CN104300092B - A kind of blue organic electroluminescent device and preparation method thereof - Google Patents
A kind of blue organic electroluminescent device and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims description 13
- 239000000463 material Substances 0.000 claims abstract description 162
- 230000004048 modification Effects 0.000 claims abstract description 57
- 238000006011 modification reaction Methods 0.000 claims abstract description 57
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 229910052741 iridium Inorganic materials 0.000 claims description 100
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 99
- 238000001704 evaporation Methods 0.000 claims description 68
- 229910052799 carbon Inorganic materials 0.000 claims description 66
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 58
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 50
- 150000001875 compounds Chemical group 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
- HKEWOTUTAYJWQJ-UHFFFAOYSA-N 2-(1H-pyrazol-5-yl)pyridine Chemical compound N1N=CC=C1C1=CC=CC=N1 HKEWOTUTAYJWQJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 16
- 239000004305 biphenyl Substances 0.000 claims description 16
- -1 acetylacetonato Phen Ketone Chemical class 0.000 claims description 15
- 235000010290 biphenyl Nutrition 0.000 claims description 15
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1H-imidazole Chemical class C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 11
- UEMGWPRHOOEKTA-UHFFFAOYSA-N 1,3-difluorobenzene Chemical compound FC1=CC=CC(F)=C1 UEMGWPRHOOEKTA-UHFFFAOYSA-N 0.000 claims description 10
- 150000003222 pyridines Chemical class 0.000 claims description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 8
- 229910052775 Thulium Inorganic materials 0.000 claims description 8
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 7
- 238000004020 luminiscence type Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- DUXRDJNQKDYVNE-UHFFFAOYSA-N 2-[5-(trifluoromethyl)-1H-pyrazol-3-yl]pyridine Chemical compound N1C(C(F)(F)F)=CC(C=2N=CC=CC=2)=N1 DUXRDJNQKDYVNE-UHFFFAOYSA-N 0.000 claims description 6
- 229910000090 borane Inorganic materials 0.000 claims description 6
- QXYQHKYVTVSQQH-UHFFFAOYSA-N pyrazol-1-ylboron Chemical compound [B]N1C=CC=N1 QXYQHKYVTVSQQH-UHFFFAOYSA-N 0.000 claims description 6
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 6
- 230000036536 Cave Effects 0.000 claims description 5
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 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 4
- 150000008048 phenylpyrazoles Chemical class 0.000 claims description 4
- AKQNYQDSIDKVJZ-UHFFFAOYSA-N triphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 AKQNYQDSIDKVJZ-UHFFFAOYSA-N 0.000 claims description 4
- NEKVEYIDGCSSOC-UHFFFAOYSA-N C1=CC=CC=2C3=CC=CC=C3NC12.O1C=CC=C1 Chemical compound C1=CC=CC=2C3=CC=CC=C3NC12.O1C=CC=C1 NEKVEYIDGCSSOC-UHFFFAOYSA-N 0.000 claims description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000003851 azoles Chemical class 0.000 claims description 3
- 125000006267 biphenyl group Chemical group 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 150000003216 pyrazines Chemical class 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 125000006617 triphenylamine group Chemical class 0.000 claims description 3
- 125000004215 2,4-difluorophenyl group Chemical group [H]C1=C([H])C(*)=C(F)C([H])=C1F 0.000 claims description 2
- LOIBXBUXWRVJCF-UHFFFAOYSA-N 4-(4-aminophenyl)-3-phenylaniline Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1C1=CC=CC=C1 LOIBXBUXWRVJCF-UHFFFAOYSA-N 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- SEPPVOUBHWNCAW-FNORWQNLSA-N (E)-4-oxonon-2-enal Chemical compound CCCCCC(=O)\C=C\C=O SEPPVOUBHWNCAW-FNORWQNLSA-N 0.000 claims 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N Phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 13
- 230000005540 biological transmission Effects 0.000 abstract description 9
- 239000000969 carrier Substances 0.000 abstract description 6
- 238000001228 spectrum Methods 0.000 abstract description 5
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 3
- 150000002910 rare earth metals Chemical class 0.000 abstract description 3
- 230000001808 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- 230000005525 hole transport Effects 0.000 abstract 1
- 238000010348 incorporation Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 250
- 239000011799 hole material Substances 0.000 description 106
- PQXKHYXIUOZZFA-UHFFFAOYSA-M Lithium fluoride Chemical group [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 26
- 238000005401 electroluminescence Methods 0.000 description 19
- SOROUYSPFADXSN-SUWVAFIASA-N Talampicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(=O)OC2C3=CC=CC=C3C(=O)O2)(C)C)=CC=CC=C1 SOROUYSPFADXSN-SUWVAFIASA-N 0.000 description 13
- 238000007740 vapor deposition Methods 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 125000005595 acetylacetonate group Chemical group 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 230000005611 electricity Effects 0.000 description 8
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 8
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 8
- 210000002381 Plasma Anatomy 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 238000000608 laser ablation Methods 0.000 description 7
- 238000001883 metal evaporation Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000004506 ultrasonic cleaning Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910015621 MoO Inorganic materials 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 230000005281 excited state Effects 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229910016460 CzSi Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000005283 ground state Effects 0.000 description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- SMWDFEZZVXVKRB-UHFFFAOYSA-N quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 3
- 235000010384 tocopherol Nutrition 0.000 description 3
- 235000019731 tricalcium phosphate Nutrition 0.000 description 3
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 2
- OEDUIFSDODUDRK-UHFFFAOYSA-N 5-phenyl-1H-pyrazole Chemical compound N1N=CC=C1C1=CC=CC=C1 OEDUIFSDODUDRK-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 230000003287 optical Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 230000001235 sensitizing Effects 0.000 description 2
- ZNXYMQNTSZXWLG-UHFFFAOYSA-N 2-(2,4-difluorobenzene-6-id-1-yl)pyridine;iridium;pyridine-2-carboxylic acid Chemical compound [Ir].OC(=O)C1=CC=CC=N1.FC1=CC(F)=C[C-]=C1C1=CC=CC=N1.FC1=CC(F)=C[C-]=C1C1=CC=CC=N1 ZNXYMQNTSZXWLG-UHFFFAOYSA-N 0.000 description 1
- PNPLRTWSLDSFET-UHFFFAOYSA-N 2-naphthalen-1-yl-5-phenyl-1,3,4-oxadiazole Chemical compound C1=CC=CC=C1C1=NN=C(C=2C3=CC=CC=C3C=CC=2)O1 PNPLRTWSLDSFET-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N Benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 240000007871 Indigofera tinctoria Species 0.000 description 1
- 101700009459 VNPB Proteins 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000051 modifying Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052904 quartz Inorganic materials 0.000 description 1
- 230000001105 regulatory Effects 0.000 description 1
- 230000000630 rising Effects 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000002520 smart material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a kind of blue organic electroluminescent device, its by substrate, anode layer, anode modification layer, hole transport electronic barrier layer, luminescent layer is dominated in hole, electronics dominates luminescent layer, hole barrier electron transfer layer, cathodic modification layer set gradually with cathode layer and to form；Wherein said electronics is dominated luminescent layer and is made up of with electron type organic host material organic sensitized material, blue organic luminous material.The application is by selecting the rare earth compounding of energy levels coupling, such as Tm (acac)3Phen or Dy (acac)3Phen is as organic sensitized material, its trace incorporation electronics is dominated in luminescent layer, play carrier and deeply fetter center and the effect of energy transmission ladder, thus improve the luminous efficiency of device, improve the spectrum stability of device, the running voltage of reduction device, the efficiency decay delaying device and the working life of raising device.
Description
Technical field
The present invention relates to technical field of organic electroluminescence, particularly relate to a kind of blue organic and cause
Luminescent device and preparation method thereof.
Background technology
Organic electroluminescence device is a kind of selfluminous element, and its principle of luminosity is: when electric charge quilt
During the organic layer being injected between hole injecting electrode and electron injection electrode, electronics and hole phase
Meet, combine and bury in oblivion subsequently, thus produce light.Organic electroluminescence device have low-voltage,
The characteristic such as high brightness, wide viewing angle, therefore organic electroluminescence device has obtained swift and violent in recent years
Development.Wherein, blue organic electroluminescent device owing to showing in monochrome, the side such as white light modulation
Mask has broad application prospects, and therefore becomes the focus of research.
All the time, trivalent complex of iridium is owing to having that luminous efficiency is high and glow color is adjustable etc.
Advantage and be considered as preferable electroluminescent organic material by academia and industrial circle.Both domestic and external permitted
Many research teams set about in terms of materials synthesis and device optimization, and blue organic to be improved causes to send out
The combination property of optical device, to meet the needs of industrialization.Such as, U.S. Pu Linsi in 2003
S.R.Forrest of university et al. uses the complex of iridium FIrpic with blue emission as sending out
Luminescent material, prepares organic electroluminescence device by the method for doping.Although this device shows
Preferably blue-light-emitting, but unbalanced carrier injects and causes the efficiency of device and brightness relatively
Low, additionally the running voltage of device is higher.
In order to solve these problems, 2008, Franky So of good fortune Flo-Rida-Low university of the U.S. et al.
By high efficiency complex of iridium being mixed the indigo plant having prepared multiple structure in preferred material of main part
Color organic electroluminescence device.This device has a higher maximum luminous efficiency, but device
Electric current density is relatively low, and luminous efficiency promptly decays along with the raising of electric current density, thus
The brightness causing device is relatively low, running voltage is higher；It addition, the device architecture of complexity also results in
The cost of manufacture of device is higher.As can be seen here, blue organic electroluminescent device luminous efficiency,
The combination properties such as brightness, spectrum stability and heat stability are not the most effectively improved.
Summary of the invention
Present invention solves the technical problem that and be to provide the blueness that a kind of combination property is higher organic
Electroluminescent device and preparation method thereof.
In view of this, this application provides a kind of blue organic electroluminescent device, including:
Substrate；
It is compound in the anode layer on described substrate；
The anode modification layer being compound on described anode layer；
It is compound in the hole transport-electronic barrier layer on described anode modification layer；
Luminescent layer is dominated in the hole being compound on described hole transport-electronic barrier layer；
It is compound in the electronics dominating on luminescent layer in described hole and dominates luminescent layer；
It is compound in hole barrier-electron transfer layer that described electronics is dominated on luminescent layer；
It is compound in the cathodic modification layer on described hole barrier-electron transfer layer；
It is compound in the cathode layer on described cathodic modification layer；
Described electronics dominates luminescent layer by organic sensitized material, blue organic luminous material and electronics
Type organic host material forms；
Described organic sensitized material closes thulium and three (acetyl selected from tri acetylacetonato Phen
Acetone) Phen closes one or both in dysprosium；
Described organic sensitized material is the 0.1wt%～0.5 of described electron type organic host material
Wt%.
Preferably, the content of described blue organic luminous material is described electron type organic main body material
8.0wt%～25.0wt% of material.
Preferably, described blue organic luminous material is selected from double (3,5-bis-fluoro-4-cyano group) pyridines
Hydrochloric acid closes iridium, double (2,4 difluorobenzene yl pyridines) four (1-pyrazolyl) boron closes iridium, three (1-
Phenyl-3-methyl benzo miaow is rattled away oxazoline-2-base-C, C2 ') close iridium, three (1-phenyl-3-methyl benzos
Miaow is rattled away oxazoline-2-base-C, C2 ') close iridium, double (2,4 difluorobenzene yl pyridines) (5-(pyridine-2-
Base)-1H-TETRAZOLE) close iridium, three [(2,6-diisopropyl phenyl) 2-phenyl-1H-imidazoles [e]
Close iridium, three (1-phenyl-3-methyl miaows rattle away oxazoline-2-base-C, C (2) ') close iridium, three (1-phenyl-3-
Methyl miaow is rattled away oxazoline-2-base-C, C (2) ') close iridium, double (1-phenyl-3 methyl miaow rattle away oxazoline-2-base-
C,C2') (2-(2H-pyrazole-3-yl)-pyridine) conjunction iridium, double (1-(4-aminomethyl phenyl)-3-methyl miaow
Oxazoline of rattling away-2-base-C, C2') (2-(2H-pyrazole-3-yl)-pyridine) conjunction iridium, double (1-(4-fluorophenyl)
-3-methyl miaow is rattled away oxazoline-2-base-C, C2') (2-(2H-pyrazole-3-yl)-pyridine) conjunction iridium, double (1-(4-
Fluorophenyl)-3-methyl miaow rattles away oxazoline-2-base-C, C2') (2-(5-trifluoromethyl-2H-pyrazole-3-yl)-
Pyridine) close iridium, three (1,3-diphenyl-benzimidazolyl-2 radicals-base-C, C2') close iridium, double (1-(4-
Fluorophenyl)-3-methyl miaow rattles away oxazoline-2-base-C, C2’) (3,5-dimethyl-2-(1H-pyrazoles-5-
Base) pyridine) close iridium, it is double that (1-(4-aminomethyl phenyl)-3-methyl miaow is rattled away oxazoline-2-base-C, C2’)
(3,5-dimethyl-2-(1H-pyrazoles-5-base) pyridine) closes iridium and three (Phenylpyrazoles) close in iridium
One or more.
Preferably, described electron type organic host material is selected from 2,6-bis-[3-(9H-9-carbazyl)
Phenyl] pyridine, 1,4-double (tri-phenyl-silane base) benzene, 2,2 '-bis-(4-(9-carbazyl) phenyl)
Biphenyl, three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine, 1,3,5-tri-[(3-pyrroles
Pyridine)-3-phenyl] benzene, 1,3-double [3,5-bis-(3-pyridine radicals) phenyl] benzene, 1,3,5-tri-(1-phenyl
-1H-benzimidazolyl-2 radicals-yl) benzene, double (triphenyl the is silica-based)-9H-of 9-(4-t-butyl-phenyl)-3,6-
One or many in carbazole and 9-(8-diphenylphosphoryl)-hexichol azoles [b, d] furan-9H-carbazole
Kind.
Preferably, to dominate luminescent layer organic by blue organic luminous material and cavity type in described hole
Material of main part forms；Described blue organic luminous material is described cavity type organic host material
8.0wt%～25.0wt%；
Described blue organic luminous material selected from double (3,5-bis-fluoro-4-cyano group) pyridine hydrochloric acid close iridium,
Double (2,4 difluorobenzene yl pyridines) four (1-pyrazolyl) boron closes iridium, three (1-phenyl-3-methyl
Benzo miaow is rattled away oxazoline-2-base-C, C2 ') close iridium, three (1-phenyl-3-methyl benzo miaow is rattled away oxazoline-2-
Base-C, C2 ') close iridium, double (2,4 difluorobenzene yl pyridines) (5-(pyridine-2-base)-1H-four
Azoles) close iridium, three [(2,6-diisopropyl phenyl) 2-phenyl-1H-imidazoles [e] closes iridium, three (1-
Phenyl-3-methyl miaow is rattled away oxazoline-2-base-C, C (2) ') close iridium, three (1-phenyl-3-methyl miaow is rattled away azoles
Quinoline-2-base-C, C (2) ') close iridium, it is double that (1-phenyl-3 methyl miaow is rattled away oxazoline-2-base-C, C2')(2-(2H-
Pyrazole-3-yl)-pyridine) close iridium, double (1-(4-aminomethyl phenyl)-3-methyl miaow rattle away oxazoline-2-base-
C,C2') (2-(2H-pyrazole-3-yl)-pyridine) closes iridium, double (1-(4-fluorophenyl)-3-methyl miaow is rattled away
Oxazoline-2-base-C, C2') (2-(2H-pyrazole-3-yl)-pyridine) conjunction iridium, double (1-(4-fluorophenyl)-3-
Methyl miaow is rattled away oxazoline-2-base-C, C2') (2-(5-trifluoromethyl-2H-pyrazole-3-yl)-pyridine) conjunction iridium,
Three (1,3-diphenyl-benzimidazolyl-2 radicals-base-C, C2') close iridium, double (1-(4-fluorophenyl)-3-
Methyl miaow is rattled away oxazoline-2-base-C, C2’) (3,5-dimethyl-2-(1H-pyrazoles-5-base) pyridine) conjunction
Iridium, double (1-(4-aminomethyl phenyl)-3-methyl miaow is rattled away oxazoline-2-base-C, C2’) (3,5-diformazan
Base-2-(1H-pyrazoles-5-base) pyridine) close the one or many in iridium and three (Phenylpyrazoles) conjunction iridium
Kind；
Described cavity type organic host material is selected from 4,4 '-N, N '-two carbazole diphenyl, 1,3-
Two carbazole-9-base benzene, 9,9'-(5-(tri-phenyl-silane base)-1,3-phenyl) two-9H-carbazoles, 1,3,5-
Three (9-carbazyl) benzene, 4,4', 4 "-three (carbazole-9-base) triphenylamines and 1,4-pair (tri-phenyl-silane bases)
One or more in biphenyl.
Preferably, the material of described hole transport-electronic barrier layer is selected from 4,4'-cyclohexyl two
[N, N-bis-(4-aminomethyl phenyl) aniline], two pyrazines [2,3-f:2 ', 3 '-h] quinoxaline-2,3,6,7,
10,11-six itrile groups, N4, N4'-bis-(naphthalene-1-base)-N4, N4'-double (4-ethenylphenyl) connection
Benzene-4,4'-diamidogen, N, double (phenyl)-2 of double (3-the aminomethyl phenyl)-N, N'-of N'-, 7-diamidogen-9,
9-spiro-bisfluorene, N, N, N', N'-tetra--(3-aminomethyl phenyl)-3-3 '-dimethyl benzidine,
2,2'-bis-(3-(N, N-bis--p-totuidine base) phenyl) biphenyl, N, N'-bis-(naphthalene-2-base)-N, N'-
Two (phenyl) benzidine, N, N'-bis-(naphthalene-1 base)-N, N' diphenyl-2,7-diamino
Base-9,9-spiro-bisfluorene, N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-2,7-diaminourea-9,
9-dimethyl fluorene, N, N'-bis-(naphthalene-1-base)-N, N'-diphenyl-2,7-diaminourea-9,9-diformazan
Base fluorenes, N, N' bis-(3-aminomethyl phenyl)-N, N' diphenyl-2,7-diaminourea-9,9-diphenyl
Fluorenes, N, N'-bis-(naphthalene-1-base)-N, N'-diphenyl-2,7-diaminourea-9,9-diphenylfluorene, N, N'-
Two (naphthalene-1-base)-N, N'-diphenyl-2,2 '-tolidine, 2,2', 7,7'-tetra-(N, N-
Diphenyl amino)-2,7-diaminourea-9,9-spiro-bisfluorene, 9,9-bis-[4-(N, N dinaphthyl-2-base-amino)
Phenyl]-9H-fluorenes, 9,9-[4-(N-naphthalene-1 base-N-aniline)-phenyl]-9H-fluorenes, 2,2 '-two [N, N-
Two (4-phenyl) amino]-9,9-spiro-bisfluorene, 2,2 '-bis-(N, N-phenylamino)-9,9-spiro-bisfluorenes,
N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-diamidogen and 4,4 '-two [N-is (right
-tolyl)-N-phenyl-amino] one or more in diphenyl.
Preferably, the material of described hole barrier-electron transfer layer is selected from three [2,4,6-trimethyl-3-
(3-pyridine radicals) phenyl] borine, 1,3,5-tri-[(3-pyridine)-3-phenyl] benzene, 1,3-double [3,5-
Two (3-pyridine radicals) phenyl] in benzene and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene one
Plant or multiple.
Preferably, the thickness of described anode modification layer is 1～10nm, described hole transport-electronics
The thickness on barrier layer is 30～60nm, and it is 5～20nm that the thickness of luminescent layer is dominated in described hole,
It is 5～20nm that described electronics dominates the thickness of luminescent layer, described hole barrier-electron transfer layer
Thickness is 30～60nm, and the thickness of described cathodic modification layer is 0.8～1.2nm, described cathode layer
Thickness be 90～300nm.
Present invention also provides the preparation method of a kind of blue organic electroluminescent device, including:
Anode layer on substrate is performed etching, on described anode layer, after drying, is deposited with sun successively
Pole decorative layer, hole transport-electronic barrier layer, luminescent layer is dominated in hole, electronics dominates luminescent layer,
Hole barrier-electron transfer layer, cathodic modification layer and cathode layer；
Described electronics dominates luminescent layer by organic sensitized material, blue organic luminous material and electronics
Type organic host material forms；
Described organic sensitized material closes thulium and three (acetyl selected from tri acetylacetonato Phen
Acetone) Phen closes one or both in dysprosium；
Described organic sensitized material is the 0.1wt%～0.5 of described electron type organic host material
Wt%.
Preferably, the evaporation rate of described anode modification layer is 0.01～0.05nm/s, described sky
Cave transmission-electronic barrier layer, hole dominate luminescent layer, electronics dominates luminescent layer and hole barrier-
In electron transfer layer, the evaporation rate of material of main part is 0.05～0.1nm/s, and described electronics is leading to be sent out
The evaporation rate of the organic sensitized material in photosphere is 0.00005～0.0005nm/s, described electronics
The evaporation rate that the blue emitting material in luminescent layer is dominated in leading luminescent layer and hole is
0.004～0.025nm/s, the evaporation rate of described cathodic modification layer is 0.005～0.05nm/s, institute
The evaporation rate stating cathode layer is 0.5～2.0nm/s.
This application provides a kind of blue organic electroluminescent device, it include substrate, anode layer,
Luminescent layer, the leading luminescence of electronics are dominated in anode modification layer, hole transport-electronic barrier layer, hole
Layer, hole barrier-electron transfer layer, cathodic modification layer and cathode layer.The luminescent material of the application
For blue emitting material, when electronics and hole are injected separately into luminescent layer, electronics and hole meeting
Meeting and be combined, and then producing an exciton, exciton can pass to energy in luminescent layer
The molecule of blue emitting material, excite an electronics to pass through to excited state, the electronics of excited state
A blue photon can be produced when the mode of radiation transistion returns to ground state, so that organic electroluminescence
Luminescent device blue light-emitting.
The application has tri acetylacetonato neighbour's Féraud by adding in dominating luminescent layer at electronics
One or both in quinoline conjunction thulium and tri acetylacetonato Phen conjunction dysprosium are as there being Smart
Material so that it is energy level and triplet energies and material of main part, the energy level of luminescent material and triplet
Energy matches, and makes organic sensitized material play during electroluminescent during carrier fetters deeply
The heart and the effect of energy transmission ladder, can not only improve the energy from material of main part to luminescent material
Amount transmission, it is possible to the distribution of equilbrium carrier, widen the luminous interval of device, thus improve and have
The luminous efficiency of organic electroluminescence devices, the spectrum stability of raising device, the work of reduction device
Make voltage, delay the efficiency of device to decay, improve the working life of device.
Accompanying drawing explanation
Fig. 1 is the structural representation of blue organic electroluminescent device of the present invention；
Fig. 2 is the voltage-to-current of the blue organic electroluminescent device of the embodiment of the present invention 1 preparation
Density-luminosity response figure；
Fig. 3 is the electric current density of the blue organic electroluminescent device of the embodiment of the present invention 1 preparation
-power efficiency-current efficiency characteristics curve chart；
Fig. 4 is that the blue organic electroluminescent device of the embodiment of the present invention 1 preparation is in brightness
20000cd/m2Time spectrogram.
Detailed description of the invention
In order to be further appreciated by the present invention, below in conjunction with embodiment to the preferred embodiment of the invention
It is described, but it is to be understood that these describe simply as further illustrating inventive feature
With advantage rather than limiting to the claimed invention.
The embodiment of the invention discloses a kind of blue organic electroluminescent device, including:
Substrate；
It is compound in the anode layer on described substrate；
The anode modification layer being compound on described anode layer；
It is compound in the hole transport-electronic barrier layer on described anode modification layer；
Luminescent layer is dominated in the hole being compound on described hole transport-electronic barrier layer；
It is compound in the electronics dominating on luminescent layer in described hole and dominates luminescent layer；
It is compound in hole barrier-electron transfer layer that described electronics is dominated on luminescent layer；
It is compound in the cathodic modification layer on described hole barrier-electron transfer layer；
It is compound in cathode layer on described cathodic modification layer；
Described electronics dominates luminescent layer by organic sensitized material, blue organic luminous material and electronics
Type organic host material forms；
Described organic sensitized material closes thulium and three (acetyl selected from tri acetylacetonato Phen
Acetone) Phen closes one or both in dysprosium；
Described organic sensitized material is the 0.1wt%～0.5 of described electron type organic host material
Wt%.
The principle of luminosity of organic electroluminescence device (OLED) is under the driving of external voltage,
Electronics and hole by electrode injection meet in Organic substance, and transfer energy to organic light emission
Molecule so that it is excited, from ground state transition to excited state, when the molecule that is stimulated is from excited state
Radiation transistion when returning to ground state and produce luminescence phenomenon.This application provides a kind of blue organic
Electroluminescent device, its blue light-emitting is owing to the luminescent material used is blue emitting material,
When electronics and hole are injected separately into luminescent layer, electronics and hole can meet and be combined,
And then produce an exciton, exciton energy pass to blue emitting material in luminescent layer point
Son, excites an electronics to return to ground state by the way of transition to excited state, the electronics of excited state
Time can produce a blue photon, thus realize organic electroluminescence device blue light-emitting.
Herein described blue organic electroluminescent device by substrate, anode layer, anode modification layer,
Hole transport-electronic barrier layer, hole dominate luminescent layer, electronics dominates luminescent layer, hole barrier
-electron transfer layer, cathodic modification layer and cathode layer are sequentially connected with setting.The wherein leading luminescence in hole
Layer dominates, with electronics, the luminescent layer that luminescent layer is blue organic electronic luminescent device.
The electronics of the present invention dominate luminescent layer by organic sensitized material, blue organic luminous material with
Electron type organic host material forms, and the most organic sensitized material plays during electroluminescent
The effect of sensitization, with improve from material of main part to luminescent material energy transmission and balance electronic and
Hole is in luminous interval distribution；The molecular dispersion of blue organic luminous material is leading of electronics
As the centre of luminescence in photosphere；Electron type organic host material plays the effect of substrate, it is provided that electricity
Sub-transmittability.In electronics dominates luminescent layer, the energy level of described organic sensitized material and triple
State energy demand matches with material of main part, the energy level of luminescent material and triplet energies, ability
The energy from material of main part to luminescent material in luminous interval distribution and is accelerated in balance electronic and hole
Amount transmission, makes blue organic electroluminescent device have preferable combination property.Therefore, this Shen
Please by choosing luminescent material, described organic sensitized material have selected rare earth compounding, institute
State organic sensitized material to close selected from the tri acetylacetonato Phen with formula (Ⅸ) structure
Thulium (Tm (acac)3And there is tri acetylacetonato neighbour's Féraud of formula (Ⅹ) structure phen)
Quinoline closes dysprosium (Dy (acac)3Phen) one or both in；
The doping that heretofore described organic sensitized material is dominated in luminescent layer at described electronics is dense
Spend the performance to organic electroluminescence device to impact.If the doping of described organic sensitized material
Concentration is too low, and sensitization effect can be caused undesirable, if doping content is too high, can reduce Organic Electricity
The combination property of electroluminescence device.Therefore, described organic sensitized material is that described electron type is organic
0.1wt%～0.5wt% of material of main part, preferably 0.2wt%～0.3wt%.
According to the present invention, described electronics dominates blue organic luminous material described in luminescent layer for this
Luminescent material known to skilled person, the application has no particular limits, but in order to make
Illumination effect is more preferable, and described blue organic luminous material is preferably selected from having formula (II1) structure
Double (3,5-bis-fluoro-4-cyano group) pyridine hydrochloric acid closes iridium (FCNIrpic), has formula (II2) structure
Double (2,4 difluorobenzene yl pyridines) four (1-pyrazolyl) boron close iridium (Fir6), there is formula (II3)
Facial-three (the 1-phenyl-3-methyl benzo miaow rattle away oxazoline-2-base-C, C2 ') of structure closes iridium
(fac-Ir(pmb)3), there is formula (II4) meridional-three (1-phenyl-3-methyl benzo miaows of structure
Oxazoline of rattling away-2-base-C, C2 ') close iridium (mer-Ir (Pmb)3), there is formula (II5) structure double
(2,4 difluorobenzene yl pyridines) (5-(pyridine-2-base)-1H-TETRAZOLE) conjunction iridium (FIrN4),
There is formula (II6) facial-three [(2,6-diisopropyl phenyl) 2-phenyl-1H-imidazoles of structure
[e] closes iridium (fac-Ir (iprpmi)3), there is formula (II7) facial-three (1-phenyl-3-of structure
Methyl miaow is rattled away oxazoline-2-base-C, C (2) ') close iridium (fac-Ir (pmi)3), there is formula (II8) structure
Meridional-three (1-phenyl-3-methyl miaow rattle away oxazoline-2-base-C, C (2) ') close iridium (mer-Ir (pmi)3)、
There is formula (II9) (1-phenyl-3 methyl miaow is rattled away oxazoline-2-base-C, C for structure double2')(2-(2H-
Pyrazole-3-yl)-pyridine) close iridium ((pmi)2Ir (pypz)), there is formula (II10) double (1-of structure
(4-aminomethyl phenyl)-3-methyl miaow is rattled away oxazoline-2-base-C, C2') (2-(2H-pyrazole-3-yl)-pyridine)
Close iridium ((mpmi)2Ir (pypz)), there is formula (II11) double (1-(4-fluorophenyl)-3-of structure
Methyl miaow is rattled away oxazoline-2-base-C, C2') (2-(2H-pyrazole-3-yl)-pyridine) conjunction iridium
((fpmi)2Ir (pypz)), there is formula (II12) double (1-(4-fluorophenyl)-3-methyl of structure
Miaow is rattled away oxazoline-2-base-C, C2') (2-(5-trifluoromethyl-2H-pyrazole-3-yl)-pyridine) conjunction iridium
((fpmi)2Ir (tfpypz)), there is formula (II13) facial-three (1, the 3-diphenyl-benzene of structure
And imidazoles-2-base-C, C2') close iridium (fac-Ir (dpbic)3), there is formula (II14) double (1-of structure
(4-fluorophenyl)-3-methyl miaow is rattled away oxazoline-2-base-C, C2’) (3,5-dimethyl-2-(1H-pyrazoles
-5-base) pyridine) close iridium ((fpmi)2Ir (dmpypz)), there is formula (II15) double (1-of structure
(4-aminomethyl phenyl)-3-methyl miaow is rattled away oxazoline-2-base-C, C2’) (3,5-dimethyl-2-(1H-
Pyrazoles-5-base) pyridine) close iridium ((mpmi)2Ir (dmpypz)) and there is formula (II16) structure
Three (Phenylpyrazole) closes iridium (Ir (ppz)3One or more in)；
In electronics dominates luminescent layer, the doping content of described blue organic luminous material also can shadow
Ring the combination property of blue organic electroluminescent device.If mixing of described blue organic luminous material
Miscellaneous concentration is too low, then can cause that device efficiency is on the low side, excitation is undesirable, and doping content is too high
Luminescent material molecule then can be caused to reunite, form quencher molecule, finally reduce the comprehensive of device
Energy.Therefore, described electronics is dominated blue organic luminous material described in luminescent layer and is preferably described
8wt%～25wt% of electron type material of main part, more preferably 10wt%～20wt%.Described electricity
Subtype material of main part plays the effect of substrate in electronics dominates luminescent layer, it is provided that electric transmission energy
Power, the material that described electron type material of main part is well known to those skilled in the art, as preferably side
Case, described electron type material of main part is preferably selected from having the 2 of formula (XI) structure, 6-bis-[3-(9H-9-
Carbazyl) phenyl] pyridine (26DCzPPy), there is the double (triphenyl of 1,4-of formula (XII) structure
Silylation) benzene (UGH2), there are 2,2 '-bis-(4-(9-carbazyl) of formula (XIII) structure
Phenyl) biphenyl (BCBP), there is [2,4,6-trimethyl-3-(the 3-pyrrole of formula (XIV) structure
Piperidinyl) phenyl] borine (3TPYMB), there are 1,3,5-tri-[(3-of formula (XV) structure
Pyridine)-3-phenyl] benzene (TmPyPB), there is the double [3,5-bis-(3-of 1,3-of formula (XVI) structure
Pyridine radicals) phenyl] benzene (BmPyPhB), there is 1,3,5-tri-(the 1-benzene of formula (XVII) structure
Base-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi), there is 9-(4-spy's fourth of formula (XVIII) structure
Base phenyl) double (triphenyl is silica-based)-9H-carbazole (CzSi) of-3,6-and there is formula (XIX)
9-(8-diphenylphosphoryl)-hexichol azoles [b, the d] furan-9H-carbazole (DFCzPO) of structure
In one or more；
Luminescent layer is dominated in hole described herein to be had by blue organic luminous material and cavity type
Machine material of main part forms, wherein the leading luminescence in hole of the molecular dispersion of blue organic luminous material
As the centre of luminescence in Ceng.Described blue organic luminous material is dominated in luminescent layer in described hole
Preferably 8.0wt%～25.00wt% of described cavity type organic host material, more preferably 10.0
Wt%～20.0wt%；The doping content of described blue organic luminous material is too low, then can cause device
Part efficiency is on the low side, excitation is undesirable, and doping content is too high, can cause luminescent material micel
Poly-, form quencher molecule, the final combination property reducing device.Described cavity type material of main part
Play the effect of substrate, it is provided that cavity transmission ability.Luminescent layer is dominated in hole described herein
Described in blue organic luminous material be preferably selected from that there is formula (II1) double (3,5-difluoros of structure
-4-cyano group) pyridine hydrochloric acid close iridium (FCNIrpic), there is formula (II2) structure double (2,4-
Difluorophenyl pyridinato) four (1-pyrazolyl) boron close iridium (Fir6), there is formula (II3) structure
Facial-three (1-phenyl-3-methyl benzo miaow rattle away oxazoline-2-base-C, C2 ') closes iridium (fac-Ir (pmb)3)、
There is formula (II4) meridional-three (the 1-phenyl-3-methyl benzo miaow rattle away oxazoline-2-base-C, C2 ') of structure
Close iridium (merIr (Pmb)3), there is formula (II5) double (2,4 difluorobenzene base pyrroles of structure
Pyridine) (5-(pyridine-2-base)-1H-TETRAZOLE) close iridium (FIrN4), there is formula (II6) structure
Facial-three [(2,6-diisopropyl phenyl) 2-phenyl-1H-imidazoles [e] closes iridium
(fac-Ir(iprpmi)3), there is formula (II7) structure facial-three (1-phenyl-3-methyl miaow is rattled away
Oxazoline-2-base-C, C (2) ') close iridium (fac-Ir (pmi)3), there is formula (II8) structure meridional-
Three (1-phenyl-3-methyl miaows rattle away oxazoline-2-base-C, C (2) ') close iridium (mer-Ir (pmi)3), have
Formula (II9) (1-phenyl-3 methyl miaow is rattled away oxazoline-2-base-C, C for structure double2') (2-(2H-pyrazoles-3-
Base)-pyridine) close iridium ((pmi)2Ir (pypz)), there is formula (II10) double (1-(4-first of structure
Base phenyl)-3-methyl miaow rattles away oxazoline-2-base-C, C2') (2-(2H-pyrazole-3-yl)-pyridine) conjunction iridium
((mpmi)2Ir (pypz)), there is formula (II11) double (1-(4-fluorophenyl)-3-first of structure
Base miaow is rattled away oxazoline-2-base-C, C2') (2-(2H-pyrazole-3-yl)-pyridine) conjunction iridium
((fpmi)2Ir (pypz)), there is formula (II12) double (1-(4-fluorophenyl)-3-methyl of structure
Miaow is rattled away oxazoline-2-base-C, C2') (2-(5-trifluoromethyl-2H-pyrazole-3-yl)-pyridine) conjunction iridium
((fpmi)2Ir (tfpypz)), there is formula (II13) facial-three (1, the 3-diphenyl-benzene of structure
And imidazoles-2-base-C, C2') close iridium (fac-Ir (dpbic)3), there is formula (II14) double (1-of structure
(4-fluorophenyl)-3-methyl miaow is rattled away oxazoline-2-base-C, C2’) (3,5-dimethyl-2-(1H-pyrazoles
-5-base) pyridine) close iridium ((fpmi)2Ir (dmpypz)), there is formula (II15) double (1-of structure
(4-aminomethyl phenyl)-3-methyl miaow is rattled away oxazoline-2-base-C, C2’) (3,5-dimethyl-2-(1H-
Pyrazoles-5-base) pyridine) close iridium ((mpmi)2Ir (dmpypz)) and there is formula (II16) structure
Three (Phenylpyrazole) closes iridium (Ir (ppz)3One or more in)；
Described cavity type organic host material is preferably selected from 4, the 4 ' N with formula (III) structure,
N ' two carbazole diphenyl (CBP), there is the 1,3-bis-carbazole-9-base benzene of formula (IV) structure
(mCP), there is the 9,9'-(5-(tri-phenyl-silane base)-1,3-phenyl) of formula (V) structure
Two-9H-carbazoles (SimCP), have formula (VI) structure 1,3,5-tri-(9-carbazyl) benzene (TCP),
There is the 4,4' of formula (VII) structure, 4 " three (carbazole 9 base) triphenylamines (TcTa) and there is formula
(VIII) one or more in the 1,4-of structure double (tri-phenyl-silane base) biphenyl (BSB)；
According to the present invention, in described blue organic electroluminescent device, described substrate can be glass
Glass substrate, quartz substrate, multicrystalline silicon substrate, monocrystalline substrate or graphene film substrate, this
Application has no particular limits.Described anode layer is preferably selected from indium tin oxide (ITO), its face
Resistance is preferably 5～25 Ω.Described anode modification layer can reduce driving voltage, accelerates hole
Injecting, described anode modification layer preferably employs molybdenum oxide (MoO3)。
The effect of hole transport-electronic barrier layer described herein is transporting holes and stops electricity
Son.The material of described hole transport-electronic barrier layer is preferably selected from having formula (I1) structure
4,4'-cyclohexyl two [N, N bis-(4-aminomethyl phenyl) aniline] (TAPC), there is formula (I2) structure
Two pyrazines [2,3-f:2 ', 3 '-h] quinoxaline-2,3,6,7,10,11-six itrile groups (HAT-CN),
There is formula (I3) N4, N4'-bis-(naphthalene-1-the base)-N4, N4'-double (4-ethenylphenyl) of structure
Biphenyl-4,4'-diamidogen (VNPB), there is formula (I4) N, N'-double (3-aminomethyl phenyl) of structure
Double (phenyl)-2 of-N, N'-, 7-diamidogen-9,9-spiro-bisfluorene (Spiro-TPD), there is formula (I5)
The N of structure, N, N', N'-tetra--(3-aminomethyl phenyl)-3-3 '-dimethyl benzidine
(HMTPD), there is formula (I6) the 2,2'-bis-(3-(N, N-bis--p-totuidine base) of structure
Phenyl) biphenyl (3DTAPBP), there is formula (I7) N, N'-bis-(naphthalene-2-base) of structure
-N, N'-bis-(phenyl) benzidine (β-NPB), there is formula (I8) N, N'-of structure
Two (naphthalene-1 base)-N, N'-diphenyl-2,7-diaminourea-9,9-spiro-bisfluorene (Spiro-NPB),
There is formula (I9) N, N'-bis-(3-aminomethyl phenyl)-N, the N'-diphenyl-2,7-diaminourea of structure
-9,9-dimethyl fluorene (DMFL-TPD), there is formula (I10) N, N'-bis-(naphthalene-1-of structure
Base)-N, N'-diphenyl-2,7-diaminourea-9,9-dimethyl fluorene (DMFL-NPB), there is formula
(Ⅰ11) N, N'-bis-(3-aminomethyl phenyl)-N, N'-diphenyl-2 of structure, 7-diaminourea-9,
9-diphenylfluorene (DPFL-TPD), there is formula (I12) N, N'-bis-(naphthalene-1-base) of structure
-N, N'-diphenyl-2,7-diaminourea-9,9-diphenylfluorene (DPFL-NPB), there is formula (I13)
The N of structure, N'-bis-(naphthalene-1-base)-N, N'-diphenyl-2,2 '-tolidine
(α-NPD), there is formula (I14) 2,2', 7,7'-tetra-(N, N-the diphenyl amino)-2,7-of structure
Diaminourea-9,9-spiro-bisfluorene (Spiro-TAD), there is formula (I15) 9,9-bis-[4-(N, the N of structure
Dinaphthyl-2-base-amino) phenyl]-9H-fluorenes (NPAPF), there is formula (I16) structure 9,9-[4-(N-
Naphthalene-1 base-N-aniline)-phenyl]-9H-fluorenes (NPBAPF), there is formula (I17) structure 2,
2 '-two [N, N-bis-(4-phenyl) amino]-9,9-spiro-bisfluorene (2,2'-Spiro-DBP), there is formula
(Ⅰ18) structure 2,2 '-bis-(N, N-phenylamino)-9,9-spiro-bisfluorenes (Spiro-BPA), tool
There is formula (I19) N, N '-diphenyl-N, N '-(1-naphthyl)-1 of structure, 1 '-biphenyl-4,4 '-
Diamidogen (NPB) and there is formula (I20) 4,4 '-two [N-(p-tolyl)-N-phenyl of structure
-amino] one or more in diphenyl (TPD)；
It is to stop hole and transmit according to the effect of hole barrier-electron transfer layer of the present invention
Electronics, promotes the injection of electronics.The material of described hole barrier-electron transfer layer is preferably selected from tool
There is three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl] borine of formula (XIV) structure
(3TPYMB), there are 1,3,5-tri-[(3-pyridine)-3-phenyl] of formula (XV) structure
Benzene (TmPyMB), there is double [3,5-bis-(3-pyridine radicals) benzene of 1,3-of formula (XVI) structure
Base] benzene (BmPyPhB) and there is the 1,3,5-tri-(1-phenyl-1H-benzo of formula (XVII) structure
Imidazoles-2-base) one or more in benzene (TPBi)；
The effect of cathodic modification layer described herein is to reduce driving voltage, accelerates the note of electronics
Entering, described cathodic modification layer is preferably lithium fluoride.Described cathode layer is preferably aluminum.
The application to the material of described hole transport-electronic barrier layer, blue organic luminous material,
Hole organic host material, organic sensitized material, electron type organic host material and hole resistance
The source of the material of gear-electron transfer layer all has no particular limits, according to those skilled in the art
Known to mode prepare the most available.
Anode layer described herein and described cathode layer intersect and form the luminous zone of device,
In herein described blue organic electroluminescent device, the thickness of every layer is on the impact of described device also
It is the biggest, if thickness is on the low side, device efficiency decay can be caused to accelerate, if thickness is higher, can
Cause device operating voltages height, life-span low.The thickness of the most described anode modification layer is preferably
1～10nm, the thickness of hole transport-electronic barrier layer is preferably 30～60nm, and hole is leading to be sent out
The thickness of photosphere is preferably 5～20nm, and electronics is dominated the thickness of luminescent layer and is preferably 5～20nm,
The thickness of hole barrier-electron transfer layer is preferably 30～60nm, and the thickness of cathodic modification layer is excellent
Electing 0.8～1.2nm as, the thickness of cathode layer is preferably 90～300nm.
Present invention also provides the preparation method of described blue organic electroluminescent device, including:
Anode layer on substrate is performed etching, on described anode layer, after drying, is deposited with sun successively
Pole decorative layer, hole transport-electronic barrier layer, luminescent layer is dominated in hole, electronics dominates luminescent layer,
Hole barrier-electron transfer layer, cathodic modification layer and cathode layer；
Luminescent layer is dominated by blue organic luminous material and cavity type organic main body material in described hole
Material mixes；
Described electronics dominates luminescent layer by organic sensitized material, blue organic luminous material and electronics
Type organic host material forms；
Described organic sensitized material is luxuriant and rich with fragrance selected from the tri acetylacetonato neighbour with formula (Ⅸ) structure
Sieve quinoline closes thulium and the tri acetylacetonato Phen with formula (Ⅹ) structure closes in dysprosium
Plant or two kinds；
Described organic sensitized material is the 0.1wt%～0.5 of described electron type organic host material
Wt%；
According to the present invention, the preparation method of described blue organic electroluminescent device particularly as follows:
First by the electrode into strips of the anode layer laser ablation on substrate, the most successively with cleaning
Liquid, deionized water ultrasonic cleaning 10～20min also put into oven for drying；
Substrate after drying puts into pretreatment vacuum chamber, in the atmosphere that vacuum is 8～15 Pa
The lower voltage with 350～500V after processing its low-voltage plasma carrying out 1～10min turns it
Move on to organic vapor deposition room；
Treat that vacuum reaches 1～2 × 10-5During Pa, the most on the anode layer evaporation anode modification layer,
Hole transport-electronic barrier layer, hole dominate luminescent layer, electronics dominates luminescent layer, hole barrier
-electron transfer layer；The device being not fully complete is transferred to metal evaporation room, 4～6 × 10-5Pa's
Evaporation cathode decorative layer and metal cathode layer successively under vacuum.
During preparing blue organic electroluminescent device, the application is by controlling evaporation speed
Rate realizes the deposition of material.According to the present invention, described anode modification layer evaporation rate controls
0.01～0.05nm/s, hole transport-electronic barrier layer, hole dominate luminescent layer, electronics is dominated
In luminescent layer, hole barrier-electron transfer layer, the evaporation rate of material of main part controls 0.05～0.1
Nm/s, the evaporation rate of organic sensitized material controls 0.00005～0.0005nm/s, and blueness has
The evaporation rate of machine luminescent material controls 0.004～0.025nm/s, the evaporation of cathodic modification layer
Rate controlled is 0.005～0.05nm/s, and metal cathode layer evaporation rate controls 0.5～2.0
nm/s.When wherein luminescent layer is dominated in evaporation hole, wherein blue organic luminous material, cavity type
Organic host material evaporates in different evaporation sources simultaneously, by regulating and controlling the evaporation of bi-material
Speed makes blue organic luminous material and the weight ratio control of cavity type organic host material of doping
System is between 8.0%～25.0%；When evaporation electronics dominates luminescent layer, the most organic sensitized material,
Blue organic luminous material, electron type organic host material evaporate in different evaporation sources simultaneously,
Make organic sensitized material of doping and electron type organic by the evaporation rate of three kinds of materials of regulation and control
The mass ratio of material of main part controls between 0.1%～0.5% so that the blue organic light emission of doping
The mass ratio of material and electron type organic host material controls between 8.0%～25.0%.
This application provides a kind of blue organic electroluminescent device, described blue organic causes to send out
Electronics in optical device is dominated the rare earth of the energy level distribution selecting to have coupling in luminescent layer and is coordinated
Thing, such as Tm (acac)3Phen or Dy (acac)3Phen is as organic sensitized material, and it rises
Deeply fetter the distribution of the effect at center, beneficially equilbrium carrier to electronics, widen sending out of device
Light is interval, thus improves the luminous efficiency of device, the running voltage of reduction device, delays device
Efficiency decay, improve device working life；Further, described organic sensitized material has
The triplet energies joined, play energy transmission ladder effect, it is possible to accelerate from material of main part to
The energy transmission of luminescent material, alleviates the main body that luminescent material carrier capture scarce capacity causes
Material emission problem, thus improve the spectrum stability of device, reduce device performance to luminous material
The dependence of material doping content.
In order to be further appreciated by the present invention, the blueness provided the present invention below in conjunction with embodiment has
Organic electroluminescence devices and preparation method thereof is described in detail, and protection scope of the present invention is not subject to
The restriction of following example.
As it is shown in figure 1, the structural representation that Fig. 1 is blue organic electroluminescent device of the present invention,
Wherein 1 is glass substrate, and 2 is anode layer, and 3 is anode modification layer, and 4 is hole transport-electricity
Sub-barrier layer, 5 dominate luminescent layer for hole, and 6 dominate luminescent layer for electronics, and 7 is hole barrier
-electron transfer layer, 8 is cathodic modification layer, and 9 is metal cathode layer.
Embodiment 1
First by the ito anode layer laser ablation electrode into strips on ito glass, use the most successively
Cleanout fluid, deionized water ultrasonic cleaning 15min also put into oven for drying.Then after drying
Substrate puts into pretreatment vacuum chamber, with the voltage of 400V under the atmosphere that vacuum is 10 Pa
It is transferred into organic vapor deposition room after ito anode is carried out the low-voltage plasma process of 3min.
It is 1～2 × 10-in vacuum5In the organic vapor deposition room of Pa, it is deposited with 3nm the most successively
Thick MoO3TAPC hole transport-electronic barrier layer 4 that anode modification layer 3,40nm are thick,
Luminescent layer 5,10nm thickness are dominated in the hole of 10nm thickness FCNIrpic doping TcTa
Tm(acac)3The electronics of phen Yu FCNIrpic codope CzSi dominates luminescent layer 6 and 40nm
Thick TmPyPB hole barrier-electron transfer layer 7.It follows that the device being not fully complete is transferred
To metal evaporation room, 4～6 × 10-5LiF thick for 1.0nm it is deposited with cloudy under the vacuum of Pa
Pole decorative layer 8, is deposited with the thick metal of 120nm finally by special mask on LiF layer
Al cathode layer 9, being prepared as structure is ITO/MoO3/ TAPC/FCNIrpic (8%):
TcTa/Tm(acac)3Phen (0.2%): FCNIrpic (18%): CzSi/TmPyPB/LiF/Al's
Organic electroluminescence device.MoO in anode modification layer 33Evaporation rate control 0.01
Nm/s, in hole transport-electronic barrier layer 4, the evaporation rate of TAPC controls at 0.05nm/s,
Hole is dominated the evaporation rate of FCNIrpic and TcTa in luminescent layer 5 and is controlled respectively 0.004
Nm/s and 0.05nm/s, electronics dominates Tm (acac) in luminescent layer 63Phen, FCNIrpic and
The evaporation rate of CzSi controls at 0.0001nm/s, 0.009nm/s and 0.05nm/s respectively, empty
In cave stop-electron transfer layer 7, the evaporation rate of TmPyPB controls at 0.05nm/s, negative electrode
In decorative layer 8, the evaporation rate of LiF controls at 0.005nm/s, Al in metal cathode layer 9
Evaporation rate controls at 1.0nm/s.
As in figure 2 it is shown, the electricity that Fig. 2 is blue organic electroluminescent device prepared by the present embodiment
Piezo-electric current density-luminosity response, in Fig. 2, zero curve is the Current density-voltage song of device
Line, curve is the brightness-voltage curve of device, according to Fig. 2, the brightness of device along with
Electric current density and the rising of driving voltage and raise, the bright voltage that rises of device is 3.0 volts, at electricity
Pressure is 9.4 volts, electric current density is 426.61 milliamperes of every square centimeter of (mA/cm2) time device obtain
High-high brightness 22963 every square metre of (cd/m of candela2)。
As it is shown on figure 3, the electricity that Fig. 3 is blue organic electroluminescent device prepared by the present embodiment
Current density-power efficiency-current efficiency characteristics curve, according to Fig. 3, the maximum electricity of device
Stream efficiency is 38.25cd/A, and maximum power efficiency is 40.03lm/W.
As shown in Figure 4, the blue organic electroluminescent device that Fig. 4 provides for the present invention is in brightness
For 10000cd/m2Time spectrogram, according to Fig. 4, spectrum main peak is positioned at 462 nanometers.
Device chromaticity coordinates is (0.140,0.175).
Embodiment 2
First by the ito anode layer laser ablation electrode into strips on ito glass, use the most successively
Cleanout fluid, deionized water ultrasonic cleaning 15min also put into oven for drying.Then after drying
Substrate puts into pretreatment vacuum chamber, with the voltage of 400V under the atmosphere that vacuum is 10 Pa
It is transferred into organic vapor deposition room after ito anode is carried out the low-voltage plasma process of 3min.
It is 1～2 × 10 in vacuum-5In the organic vapor deposition room of Pa, it is deposited with 3nm the most successively
Thick MoO3TAPC hole transport-electronic barrier layer 4 that anode modification layer 3,40nm are thick,
Luminescent layer 5,10nm thickness are dominated in the hole of 10nm thickness FCNIrpic doping mCP
Tm(acac)3The electronics of phen Yu FCNIrpic codope 26DCzPPy dominate luminescent layer 6 and
TmPyPB hole barrier-electron transfer layer 7 that 40nm is thick.It follows that the device being not fully complete
It is transferred to metal evaporation room, 4～6 × 10-51.0nm thickness it is deposited with under the vacuum of Pa
LiF cathodic modification layer 8, is deposited with 120nm finally by special mask thick on LiF layer
Metal Al cathode layer 9, being prepared as structure is ITO/MoO3/ TAPC/FCNIrpic (10%):
mCP/Tm(acac)3Phen (0.2%): FCNIrpic (20%): 26DCzPPy/TmPyPB/LiF/Al
Organic electroluminescence device.MoO in anode modification layer 33Evaporation rate control 0.01
Nm/s, in hole transport-electronic barrier layer 4, the evaporation rate of TAPC controls at 0.05nm/s,
Hole is dominated the evaporation rate of FCNIrpic and mCP in luminescent layer 5 and is controlled respectively 0.005
Nm/s and 0.05nm/s, electronics dominates Tm (acac) in luminescent layer 63Phen, FCNIrpic and
The evaporation rate of 26DCzPPy controls respectively at 0.0001nm/s, 0.01nm/s and 0.05nm/s,
In hole barrier-electron transfer layer, the evaporation rate of TmPyPB controls at 0.05nm/s, negative electrode
In decorative layer, the evaporation rate of LiF controls the evaporation of Al in 0.005nm/s, metal cathode layer
Rate controlled is at 1.0nm/s.
The performance of blue organic electroluminescent device prepared by detection the present embodiment, experimental result table
Bright, under DC source drives, the blue light being positioned at 462 ran launched by device.Work as brightness
For 10000cd/m2Time, the chromaticity coordinates of device is (0.141,0.173)；Change along with running voltage
Changing, the chromaticity coordinates of device is almost unchanged.The bright voltage that rises of device is 3.0 volts, the maximum of device
Brightness is 21678cd/m2.The maximum current efficiency of device is 36.92cd/A, and peak power is imitated
Rate is 38.64lm/W.
Embodiment 3
First by the ito anode layer laser ablation electrode into strips on ito glass, use the most successively
Cleanout fluid, deionized water ultrasonic cleaning 15min also put into oven for drying.Then after drying
Substrate puts into pretreatment vacuum chamber, with the voltage of 400V under the atmosphere that vacuum is 10 Pa
It is transferred into organic vapor deposition room after ito anode is carried out the low-voltage plasma process of 3min.
It is 1～2 × 10 in vacuum-5In the organic vapor deposition room of Pa, it is deposited with 3nm the most successively
Thick MoO3TAPC hole transport-electronic barrier layer 4 that anode modification layer 3,40nm are thick,
Luminescent layer 5,10nm thickness are dominated in the hole of 10nm thickness FCNIrpic doping TcTa
Dy(acac)3The electronics of phen Yu FCNIrpic codope 26DCzPPy dominate luminescent layer 6 and
TmPyPB hole barrier-electron transfer layer 7 that 40nm is thick.It follows that the device being not fully complete
It is transferred to metal evaporation room, 4～6 × 10-51.0nm thickness it is deposited with under the vacuum of Pa
LiF cathodic modification layer 8, is deposited with 120nm finally by special mask thick on LiF layer
Metal Al cathode layer 9, being prepared as structure is ITO/MoO3/ TAPC/FCNIrpic (8%):
TcTa/Dy(acac)3Phen (0.3%): FCNIrpic (20%): 26DCzPPy/TmPyPB/LiF/Al
Organic electroluminescence device.MoO in anode modification layer 33Evaporation rate control 0.01
Nm/s, in hole transport-electronic barrier layer 4, the evaporation rate of TAPC controls at 0.05 nm/s,
Hole is dominated the evaporation rate of FCNIrpic and TcTa in luminescent layer 5 and is controlled respectively 0.004
Nm/s and 0.05nm/s, electronics dominates Dy (acac) in luminescent layer 63Phen, FCNIrpic and
The evaporation rate of 26DCzPPy controls respectively at 0.0003nm/s, 0.02nm/s and 0.1nm/s,
In hole barrier-electron transfer layer 7, the evaporation rate of TmPyPB controls at 0.05nm/s, cloudy
In pole decorative layer 8, the evaporation rate of LiF controls at 0.005nm/s, Al in metal cathode layer 9
Evaporation rate control at 1.0nm/s.
The performance of blue organic electroluminescent device prepared by detection the present embodiment, experimental result table
Bright, device, under DC source drives, launches the blue light being positioned at 462 ran.Work as brightness
For 10000cd/m2Time, the chromaticity coordinates of device is (0.140,0.176)；Change along with running voltage
Changing, the chromaticity coordinates of device is almost unchanged.The bright voltage that rises of device is 3.0 volts, the maximum of device
Brightness is 20892cd/m2.The maximum current efficiency of device is 37.78cd/A, and peak power is imitated
Rate is 39.54lm/W.
Embodiment 4
First by the ito anode layer laser ablation electrode into strips on ito glass, use the most successively
Cleanout fluid, deionized water ultrasonic cleaning 15min also put into oven for drying.Then after drying
Substrate puts into pretreatment vacuum chamber, with the voltage of 400V under the atmosphere that vacuum is 10 Pa
It is transferred into organic vapor deposition room after ito anode is carried out the low-voltage plasma process of 3min.
It is 1～2 × 10 in vacuum-5In the organic vapor deposition room of Pa, it is deposited with 5nm the most successively
Thick MoO3TAPC hole transport-electronic barrier layer 4 that anode modification layer 3,30nm are thick,
Luminescent layer 5,15nm thickness Tm (acac) are dominated in the hole of 15nm thickness FIr6 doping mCP3phen
The 3TPYMB that luminescent layer 6 and 35nm is thick is dominated with the electronics of FIr6 codope 26DCzPPy
Hole barrier-electron transfer layer 7.It follows that the device being not fully complete is transferred to metal evaporation room,
4～6 × 10-5The thick LiF cathodic modification layer 8 of 1.1nm it is deposited with, finally under the vacuum of Pa
On LiF layer, the thick metal Al cathode layer 9 of 250nm, system it is deposited with by special mask
Standby one-tenth structure is ITO/MoO3/ TAPC/FIr6 (10%): mCP/Tm (acac)3Phen (0.1%):
FIr6 (10%): the organic electroluminescence device of 26DCzPPy/3TPYMB/LiF/Al.Anode is repaiied
MoO in decorations layer 33Evaporation rate control at 0.05nm/s, hole transport-electronic barrier layer 4
The evaporation rate of middle TAPC controls at 0.06nm/s, hole dominate in luminescent layer 5 FIr6 and
The evaporation rate of mCP controls at 0.008nm/s and 0.08nm/s respectively, and electronics dominates luminescent layer
Tm (acac) in 63The evaporation rate of phen, FIr6 and 26DCzPPy controls respectively 0.0001
Nm/s, 0.01nm/s and 0.1nm/s, 3TPYMB in hole barrier-electron transfer layer 7
Evaporation rate controls at 0.08nm/s, and in cathodic modification layer 8, the evaporation rate of LiF controls
0.008nm/s, in metal cathode layer 9, the evaporation rate of Al controls at 0.9nm/s.
The performance of blue organic electroluminescent device prepared by detection the present embodiment, experimental result table
Bright, device, under DC source drives, launches the blue light being positioned at 462 ran.Work as brightness
For 10000cd/m2Time, the chromaticity coordinates of device is (0.139,0.178)；Change along with running voltage
Changing, the chromaticity coordinates of device is almost unchanged.The bright voltage that rises of device is 3.0 volts, the maximum of device
Brightness is 19657cd/m2.The maximum current efficiency of device is 36.62cd/A, and peak power is imitated
Rate is 38.33lm/W.
Embodiment 5
First by the ito anode layer laser ablation electrode into strips on ito glass, use the most successively
Cleanout fluid, deionized water ultrasonic cleaning 15min also put into oven for drying.Then after drying
Substrate puts into pretreatment vacuum chamber, with the voltage of 400V under the atmosphere that vacuum is 10 Pa
It is transferred into organic vapor deposition room after ito anode is carried out the low-voltage plasma process of 3min.
It is 1～2 × 10 in vacuum-5In the organic vapor deposition room of Pa, it is deposited with 6nm the most successively
Thick MoO3TAPC hole transport-electronic barrier layer 4 that anode modification layer 3,50nm are thick,
12nm thickness fac-Ir (Pmb)3Luminescent layer 5,16nm thickness are dominated in the hole of doping TCP
Dy(acac)3Phen Yu fac-Ir (Pmb)3The electronics of codope UGH2 dominates luminescent layer 6 and 45
BmPyPhB hole barrier-electron transfer layer 7 that nm is thick.It follows that the device quilt being not fully complete
Transfer to metal evaporation room, 4～6 × 10-5The thick LiF of 1.1nm it is deposited with under the vacuum of Pa
Cathodic modification layer 8, is deposited with the thick gold of 240nm finally by special mask on LiF layer
Belonging to Al cathode layer 9, being prepared as structure is ITO/MoO3/TAPC/fac-Ir(Pmb)3(22%):
TCP/Dy(acac)3Phen (0.3%): fac-Ir (Pmb)3(19%): UGH2/BmPyPhB/LiF/Al
Organic electroluminescence device.MoO in anode modification layer 33Evaporation rate control 0.01
Nm/s, in hole transport-electronic barrier layer 4, the evaporation rate of TAPC controls at 0.08nm/s,
Ir (mppy) in luminescent layer 5 is dominated in hole3Control respectively 0.022 with the evaporation rate of TCP
Nm/s and 0.1nm/s, electronics dominates Dy (acac) in luminescent layer 63phen、fac-Ir(Pmb)3
Control respectively at 0.0003nm/s, 0.019nm/s and 0.1nm/s with the evaporation rate of UGH2,
In hole barrier-electron transfer layer 7, the evaporation rate of BmPyPhB controls at 0.09nm/s, cloudy
In pole decorative layer 8, the evaporation rate of LiF controls at 0.012nm/s, Al in metal cathode layer 9
Evaporation rate control at 1.2nm/s.
The performance of blue organic electroluminescent device prepared by detection the present embodiment, experimental result table
Bright, device, under DC source drives, launches the blue light being positioned at 462 ran.Work as brightness
For 10000cd/m2Time, the chromaticity coordinates of device is (0.139,0.175)；Change along with running voltage
Changing, the chromaticity coordinates of device is almost unchanged.The bright voltage that rises of device is 3.1 volts, the maximum of device
Brightness is 21275cd/m2.The maximum current efficiency of device is 36.89cd/A, and peak power is imitated
Rate is 37.37lm/W.
Embodiment 6
First by the ito anode layer laser ablation electrode into strips on ito glass, use the most successively
Cleanout fluid, deionized water ultrasonic cleaning 15min also put into oven for drying.Then after drying
Substrate puts into pretreatment vacuum chamber, with the voltage of 400V under the atmosphere that vacuum is 10 Pa
It is transferred into organic vapor deposition room after ito anode is carried out the low-voltage plasma process of 3min.
It is 1～2 × 10 in vacuum-5In the organic vapor deposition room of Pa, it is deposited with 3nm the most successively
Thick MoO3TAPC hole transport-electronic barrier layer 4 that anode modification layer 3,40nm are thick,
10nm thickness mer-Ir (Pmb)3Luminescent layer 5,10nm thickness are dominated in the hole of doping BSB
Tm(acac)3Phen Yu mer-Ir (Pmb)3The electronics of codope BCBP dominates luminescent layer 6 and 40
TPBi hole barrier-electron transfer layer 7 that nm is thick.It follows that the device being not fully complete is transferred
To metal evaporation room, 4～6 × 10-5LiF thick for 1.0nm it is deposited with cloudy under the vacuum of Pa
Pole decorative layer 8, is deposited with the thick metal of 120nm finally by special mask on LiF layer
Al cathode layer 9, being prepared as structure is ITO/MoO3/TAPC/mer-Ir(Pmb)3(9%):
BSB/Tm(acac)3Phen (0.3%): mer-Ir (Pmb)3(9%): BCBP/TPBi/LiF/Al's
Organic electroluminescence device.MoO in anode modification layer 33Evaporation rate control 0.06
Nm/s, in hole transport-electronic barrier layer 4, the evaporation rate of TAPC controls at 0.08nm/s,
Mer-Ir (Pmb) in luminescent layer 5 is dominated in hole3Control respectively 0.009 with the evaporation rate of BSB
Nm/s and 0.1nm/s, electronics dominates Tm (acac) in luminescent layer 63phen、mer-Ir(Pmb)3
Control respectively at 0.0003nm/s, 0.009nm/s and 0.1nm/s with the evaporation rate of BCBP,
In hole barrier-electron transfer layer 7, the evaporation rate of TPBi controls at 0.08nm/s, and negative electrode is repaiied
In decorations layer 8, the evaporation rate of LiF controls at 0.005nm/s, the steaming of Al in metal cathode layer 9
Send out rate controlled at 1.5nm/s.
The performance of blue organic electroluminescent device prepared by detection the present embodiment, experimental result table
Bright, device, under DC source drives, launches the blue light being positioned at 462 ran.Work as brightness
For 10000cd/m2Time, the chromaticity coordinates of device is (0.140,0.174)；Change along with running voltage
Changing, the chromaticity coordinates of device is almost unchanged.The bright voltage that rises of device is 3.1 volts, the maximum of device
Brightness is 20095cd/m2.The maximum current efficiency of device is 37.08cd/A, and peak power is imitated
Rate is 37.56lm/W.
The explanation of above example is only intended to help to understand that the method for the present invention and core thereof are thought
Think.It should be pointed out that, for those skilled in the art, without departing from this
On the premise of bright principle, it is also possible to the present invention is carried out some improvement and modification, these improve and
Modify in the protection domain also falling into the claims in the present invention.
Described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of
Or the use present invention.Those skilled in the art are come by the multiple amendment to these embodiments
Saying and will be apparent from, generic principles defined herein can be without departing from the present invention's
In the case of spirit or scope, realize in other embodiments.Therefore, the present invention will not be by
It is limited to the embodiments shown herein, and is to fit to and principles disclosed herein and new
The widest scope that grain husk feature is consistent.
Claims (10)
1. a blue organic electroluminescent device, it is characterised in that including:
Substrate；
It is compound in the anode layer on described substrate；
The anode modification layer being compound on described anode layer；
It is compound in the hole transport-electronic barrier layer on described anode modification layer；
Luminescent layer is dominated in the hole being compound on described hole transport-electronic barrier layer；
It is compound in the electronics dominating on luminescent layer in described hole and dominates luminescent layer；
It is compound in hole barrier-electron transfer layer that described electronics is dominated on luminescent layer；
It is compound in the cathodic modification layer on described hole barrier-electron transfer layer；
It is compound in the cathode layer on described cathodic modification layer；
Described electronics dominates luminescent layer by organic sensitized material, blue organic luminous material and electron type
Organic host material forms；
Described organic sensitized material closes thulium and three (levulinics selected from tri acetylacetonato Phen
Ketone) Phen closes one or both in dysprosium；
Described organic sensitized material is 0.1wt%～0.5wt% of described electron type organic host material.
Blue organic electroluminescent device the most according to claim 1, it is characterised in that institute
State the 8.0wt%～25.0 that content is described electron type organic host material of blue organic luminous material
Wt%.
Blue organic electroluminescent device the most according to claim 1 and 2, it is characterised in that
Described blue organic luminous material selected from double (3,5-bis-fluoro-4-cyano group) pyridine hydrochloric acid close iridium, double (2,
4-difluorophenyl pyridinato) four (1-pyrazolyl) boron closes iridium, three (1-phenyl-3-methyl benzo miaow is rattled away azoles
Quinoline-2-base-C, C2 ') close iridium, three (1-phenyl-3-methyl benzo miaows rattle away oxazoline-2-base-C, C2 ') close iridium,
Double (2,4 difluorobenzene yl pyridines) (5-(pyridine-2-base)-1H-TETRAZOLE) close iridium, three [(2,6-
Diisopropyl phenyl) 2-phenyl-1H-imidazoles [e] closes iridium, three (1-phenyl-3-methyl miaow is rattled away oxazoline-2-
Base-C, C (2) ') close iridium, three (1-phenyl-3-methyl miaows rattle away oxazoline-2-base-C, C (2) ') close iridium, double
(1-phenyl-3 methyl miaow is rattled away oxazoline-2-base-C, C2′) (2-(2H-pyrazole-3-yl)-pyridine) conjunction iridium, double (1-
(4-aminomethyl phenyl)-3-methyl miaow is rattled away oxazoline-2-base-C, C2′) (2-(2H-pyrazole-3-yl)-pyridine) conjunction iridium,
It is double that (1-(4-fluorophenyl)-3-methyl miaow is rattled away oxazoline-2-base-C, C2′) (2-(2H-pyrazole-3-yl)-pyridine)
Close iridium, double (1-(4-fluorophenyl)-3-methyl miaow is rattled away oxazoline-2-base-C, C2′) (2-(5-trifluoromethyl-2H-
Pyrazole-3-yl)-pyridine) close iridium, three (1,3-diphenyl-benzimidazolyl-2 radicals-base-C, C2′) close iridium, double (1-
(4-fluorophenyl)-3-methyl miaow is rattled away oxazoline-2-base-C, C2’) (3,5-dimethyl-2-(1H-pyrazoles-5-
Base) pyridine) close iridium, it is double that (1-(4-aminomethyl phenyl)-3-methyl miaow is rattled away oxazoline-2-base-C, C2’)(3,5-
Dimethyl-2-(1H-pyrazoles-5-base) pyridine) close iridium and three (Phenylpyrazoles) close the one in iridium or
Multiple.
Blue organic electroluminescent device the most according to claim 1, it is characterised in that institute
State electron type organic host material selected from 2,6-bis-[3-(9H-9-carbazyl) phenyl] pyridine, 1,4-double (three
Phenyl silane base) benzene, 2,2 '-bis-(4-(9-carbazyl) phenyl) biphenyl, three [2,4,6-trimethyl-3-
(3-pyridine radicals) phenyl] borine, 1,3,5-tri-[(3-pyridine)-3-phenyl] benzene, 1,3-double [3,5-
Two (3-pyridine radicals) phenyl] benzene, 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, 9-(4-
T-butyl-phenyl) double (triphenyl the is silica-based)-9H-carbazole of-3,6-and 9-(8-diphenylphosphoryl)-
One or more in hexichol azoles [b, d] furan-9H-carbazole.
Blue organic electroluminescent device the most according to claim 1, it is characterised in that institute
State hole to dominate luminescent layer and be made up of blue organic luminous material and cavity type organic host material；Institute
State 8.0wt%～25.0wt% that blue organic luminous material is described cavity type organic host material；
Described blue organic luminous material closes iridium, double selected from double (3,5-bis-fluoro-4-cyano group) pyridine hydrochloric acid
(2,4 difluorobenzene yl pyridines) four (1-pyrazolyl) boron closes iridium, three (1-phenyl-3-methyl benzos
Miaow is rattled away oxazoline-2-base-C, C2 ') close iridium, three (1-phenyl-3-methyl benzo miaows rattle away oxazoline-2-base-C, C2 ')
Close iridium, double (2,4 difluorobenzene yl pyridines) (5-(pyridine-2-base)-1H-TETRAZOLE) close iridium, three [(2,
6-diisopropyl phenyl) 2-phenyl-1H-imidazoles [e] closes iridium, three (1-phenyl-3-methyl miaow is rattled away oxazoline-2-
Base-C, C (2) ') close iridium, three (1-phenyl-3-methyl miaows rattle away oxazoline-2-base-C, C (2) ') close iridium, double
(1-phenyl-3 methyl miaow is rattled away oxazoline-2-base-C, C2′) (2-(2H-pyrazole-3-yl)-pyridine) conjunction iridium, double (1-
(4-aminomethyl phenyl)-3-methyl miaow is rattled away oxazoline-2-base-C, C2′) (2-(2H-pyrazole-3-yl)-pyridine) conjunction iridium,
It is double that (1-(4-fluorophenyl)-3-methyl miaow is rattled away oxazoline-2-base-C, C2′) (2-(2H-pyrazole-3-yl)-pyridine)
Close iridium, double (1-(4-fluorophenyl)-3-methyl miaow is rattled away oxazoline-2-base-C, C2′) (2-(5-trifluoromethyl-2H-
Pyrazole-3-yl)-pyridine) close iridium, three (1,3-diphenyl-benzimidazolyl-2 radicals-base-C, C2′) close iridium, double (1-
(4-fluorophenyl)-3-methyl miaow is rattled away oxazoline-2-base-C, C2’) (3,5-dimethyl-2-(1H-pyrazoles-5-
Base) pyridine) close iridium, it is double that (1-(4-aminomethyl phenyl)-3-methyl miaow is rattled away oxazoline-2-base-C, C2’)(3,5-
Dimethyl-2-(1H-pyrazoles-5-base) pyridine) close iridium and three (Phenylpyrazoles) close the one in iridium or
Multiple；
Described cavity type organic host material is selected from 4,4 '-N, N '-two carbazole diphenyl, 1,3-bis-click
Azoles-9-base benzene, 9,9 '-(5-(tri-phenyl-silane base)-1,3-phenyl) two-9H-carbazoles, 1,3,5-tri-(9-
Carbazyl) benzene, 4,4 ', 4 " in double (tri-phenyl-silane base) biphenyl of-three (carbazole-9-base) triphenylamines and 1,4-
One or more.
Blue organic electroluminescent device the most according to claim 1, it is characterised in that institute
State the material of hole transport-electronic barrier layer selected from 4,4 '-cyclohexyl two [N, N-bis-(4-aminomethyl phenyl) benzene
Amine], two pyrazines [2,3-f:2 ', 3 '-h] quinoxaline-2,3,6,7,10,11-six itrile groups, N4, N4 '-
Two (naphthalene-1-base)-N4, N4 '-bis-(4-ethenylphenyl) biphenyl-4,4 '-diamidogen, N, N '-bis-(3-
Aminomethyl phenyl)-N, N '-bis-(phenyl)-2,7-diamidogen-9,9-spiro-bisfluorene, N, N, N ', N '-four-(3-
Aminomethyl phenyl)-3-3 '-dimethyl benzidine, 2,2 '-two (3-(N, N-bis--p-totuidine base)
Phenyl) biphenyl, N, N '-two (naphthalene-2-base)-N, N '-two (phenyl) benzidine, N, N '-two
(naphthalene-1 base)-N, N ' diphenyl-2,7-diaminourea-9,9-spiro-bisfluorene, N, N '-two (3-methylbenzene
Base)-N, N '-diphenyl-2,7-diaminourea-9,9-dimethyl fluorene, N, N '-two (naphthalene-1-base)-N, N '-
Diphenyl-2,7-diaminourea-9,9-dimethyl fluorene, N, N ' two (3-aminomethyl phenyl)-N, N ' hexichol
Base-2,7-diaminourea-9,9-diphenylfluorene, N, N '-two (naphthalene-1-base)-N, N '-diphenyl-2,7-bis-
Amino-9,9-diphenylfluorene, N, N '-two (naphthalene-1-base)-N, N '-diphenyl-2,2 '-dimethyl diaminourea
Biphenyl, 2,2 ', 7,7 '-four (N, N-diphenyl amino)-2,7-diaminourea-9,9-spiro-bisfluorene, 9,9-bis-
[4-(N, N dinaphthyl-2-base-amino) phenyl]-9H-fluorenes, 9,9-[4-(N-naphthalene-1 base-N-aniline)-benzene
Base]-9H-fluorenes, 2,2 '-two [N, N-bis-(4-phenyl) amino]-9,9-spiro-bisfluorene, 2,2 '-bis-(N, N-
Phenylamino)-9,9-spiro-bisfluorene, N, N '-diphenyl-N, N '-(1-naphthyl)-1,1 '-biphenyl-4,4 '-
Diamidogen and 4, one or more in 4 '-two [N-(p-tolyl)-N-phenyl-amino] diphenyl.
Blue organic electroluminescent device the most according to claim 1, it is characterised in that institute
State the material of hole barrier-electron transfer layer selected from three [2,4,6-trimethyl-3-(3-pyridine radicals) phenyl]
Borine, 1,3,5-tri-[(3-pyridine)-3-phenyl] benzene, 1,3-double [3,5-bis-(3-pyridine radicals) phenyl]
One or more in benzene and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene.
Blue organic electroluminescent device the most according to claim 1, it is characterised in that institute
The thickness stating anode modification layer is 1～10nm, and the thickness of described hole transport-electronic barrier layer is
30～60nm, it is 5～20nm that the thickness of luminescent layer is dominated in described hole, the leading luminescence of described electronics
The thickness of layer is 5～20nm, and the thickness of described hole barrier-electron transfer layer is 30～60nm, institute
The thickness stating cathodic modification layer is 0.8～1.2nm, and the thickness of described cathode layer is 90～300nm.
9. the preparation method of a blue organic electroluminescent device, it is characterised in that including:
Anode layer on substrate is performed etching, on described anode layer, after drying, is deposited with anode successively
Decorative layer, hole transport-electronic barrier layer, luminescent layer is dominated in hole, electronics dominates luminescent layer, sky
Cave stop-electron transfer layer, cathodic modification layer and cathode layer；
Described electronics dominates luminescent layer by organic sensitized material, blue organic luminous material and electron type
Organic host material forms；
Described organic sensitized material closes thulium and three (levulinics selected from tri acetylacetonato Phen
Ketone) Phen closes one or both in dysprosium；
Described organic sensitized material is 0.1wt%～0.5wt% of described electron type organic host material.
Preparation method the most according to claim 9, it is characterised in that described anode modification
The evaporation rate of layer is 0.01～0.05nm/s, and described hole is dominated luminescent layer and dominated luminescent layer with electronics
The evaporation rate of middle material of main part is 0.05～0.1nm/s, and it is organic that described electronics is dominated in luminescent layer
The evaporation rate of sensitized material is 0.00005～0.0005nm/s, and described electronics dominates luminescent layer with empty
It is 0.004～0.025nm/s that the evaporation rate of the blue emitting material in luminescent layer is dominated in cave, described sky
Cave transmission-electronic barrier layer is 0.05～0.1 with the evaporation rate of material in hole barrier-electron transfer layer
Nm/s, the evaporation rate of described cathodic modification layer is 0.005～0.05nm/s, the steaming of described cathode layer
Sending out speed is 0.5～2.0nm/s.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410610118.6A CN104300092B (en) | 2014-10-30 | A kind of blue organic electroluminescent device and preparation method thereof | |
| PCT/CN2014/091781 WO2016065678A1 (en) | 2014-10-30 | 2014-11-20 | Blue organic electroluminescent device and preparation method thereof |
| JP2017523422A JP6456497B2 (en) | 2014-10-30 | 2014-11-20 | Blue organic electroluminescence device and method for producing the same |
| US15/522,635 US10700294B2 (en) | 2014-10-30 | 2014-11-20 | Blue organic electroluminescent device and preparation method thereof |
| EP14904709.4A EP3214667B1 (en) | 2014-10-30 | 2014-11-20 | Blue organic electroluminescent device and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410610118.6A CN104300092B (en) | 2014-10-30 | A kind of blue organic electroluminescent device and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104300092A CN104300092A (en) | 2015-01-21 |
| CN104300092B true CN104300092B (en) | 2017-01-04 |
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