CN109438350B - Organic small molecule luminescent material and organic electroluminescent device - Google Patents
Organic small molecule luminescent material and organic electroluminescent device Download PDFInfo
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- CN109438350B CN109438350B CN201811378536.1A CN201811378536A CN109438350B CN 109438350 B CN109438350 B CN 109438350B CN 201811378536 A CN201811378536 A CN 201811378536A CN 109438350 B CN109438350 B CN 109438350B
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- 239000000463 material Substances 0.000 title claims abstract description 96
- 150000003384 small molecules Chemical class 0.000 title claims abstract description 33
- KERRHNRYIAXFMZ-UHFFFAOYSA-N spiro[10H-acridine-9,2'-adamantane] Chemical compound C12C3(C4CC(CC(C1)C4)C2)C1=CC=CC=C1NC=1C=CC=CC=13 KERRHNRYIAXFMZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000008878 coupling Effects 0.000 claims abstract description 8
- 238000010168 coupling process Methods 0.000 claims abstract description 8
- 238000005859 coupling reaction Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 claims description 6
- 230000005525 hole transport Effects 0.000 claims description 6
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical compound BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 claims description 5
- IYKFYARMMIESOX-SPJNRGJMSA-N adamantanone Chemical compound C([C@H](C1)C2)[C@H]3C[C@@H]1C(=O)[C@@H]2C3 IYKFYARMMIESOX-SPJNRGJMSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
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- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 abstract description 20
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000746 purification Methods 0.000 abstract description 8
- 238000005424 photoluminescence Methods 0.000 abstract description 7
- 238000006862 quantum yield reaction Methods 0.000 abstract description 7
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- 230000008022 sublimation Effects 0.000 abstract description 6
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- 125000003118 aryl group Chemical group 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
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- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 11
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 10
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 10
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- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 6
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 6
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- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ATTVYRDSOVWELU-UHFFFAOYSA-N 1-diphenylphosphoryl-2-(2-diphenylphosphorylphenoxy)benzene Chemical compound C=1C=CC=CC=1P(C=1C(=CC=CC=1)OC=1C(=CC=CC=1)P(=O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 ATTVYRDSOVWELU-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
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- 238000010438 heat treatment Methods 0.000 description 5
- AYHGAQGOMUQMTR-UHFFFAOYSA-N 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine Chemical compound C1=CC(Br)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 AYHGAQGOMUQMTR-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 4
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- 239000012074 organic phase Substances 0.000 description 4
- 229920006391 phthalonitrile polymer Polymers 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- LSAQBBSMSWPVOL-UHFFFAOYSA-N tert-butyl N-(4-bromophenyl)-N-phenylcarbamate Chemical compound C(C)(C)(C)OC(N(C1=CC=CC=C1)C1=CC=C(C=C1)Br)=O LSAQBBSMSWPVOL-UHFFFAOYSA-N 0.000 description 4
- WAAWAHYRHUWAFM-UHFFFAOYSA-N 2-bromo-n-phenylaniline Chemical compound BrC1=CC=CC=C1NC1=CC=CC=C1 WAAWAHYRHUWAFM-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
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- HBQUOLGAXBYZGR-UHFFFAOYSA-N 2,4,6-triphenyl-1,3,5-triazine Chemical compound C1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 HBQUOLGAXBYZGR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
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- 239000012362 glacial acetic acid Substances 0.000 description 2
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- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 2
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- ZGNPLWZYVAFUNZ-UHFFFAOYSA-N tert-butylphosphane Chemical compound CC(C)(C)P ZGNPLWZYVAFUNZ-UHFFFAOYSA-N 0.000 description 2
- OETBGSAJFWSUDM-UHFFFAOYSA-N thianthrene 5,5,10,10-tetraoxide Chemical compound C1=CC=C2S(=O)(=O)C3=CC=CC=C3S(=O)(=O)C2=C1 OETBGSAJFWSUDM-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- VVPDQUPMOSDHEK-UHFFFAOYSA-N tris(2,6-dimethylphenyl)borane Chemical compound CC1=CC=CC(C)=C1B(C=1C(=CC=CC=1C)C)C1=C(C)C=CC=C1C VVPDQUPMOSDHEK-UHFFFAOYSA-N 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- LPNHNONXUQKYFW-UHFFFAOYSA-N 2-(4-bromophenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Chemical compound BrC1=CC=C(C=C1)C1=NC(=NC(=N1)C1=C(C=C(C=C1)C)C)C1=C(C=C(C=C1)C)C LPNHNONXUQKYFW-UHFFFAOYSA-N 0.000 description 1
- SUUVDNNGKHNPGN-UHFFFAOYSA-N 2-(4-bromophenyl)-4,6-bis(2-methylphenyl)-1,3,5-triazine Chemical compound BrC1=CC=C(C=C1)C1=NC(=NC(=N1)C1=C(C=CC=C1)C)C1=C(C=CC=C1)C SUUVDNNGKHNPGN-UHFFFAOYSA-N 0.000 description 1
- SVSJPNMDLPIZEK-UHFFFAOYSA-N 2-(4-bromophenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine Chemical compound C1=CC(C)=CC=C1C1=NC(C=2C=CC(C)=CC=2)=NC(C=2C=CC(Br)=CC=2)=N1 SVSJPNMDLPIZEK-UHFFFAOYSA-N 0.000 description 1
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- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical group C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
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- 239000003446 ligand Substances 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
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- 238000007738 vacuum evaporation Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/20—Spiro-condensed ring systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
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Abstract
The invention provides an organic small-molecule luminescent material and an organic electroluminescent device. The organic micromolecule luminescent material is obtained by coupling a novel acridine donor unit 10H-spiro [ acridine-9, 2' -adamantane ] with a receptor unit, has a single structure, determined molecular weight, convenient purification, good reproducibility of repeated synthesis, lower sublimation temperature and higher decomposition temperature, and stable film form, and has very high photoluminescence quantum yield in a film state because non-aromatic rigid structure adamantane is used as a donor part structure.
Description
Technical Field
The invention relates to the field of organic electroluminescence, in particular to an organic small molecular luminescent material and an organic electroluminescent device adopting the organic small molecular luminescent material.
Background
An organic electroluminescent (O L ED) device is a self-luminescent device, has the advantages of low voltage, wide viewing angle, fast response speed, good temperature adaptability and the like, is a new generation of display technology, a few manufacturers produce O L ED panels at present, and more companies enter research, development and mass production stages.
The principle of the organic electroluminescent device is that under the action of an electric field, holes and electrons are respectively injected from an anode and a cathode, and are respectively compounded in a luminescent layer through a hole injection layer, a hole transport layer, an electron injection layer and an electron transport layer to form excitons, and the excitons emit attenuated luminescence.
The organic electroluminescent material is used as a core component of an organic electroluminescent device, and has great influence on the service performance of the device. Among them, fluorescence characteristics with high quantum efficiency, good semiconductor characteristics, high-quality film formation characteristics, good chemical and thermal stability, good processability, and the like are main performance factors. The organic light-emitting material is classified by the light-emitting wavelength range according to the molecular structural characteristics, and includes organic small molecule light-emitting materials, organic complex light-emitting materials, and organic polymer light-emitting materials.
In order to improve the efficiency and the service life of an organic photoelectric device, an organic complex luminescent material is basically a heavy metal complex, the production cost is high, the mass production is not facilitated, the organic complex luminescent material has a serious efficiency roll-off phenomenon under high current density, in addition, the stability of the organic complex luminescent material is not good, and compared with a polymer material, the organic small molecule luminescent material can obtain higher device efficiency due to the fact that the preparation steps are few, the structure is stable, and the purification is convenient, so that the commercial application is more likely to be obtained.
Organic light emitting diodes have been advanced to a great extent so far, and scientists have proposed various theories to explain the mechanism of light emission. However, the organic small-molecule photoelectric materials which have simple structures, good performances and meet the commercial requirements are still very limited, and the development of new organic photoelectric materials still has great significance.
Disclosure of Invention
The invention aims to provide an organic small molecule luminescent material which has very high photoluminescence quantum yield in a thin film state and is a luminescent guest material with good electron-hole double-transmission property.
The invention also aims to provide an organic electroluminescent device, wherein the luminescent layer adopts the organic small molecule luminescent material, and has higher external quantum efficiency and excellent luminescent performance.
In order to achieve the above object, the present invention provides an organic small molecule luminescent material, which uses 10H-spiro [ acridine-9, 2' -adamantane ] as a donor unit and is obtained by coupling an acceptor unit and the donor unit;
10H-spiro [ acridine-9, 2' -adamantane]Has the chemical structural formula of
The chemical structural general formula of the organic micromolecule luminescent material is shown as the following formula (I),
in the formula (I), Ar is an aromatic substituent with electron deficiency.
The organic small molecule luminescent material takes 2,4, 6-triphenyl triazine, 1, 3-phthalonitrile, 3, 5-phthalonitrile, diphenylphosphinyl, diphenyl sulphonyl, phenoxazine-10, 10' -dioxide, tri (2, 6-xylyl) boron, thianthrene-5, 5,10, 10-tetraoxide, 9-thioxanthone or 9-xanthone as a receptor unit.
In the formula (I), Ar is
The chemical structural formula of the organic micromolecule luminescent material is shown as
The organic micromolecule luminescent material is prepared by taking a donor unit 10H-spiro [ acridine-9, 2' -adamantane ] and an acceptor unit as raw materials through Hartwig-Buchwald coupling reaction.
10H-spiro [ acridine-9, 2' -adamantane]Aniline, o-bromoiodobenzene and adamantanone are used as starting materials, and are subjected to Hartwig-Buchwald coupling reaction (Boc)2O is added to protect reaction.
The invention also provides an organic electroluminescent device, which comprises a light-transmitting substrate, an anode layer, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer and a cathode layer which are arranged in a stacked manner;
the light-emitting layer contains the organic small molecule light-emitting material as described above.
The organic small molecule luminescent material is used as a luminescent object material in the luminescent layer.
The light-emitting layer contains one or more organic small molecule light-emitting materials with different structural formulas.
The luminescent layer is prepared and formed by means of thermal evaporation, spin coating, brushing, spraying, dip coating, roll coating, printing or ink-jet printing.
The invention has the beneficial effects that: the organic micromolecule luminescent material is obtained by coupling a novel acridine donor unit 10H-spiro [ acridine-9, 2 '-adamantane ] based on nonaromatic rigid structure adamantane with an acceptor unit, has a single structure, determined molecular weight, convenient purification, good reproducibility of repeated synthesis, lower sublimation temperature and higher decomposition temperature, and stable film form, has very rigid structure due to the donor unit 10H-spiro [ acridine-9, 2' -adamantane ], takes nonaromatic rigid structure adamantane as a donor part structure, has very high photoluminescence quantum yield in a film state, and can effectively solve the problem that excited molecules cause severe non-radiative decay to cause low device efficiency due to configuration relaxation when being applied to an organic electroluminescent device, and the material characteristics such as luminous color, molecular weight, electrophilicity and the like of the material can be adjusted by changing the type of the acceptor unit connected with the 10H-spiro [ acridine-9, 2' -adamantane ], the conjugation length and intramolecular charge transfer of the material can be effectively regulated, and the energy levels of the highest occupied orbit and the lowest unoccupied orbit are adjusted to meet the requirements of the organic electroluminescent device, so that the device can be endowed with more excellent performance when the material is applied to the organic electroluminescent device. According to the organic electroluminescent device, the luminescent layer is made of the organic micromolecule luminescent material, so that the external quantum efficiency of the organic electroluminescent device can be effectively improved, and the organic electroluminescent device has excellent device performance.
For a better understanding of the nature and technical aspects of the present invention, reference should be made to the following detailed description of the invention, taken in conjunction with the accompanying drawings, which are provided for purposes of illustration and description and are not intended to limit the invention.
Drawings
The technical solution and other advantages of the present invention will become apparent from the following detailed description of specific embodiments of the present invention, which is to be read in connection with the accompanying drawings.
In the drawings, there is shown in the drawings,
FIG. 1 is a thermogravimetric analysis of molecule 1 prepared in example 7;
FIG. 2 is an absorption spectrum in toluene solution of molecules 1, 2, 3 and 4 prepared in examples 7, 8, 9 and 10;
FIG. 3 is a fluorescence emission spectrum of molecules 1, 2, 3 and 4 prepared in examples 7, 8, 9 and 10 in toluene solution;
FIG. 4 is a graph of current density-voltage-luminance of an organic electroluminescent device using the molecule 1 prepared in example 7 as a guest material of a light-emitting layer;
FIG. 5 is a graph showing a current efficiency-luminance relationship of an organic electroluminescent device using the molecule 1 prepared in example 7 as a guest material of a light-emitting layer;
FIG. 6 is a graph showing the external quantum efficiency-luminance relationship of an organic electroluminescent device using the molecule 1 prepared in example 7 as a guest material of a light-emitting layer;
FIG. 7 is a luminescence spectrum of an organic electroluminescent device using molecule 1 prepared in example 7 as a guest material of a light-emitting layer;
FIG. 8 is a graph of current density-voltage-luminance for an organic electroluminescent device using the compound DMAc-TRZ as the guest material of the light-emitting layer;
FIG. 9 is a graph of current efficiency versus luminance for an organic electroluminescent device having the compound DMAc-TRZ as the guest material of the light-emitting layer;
FIG. 10 is a graph of external quantum efficiency versus luminance for an organic electroluminescent device having the compound DMAc-TRZ as the guest material of the light-emitting layer;
FIG. 11 shows the emission spectrum of an organic electroluminescent device using DMAc-TRZ as the guest material of the light-emitting layer.
Detailed Description
To further illustrate the technical means and effects of the present invention, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
The invention provides an organic micromolecule luminescent material, which is obtained by adopting a novel acridine donor unit 10H-spiro [ acridine-9, 2 '-adamantane ] based on nonaromatic rigid structure adamantane and coupling the donor unit 10H-spiro [ acridine-9, 2' -adamantane ] with an acceptor unit through Hartwig-Buchwald coupling reaction.
Wherein, the 10H-spiro [ acridine-9, 2' -adamantane]Is sequentially subjected to Hartwig-Buchwald reaction, (Boc)2O addition protective reaction, low-temperature reaction, normal-temperature or high-temperature ring-closing reaction and the like, and the chemical structural formula of the compound is
Because the inherent rigid structure of adamantane can improve the rigidity of the whole molecule, the energy loss of the organic small-molecule luminescent material molecule formed by the adamantane due to the geometric configuration deformation in an excited state can be effectively reduced, and the organic small-molecule luminescent material obtained by utilizing the donor unit 10H-spiro [ acridine-9, 2' -adamantane ] has very high photoluminescence quantum yield in a thin film state, thereby being beneficial to improving the efficiency and the stability of a device.
The chemical structural general formula of the organic micromolecule luminescent material is shown as the following formula (I),
in the formula (I), Ar is an aromatic substituent with electron deficiency.
Specifically, the organic small molecule luminescent material takes common electron-deficient aromatic compounds and derivatives thereof such as 2,4, 6-triphenyl triazine, 1, 3-phthalonitrile, 3, 5-phthalonitrile, diphenylphosphonyl, diphenyl sulfosulfone, phenoxazine-10, 10' -dioxide, tri (2, 6-xylyl) boron, thianthrene-5, 5,10, 10-tetraoxide, 9-thioxanthone or 9-xanthone as acceptor units.
In formula (1), Ar may be
The chemical structural formula of the organic micromolecule luminescent material is correspondingly
Specifically, 10H-spiro [ acridine-9, 2' -adamantane]Aniline, o-bromoiodobenzene and adamantanone are used as starting materials, and are subjected to Hartwig-Buchwald coupling reaction (Boc)2O is added to protect reaction and the like.
The organic micromolecule luminescent material is obtained by coupling a novel acridine donor unit 10H-spiro [ acridine-9, 2 '-adamantane ] based on nonaromatic rigid structure adamantane with an acceptor unit, has a single structure, determined molecular weight, convenient purification, good reproducibility of repeated synthesis, lower sublimation temperature and higher decomposition temperature, and stable film form, and can effectively solve the problem of low device efficiency caused by serious nonradiative attenuation due to configuration relaxation of excited molecules when being applied to an organic electroluminescent device because the organic micromolecule luminescent material obtained by the donor unit has very high photoluminescence quantum yield in a film state because the donor unit 10H-spiro [ acridine-9, 2' -adamantane ] has a very rigid structure and the nonaromatic rigid structure adamantane is used as a donor partial structure, and the material characteristics such as luminous color, molecular weight, electrophilicity and the like of the material can be adjusted by changing the type of the acceptor unit connected with the 10H-spiro [ acridine-9, 2' -adamantane ], the conjugation length and intramolecular charge transfer of the material can be effectively regulated, and the energy levels of the highest occupied orbit and the lowest unoccupied orbit are adjusted to meet the requirements of the organic electroluminescent device, so that the device can be endowed with more excellent performance when the material is applied to the organic electroluminescent device.
Based on the organic small molecule luminescent material, the invention also provides an organic electroluminescent device, which comprises a light-transmitting substrate, an anode layer, a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer and a cathode layer which are arranged in a stacked manner; the light-emitting layer contains the organic small molecule light-emitting material.
Specifically, the organic small molecule light-emitting material serves as a light-emitting guest material in the light-emitting layer.
Specifically, the light-emitting layer contains one or more organic small molecule light-emitting materials with different structural formulas.
Specifically, the light-emitting layer may be prepared by thermal evaporation, spin coating, brush coating, spray coating, dip coating, roll coating, printing, or inkjet printing.
According to the organic electroluminescent device, the organic micromolecular luminescent material adopted by the luminescent layer is obtained by coupling the donor unit 10H-spiro [ acridine-9, 2' -adamantane ] and the receptor unit through Hartwig-Buchwald coupling reaction, and the organic electroluminescent device has high external quantum efficiency and excellent luminescent performance.
The present invention will be described in detail with reference to specific examples, but the present invention is not limited to the scope of the examples.
Example 1
The synthesis method 1 of the 2-bromo-N-phenylaniline has the following chemical reaction formula:
in a 250m L three-necked flask, aniline (0.2mol, 18.6g), o-bromoiodobenzene (0.2mol, 56.58g), palladium acetate (0.6mmol, 134.4mg) and sodium tert-butoxide (0.4mol) were added successively at room temperature, and then 150m L of toluene was added thereto, followed by N2After 20 min, tert-butylphosphine (1.2mmol, 1.2ml) was added and the N feed was continued2For 20 minutes, heat to reflux and stir for 12 hours. The temperature was lowered to room temperature, sodium t-butoxide was removed by suction filtration, the solvent was removed by distillation under pressure, and a colorless oily liquid was obtained by separation and purification with a silica gel column (27.8g, yield 56%).
Example 2
The synthesis method 2 of the 2-bromo-N-phenylaniline has the following chemical reaction formula:
in a 250m L three-necked flask, aniline (0.2mol, 18.6g), o-bromoiodobenzene (0.2mol, 56.58g), palladium acetate (0.6mmol, 134.4mg) and sodium tert-butoxide (0.4mol) were added successively at room temperature to the flask, o-bis (2-phenyl) bis (diphenylphosphine) (0.6mmol, 340mg) was added, 150m L of toluene was then added, and N was introduced2For 20 minutes, heat to reflux and stir for 12 hours. The temperature was lowered to room temperature, sodium t-butoxide was removed by suction filtration, the solvent was removed by distillation under pressure, and a colorless oily liquid (44.2g, 89% yield) was obtained by separation and purification on a silica gel column.
Upon comparing example 1 and example 2 above, it was found that by changing the catalyst ligand from tert-butylphosphine to o-bis (2-phenyl) bis (diphenylphosphine), the 2-bromo-N-phenylaniline yield increased from 56% to 89%.
Example 3
Preparation of tert-butyl (4-bromophenyl) -phenyl-carbamate method 1, chemical reaction formula:
in a 500 ml single-neck flask, di-tert-butyl dicarbonate (BOC) (0.2mol, 43.6g) was added to 400 ml of tetrahydrofuran at room temperature, followed by addition of p-N- (dibromophenyl) aniline (0.1mol, 24.8g), heating to reflux and stirring for 24 hours, then the mixture was poured into 1L water, and the product was extracted with dichloromethane, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed after separation, and the mixture was purified by silica gel chromatography to give a colorless oily liquid (32.0g, 92% yield).
Example 4
Preparation of (4-bromophenyl) -phenyl-carbamic acid tert-butyl ester method 2:
in a 500 ml one-neck flask, di-tert-butyl dicarbonate (BOC) (0.2mol, 43.6g) was added to 400 ml of tetrahydrofuran at room temperature, followed by p-N- (dibromophenyl) aniline (0.1mol, 24.8g) and N-N2After 20 minutes and heating to reflux and stirring for 24 hours, the mixture was poured into 1L water and the product was extracted with dichloromethane the organic phase was dried over anhydrous magnesium sulfate, separated to remove the solvent and purified by silica gel column chromatography to give a colorless oily liquid (33.0g, 95% yield).
By analysis of examples 3 and 4, it was found that2And is not communicated with N2The reaction yield is not greatly influenced, which indicates that the reaction is not sensitive to oxygen.
Example 5
Method 1 for preparing 10H-spiro [ acridine-9, 2' -adamantane ], the chemical reaction formula is as follows:
in a 200 ml three-necked flask, (4-bromophenyl) -phenyl-carbamic acid tert-butyl ester (8mmol, 2.8g) prepared in example 3 or example 4 was added to 60 ml of anhydrous tetrahydrofuran, then cooled to-80 ℃, further added dropwise 1.6M n-butyllithium (9mmol, 5.2M L) slowly, stirred under argon atmosphere for 2 hours, added with a solution of adamantanone (8.1mmol, 1.2g) in 25 ml of tetrahydrofuran, stirred for 2 hours and then slowly warmed to room temperature, then added with 15 ml of dilute hydrochloric acid (1M), stirred for 12 hours, the mixture was poured into 500 ml of water, and the product was extracted with dichloromethane, dried over anhydrous magnesium sulfate, the solvent was removed after separation, and purified by silica gel chromatography to give a white solid (0.5g, 20.7%).
Example 6
(4-bromophenyl) -phenyl-carbamic acid tert-butyl ester (8mmol, 2.8g) obtained in example 3 or example 4 was added to 60 ml of anhydrous tetrahydrofuran in a 200 ml three-necked flask, then cooled to-80 ℃, and further slowly dropped with 1.6M N-butyllithium (9mmol, 5.2M L). stirring was continued for 2 hours under an argon atmosphere.A solution of adamantanone (8.1mmol, 1.2g) in 25 ml of tetrahydrofuran was added, stirring was continued for 2 hours and then slowly warmed to room temperature.the solvent was distilled off under pressure, 100M L glacial acetic acid was added, and N was introduced2After 20 minutes, 5 ml of concentrated hydrochloric acid were added and heated to reflux and stirred for 24 hours, the mixture was poured into 500 ml of water and the product was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, separated, the solvent was removed, and the residue was purified by silica gel chromatography to give a white solid (1.5g, 62%).
By analytically comparing example 5 and example 6 above, it was found that the reaction process using glacial acetic acid, concentrated hydrochloric acid and heat was effective in promoting the reaction.
Example 7
Preparation of organic small molecule luminescent material based on 10H-spiro [ acridine-9, 2' -adamantane ] donor unit with structural formula 1, chemical reaction formula is as follows:
to a reaction flask were added 10H-spiro [ acridine-9, 2' -adamantane ] (2.4mmol, 0.72g) and 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (2.8mmol, 1.09g), 50 ml of toluene as a solvent, 60 mg of palladium acetate, tri-tert-butylphosphine (0.5mmol, 0.11g) and 0.48 g of sodium tert-butoxide under an argon atmosphere. The reaction was stirred under heating reflux for 24 hours, after cooling, the mixture was poured into 200 ml of water and the product was extracted with dichloromethane. The organic phase is dried by anhydrous magnesium sulfate, the solvent is removed after separation, and a light cyan solid is obtained by silica gel chromatographic column separation and purification. After drying, sublimation was carried out under vacuum to obtain a high purity product (0.72g, 49%). The molecular formula is: C43H36N 4; the molecular weight is: 608.29, respectively; the elemental analysis results were: c, 84.84; h, 5.96; and N, 9.20.
Example 8
Preparation of organic small molecule luminescent material based on 10H-spiro [ acridine-9, 2' -adamantane ] donor unit with structural formula 2, chemical reaction formula is as follows:
compared with example 7, except that 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine was replaced with equimolar amount of 2- (4-bromophenyl) -4, 6-bis (4-methylphenyl) -1,3, 5-triazine, and other materials and procedures were the same as example 7, the yield of the solid product was 75%. The molecular formula of the product is as follows: C45H40N 4; molecular weight: 636.33, respectively; the elemental analysis results were: c, 84.87; h, 6.33; and N, 8.80.
Example 9
Preparation of organic small molecule luminescent material based on 10H-spiro [ acridine-9, 2' -adamantane ] donor unit with structural formula 3, chemical reaction formula is as follows:
compared with example 7, except that 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine was replaced with equimolar amount of 2- (4-bromophenyl) -4, 6-bis (2-methylphenyl) -1,3, 5-triazine, and other materials and procedures were the same as example 7, the yield of the solid product was 75%. The molecular formula of the product is as follows: C45H40N 4; molecular weight: 636.32, respectively; the elemental analysis results were: c, 84.87; h, 6.30; and N, 8.83.
Example 10
Preparation of organic small molecule luminescent material based on 10H-spiro [ acridine-9, 2' -adamantane ] donor unit with structural formula 4, chemical reaction formula is as follows:
compared with example 7, except that 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine was replaced with equimolar amount of 2- (4-bromophenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, the other raw materials and procedures were the same as in example 7, and the yield of the solid product was 65%. The molecular formula of the product is as follows: C47H44N 4; the molecular weight is: 664.36, respectively; the elemental analysis results were: c, 84.90; h, 6.67; n, 8.43.
Example 11
This example tests the 10H-spiro [ acridine-9, 2' -adamantane-based preparation prepared in example 7]The thermal stability of the organic small molecule luminescent material 1 of the donor unit is used for determining the molecular stability of the material and the feasibility of applying the material in an organic luminescent device in a vacuum evaporation mode. The specific implementation steps are as follows: thermogravimetric analysis (TGA) was measured on Netzsch TG 209 with a heating rate of 10 ℃ for min under nitrogen protection-1The heating end point was greater than 600 deg.C, as shown in FIG. 1, and the thermal decomposition temperature of molecule 1 was tested to be 420 deg.C. Has very high decomposition temperature, is easy to obtain high-purity photoelectric material by a gradient sublimation mode, and is suitable for electroluminescent devices.
Example 12
Preparation of organic electroluminescent device
In this example, an organic electroluminescent device using the organic small molecule light-emitting material molecule 1 based on 10H-spiro [ acridine-9, 2' -adamantane ] donor unit prepared in example 7 as a guest material of a light-emitting layer was prepared, and the specific stacked structure is as follows:
glass substrate/indium tin oxide (125 nm)/TAPC (40 nm)/20 wt% or 30 wt% molecules 1: DPEPO (30 nm)/TmPyPB (50 nm)/lithium fluoride (1 nm)/aluminum (100 nm). Indium tin oxide is used as an anode, TAPC is used as a hole transport layer, TmPyPB is used as an electron transport layer, lithium fluoride is used as an electron injection layer, aluminum is used as a cathode, and 1: DPEPO is used as a light emitting layer.
The preparation method comprises the following steps: and ultrasonically cleaning the transparent conductive indium tin oxide glass substrate for 15 minutes by using acetone, a micron-sized semiconductor special detergent, deionized water and isopropanol in sequence to remove dirt on the surface of the substrate. And then putting the mixture into a thermostat to dry at 80 ℃ for later use. And (4) treating the dried indium tin oxide substrate for 4 minutes by using an oxygen plasma starting device to further remove organic pollutants attached to the surface. TAPC, a light emitting layer material, TmPyPB, lithium fluoride, and aluminum were thermally deposited on the light emitting layer by vacuum thermal evaporation to obtain the organic electroluminescent device of the present example.
Comparative example 13
Preparation of organic electroluminescent device
This example produced an organic electroluminescent device using 10- (4- (4, 6-phenyl-1, 3, 5-triazin-2-yl) phenyl) -9, 9-dimethyl-9, 10-dihydroacridine (abbreviated as DMAc-TRZ) (structure shown below) as a guest material for a light-emitting layer.
The specific lamination structure of the organic electroluminescent device is as follows: glass substrate/indium tin oxide (125 nm)/TAPC (40 nm)/20 wt% or 30 wt% DMAc-TRZ DPEPO (40 nm)/TmPyPB (50 nm)/lithium fluoride (1 nm)/aluminum (100 nm). Indium tin oxide as anode, TAPC as hole transport layer, TmPyPB as electron transport layer, lithium fluoride as electron injection layer, aluminum as cathode, DMAc-TRZ DPEPO as light emitting layer.
The method for fabricating the organic electroluminescent device in this embodiment was the same as that of example 12.
Evaluation of Performance of organic photoelectric device
The current at different voltages of the organic electroluminescent devices prepared according to example 12 and comparative example 13 was measured by Keithley 2400 digital nanovolts, and the current density at different voltages of the organic electroluminescent device was obtained by dividing the current by the area for parity.
The brightness and radiant energy density of the organic electroluminescent devices prepared according to example 12 and comparative example 13 at different voltages were tested using a CS-200 spectroradiometer and a PR745 spectro-meter. The current efficiency and the External Quantum Efficiency (EQE) of the organic electroluminescent device are obtained according to the current density and the brightness of the organic electroluminescent device under different voltages.
The current density-voltage-luminance relationship graph, the current efficiency-luminance relationship graph, the external quantum efficiency-luminance relationship graph, and the emission spectrum graph of the organic electroluminescent device of example 12 are shown in fig. 4, 5, 6, and 7, respectively.
A current density-voltage-luminance relationship graph, a current efficiency-luminance relationship graph, an external quantum efficiency-luminance relationship graph, and an emission spectrum graph of the organic electroluminescent device of example 13 are shown in fig. 8, 9,10, and 11, respectively.
Data of the organic electroluminescent devices of examples 12 and 13, such as the starting voltage, the maximum current efficiency, the maximum external quantum efficiency, the CIE coordinates, and the like, are summarized as shown in table 1 below.
TABLE 1
The following conclusions can be drawn by comparative analysis of example 12 and example 13: under the same device conditions, molecule 1 achieved superior external quantum efficiency and a bluer electroluminescence spectrum compared to molecule DMAc-TRZ, probably because: by substitution of two CH's of an acridine group3Effectively reducing the effect of hyperconjugated electron donor in molecule 1, and is further prepared from 10H-spiro [ acridine-9, 2' -adamantane]Molecules consisting of donor unitsThe compound has a very rigid molecular structure, effectively inhibits the relaxation process of the molecular configuration of the molecule under the condition of an excited state, and reduces the Stokes shift of the molecule 1. A bluer electroluminescence spectrum results from the two reasons mentioned above. Higher external quantum efficiencies are obtained compared to DMAc-TRZ, probably because the rigid structure inhibits the non-radiative decay processes of the molecule, increasing the molecular photoluminescence quantum yield and thus the efficiency of the molecule 1-based device. This shows that the organic small molecule light-emitting material of the present invention has a function as a doped guest material in a light-emitting layer. The blue luminescent material has very important significance for full-color display and white light photos, so that the preparation of the high-efficiency blue luminescent material with application potential has great significance.
The molecular structural formulae of TAPC, mCP, DPEPO, and TmPyPB described in example 12 and example 13 are respectively as follows:
the above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications that are made without departing from the spirit and principle of the present invention are all equivalent substitutions included in the protection scope of the present invention.
In conclusion, the organic small-molecule luminescent material is obtained by coupling a novel acridine donor unit 10H-spiro [ acridine-9, 2 '-adamantane ] based on nonaromatic rigid structure adamantane with an acceptor unit, has a single structure, determined molecular weight, convenient purification, good reproducibility of multiple synthesis, lower sublimation temperature and higher decomposition temperature, and stable film form, because the donor unit 10H-spiro [ acridine-9, 2' -adamantane ] has a very rigid structure, and the nonaromatic rigid structure adamantane is used as a donor part structure, the organic small-molecule luminescent material has very high photoluminescence quantum yield in a film state, and can effectively solve the problem that an excited molecule is low in device efficiency due to severe nonradiative attenuation caused by configuration relaxation when being applied to an organic electroluminescent device, and the material characteristics such as luminous color, molecular weight, electrophilicity and the like of the material can be adjusted by changing the type of the acceptor unit connected with the 10H-spiro [ acridine-9, 2' -adamantane ], the conjugation length and intramolecular charge transfer of the material can be effectively regulated, and the energy levels of the highest occupied orbit and the lowest unoccupied orbit are adjusted to meet the requirements of the organic electroluminescent device, so that the device can be endowed with more excellent performance when the material is applied to the organic electroluminescent device. According to the organic electroluminescent device, the luminescent layer is made of the organic micromolecule luminescent material, so that the external quantum efficiency of the organic electroluminescent device can be effectively improved, and the organic electroluminescent device has excellent device performance.
As described above, it will be apparent to those skilled in the art that other various changes and modifications may be made based on the technical solution and concept of the present invention, and all such changes and modifications are intended to fall within the scope of the appended claims.
Claims (7)
1. An organic micromolecule luminescent material is characterized in that 10H-spiro [ acridine-9, 2' -adamantane ] is used as a donor unit, and the luminescent material is obtained by coupling an acceptor unit and the donor unit;
10H-spiro [ acridine-9, 2' -adamantane]Has the chemical structural formula of
The chemical structural formula of the organic micromolecule luminescent material is shown as
2. A method for preparing an organic micromolecule luminescent material is characterized in that a donor unit 10H-spiro [ acridine-9, 2' -adamantane ] and an acceptor unit are used as raw materials and are prepared by Hartwig-Buchwald coupling reaction;
wherein, the 10H-spiro [ acridine-9, 2' -adamantane]Has the chemical structural formula of
The acceptor unit is:
the chemical structural formula of the organic micromolecule luminescent material is as follows:
3. the method for preparing the organic small-molecule luminescent material according to claim 2, wherein the 10H-spiro [ acridine-9, 2' -adamantane ] is prepared by taking aniline, o-bromoiodobenzene and adamantanone as raw materials, and the specific preparation process is as follows:
step 1,
Step 2,
Step 3,
4. An organic electroluminescent device is characterized by comprising a light-transmitting substrate, an anode layer, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer and a cathode layer which are arranged in a stacking manner; the light-emitting layer comprises the organic small molecule light-emitting material according to claim 1.
5. The organic electroluminescent device according to claim 4, wherein the organic small molecule light emitting material serves as a light emitting guest material in the light emitting layer.
6. The organic electroluminescent device according to claim 4, wherein the light-emitting layer comprises one or more of the organic small molecule light-emitting materials having different structural formulae.
7. The organic electroluminescent device according to claim 4, wherein the light-emitting layer is formed by thermal evaporation, spin coating, brush coating, spray coating, dip coating, roll coating, printing or ink jet printing.
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| KR20210137594A (en) * | 2020-05-07 | 2021-11-18 | 삼성디스플레이 주식회사 | Heterocyclic compound and light emitting device including the same |
| KR20210153188A (en) * | 2020-06-09 | 2021-12-17 | 삼성디스플레이 주식회사 | Heterocyclic compound and light emitting device including the same |
| CN114516829A (en) * | 2022-02-16 | 2022-05-20 | 闽都创新实验室 | Stilbene derivative, preparation and application thereof |
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| US9944627B2 (en) * | 2016-05-09 | 2018-04-17 | National Taiwan University | Spiroacridine-triazine hybrids and applications for electroluminescent devices |
| KR20180063426A (en) * | 2016-12-01 | 2018-06-12 | 삼성디스플레이 주식회사 | Aromatic compound and organic electroluminescence device including the same |
| KR102649432B1 (en) * | 2016-12-29 | 2024-03-19 | 엘지디스플레이 주식회사 | Organic compounds, organic light emitting diode and organic light emitting device having the compounds |
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