the second green luminescence layer, the second electron transfer layer and electron injecting layer;
On described electron injecting layer, evaporation is prepared cathode layer, obtains described organic electroluminescence device.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109473563A (en) * | 2017-09-08 | 2019-03-15 | 上海和辉光电有限公司 | A kind of OLED luminescent device |
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| CN102655219A (en) * | 2012-02-23 | 2012-09-05 | 京东方科技集团股份有限公司 | Multicolour OLED (organic light-emitting diode), multicolour OLED unit and display device |
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