WO2013070026A1 - 1,1'-binaphthyl-4,4'-diamine derivatives for luminescence of organic electroluminescent device and organic electroluminescent device using them - Google Patents

1,1'-binaphthyl-4,4'-diamine derivatives for luminescence of organic electroluminescent device and organic electroluminescent device using them Download PDF

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WO2013070026A1
WO2013070026A1 PCT/KR2012/009470 KR2012009470W WO2013070026A1 WO 2013070026 A1 WO2013070026 A1 WO 2013070026A1 KR 2012009470 W KR2012009470 W KR 2012009470W WO 2013070026 A1 WO2013070026 A1 WO 2013070026A1
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chemical formula
electroluminescent device
organic electroluminescent
organic
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French (fr)
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Min Sun Lee
Chun Rim Oh
Young Sung Kim
Bong Seok Moon
In Young So
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Samyangems Co., Ltd.
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    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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    • 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
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    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
    • Y02B20/30—Semiconductor lamps, e.g. solid state lamps [SSL] light emitting diodes [LED] or organic LED [OLED]
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Definitions

  • the present invention relates to binaphthyl amine derivatives suitable for use in light sources of displays such as mobile phones, navigation systems, TV sets, etc., and more particularly to a 1,1'-binaphthyl-4,4'-diamine derivative for luminescence of an organic electroluminescent device.
  • an organic light-emitting device is configured such that an organic layer is disposed between a cathode and an anode.
  • the overall configuration of the device is composed of a transparent anode comprising indium tin oxide (ITO), a hole injection layer (HIL), a hole transport layer (HTL), an emissive layer (EL), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL) and a cathode comprising LiAl.
  • ITO indium tin oxide
  • HIL hole injection layer
  • HTL hole transport layer
  • EL emissive layer
  • HBL hole blocking layer
  • ETL electron transport layer
  • EIL electron injection layer
  • cathode comprising LiAl.
  • One or two layers may be omitted in the organic layer structure, depending on needs.
  • Such luminescent materials are classified into a fluorescent material and a phosphorescent material, and formation of the emissive layer includes methods of doping a fluorescent host (a pure organic material) with a phosphorescent material (an organic metal), doping a fluorescent host with a fluorescent dopant (an organic material containing nitrogen, etc.), applying a dopant (DCM, Rubrene, DCJTB or the like) to a luminescent material to achieve a long wavelength, etc.
  • a dopant DCM, Rubrene, DCJTB or the like
  • the luminescent materials include a symmetric/asymmetric host/dopant having high blue emission efficiency in OLEDs.
  • Generally materials for emissive layers have structures comprising a center such as benzene, naphthalene, fluorene, spirofluorene, anthracene, pyrene, carbazole, etc., a ligand such as phenyl, biphenyl, naphthalene, heterocycle or the like, a bonding position of ortho, meta and para, and a substituent such as amine, cyane, fluorine, methyl, trimethyl, etc.
  • the target to be solved is a blue luminescent material, and high-performance luminescent materials are required toward blue and deep blue from sky blue at present.
  • the device is required to have high emission efficiency at low driving voltage and glass transition temperature which increases thermal stability in chemical structures of materials.
  • DNBN blue emission host
  • Mol. Cryst. Liq. Cryst., Vol. 531: pp. 55/[355]64 [364]
  • TPBND TPBND
  • BN1 blue emission dopant and HTL
  • the present inventors carried out thorough research into developing materials which have two amines directly bonded to 4,4' positions of 1,1'-binaphthyl different from DNBN (4,4'-(dinaphthalen-2-yl)-1,1'-binaphthyl) and BN1 (4,4'-(1,1'-binaphthyl-4,4'-diyl)bis(N,N-diphenylaniline)) and may be used as luminescent materials, unlike hole materials (a hole transport material or a hole injection material) of the prior literatures, for example, TPBND (3,3'-dimethyl-N4,N4,N4',N4'-tetraphenyl-1,1'-binaphthyl-4,4'-diamine), and compounds disclosed in Korean Patent Application Nos. 2006-0080471 and 2008-0040498 and Japanese Register Patent No. 4215837, thereby providing compounds represented by Chemical Formula 1 for luminescence of organic electroluminescent devices.
  • the present invention is intended to provide a 1,1'-binaphthyl-4,4'-diamine derivative for luminescence of an organic electroluminescent device, having superior thermal stability in a chemical structure.
  • the present invention is intended to provide a method of preparing the 1,1'-binaphthyl-4,4'-diamine derivative for luminescence of an organic electroluminescent device.
  • the present invention is intended to provide an organic electroluminescent device including the 1,1'-binaphthyl-4,4'-diamine derivative.
  • An aspect of the present invention provides a 1,1'-binaphthyl-4,4'-diamine derivative represented by Chemical Formula 1 below for luminescence of an organic electroluminescent device.
  • Ar 1 and Ar 2 , and R 1 and R 2 are independently the same as or different from each other, Ar 1 and Ar 2 are phenyl, naphthalene, anthracene, phenanthracene or pyrene, R 1 is a substituted or unsubstituted C6 ⁇ C30 aryl or a substituted or unsubstituted C5 ⁇ C30 heteroaryl, R 2 is phenyl, toluene, naphthalene, anthracene, phenanthracene, pyrene, or carbazole, and n and m are an integer ranging from 0 to 3.
  • R 1 which is a substituted or unsubstituted C6 ⁇ C30 aryl or a substituted or unsubstituted C5 ⁇ C30 heteroaryl may be any one selected from among compounds described in Table 1 below.
  • Another aspect of the present invention provides a method of preparing the compound of Chemical Formula 1, comprising subjecting a compound represented by Chemical Formula A below to a carbon-carbon coupling reaction to synthesize a compound represented by Chemical Formula B below; and subjecting the compound represented by Chemical Formula B to amination thus preparing the compound represented by Chemical Formula 1 in the following Scheme 1.
  • a further aspect of the present invention provides an organic electroluminescent device comprising the compound represented by Chemical Formula 1.
  • the use of a 1,1'-binaphthyl-4,4'-diamine derivative for luminescence of an OLED can result in blue luminescence, high emission efficiency and a long lifetime.
  • an OLED can be actually utilized and is very industrially available.
  • the OLED of the invention can be appropriately applied to flat panel displays, flat panel light-emitting materials, light-emitting materials of OLEDs for lighting surface emission, flexible light-emitting materials, copiers, printers, light sources of meters or LCD backlights, display plates, indicators, etc.
  • FIG. 1 schematically illustrates the construction of an OLED
  • FIG. 2 illustrates the multilayer structure of the OLED
  • FIG. 3 illustrates the multilayer structure having no hole blocking layer
  • FIG. 4 illustrates the NMR of an intermediate [1]
  • FIGS. 5a, 5b, 5d and 5d illustrate the DSC data of compounds A-1, A-2, A-5 and A-7, respectively.
  • a 1,1'-binaphthyl-4,4'-diamine derivative for luminescence of an organic electroluminescent device is provided, as is represented by Chemical Formula 1 below.
  • Ar 1 and Ar 2 , and R 1 and R 2 are independently the same as or different from each other, Ar 1 and Ar 2 are phenyl, naphthalene, anthracene, phenanthracene or pyrene, R 1 is a substituted or unsubstituted C6 ⁇ C30 aryl or a substituted or unsubstituted C5 ⁇ C30 heteroaryl, R 2 is phenyl, toluene, naphthalene, anthracene, phenanthracene, pyrene, or carbazole, and n and m are an integer ranging from 0 to 3.
  • R 1 of Chemical Formula 1 used for luminescence of an organic electroluminescent device is selected from among compounds of Table 1 below.
  • a method of preparing the 1,1'-binaphthyl-4,4'-diamine derivative compound represented by Chemical Formula 1 below for luminescence of an organic electroluminescent device comprises subjecting a compound represented by Chemical Formula A below to a carbon-carbon coupling reaction to synthesize a compound represented by Chemical Formula B below; and subjecting the compound of Chemical Formula B to amination thus preparing the compound of Chemical Formula 1 in the following Scheme 1.
  • Ar 1 and Ar 2 , and R 1 and R 2 are independently the same as or different from each other, Ar 1 and Ar 2 are phenyl, naphthalene, anthracene, phenanthracene or pyrene, R 1 is a substituted or unsubstituted C6 ⁇ C30 aryl or a substituted or unsubstituted C5 ⁇ C30 heteroaryl, R 2 is phenyl, toluene, naphthalene, anthracene, phenanthracene, pyrene, or carbazole, and n and m are an integer ranging from 0 to 3.
  • R 1 which is a substituted or unsubstituted C6 ⁇ C30 aryl or a substituted or unsubstituted C5 ⁇ C30 heteroaryl is any one selected from among compounds of Table 1.
  • the compound of Chemical Formula B is prepared as follows.
  • N-phenyl-1-naphthylamine [Chemical Formula A] is dissolved in CH 2 Cl 2 under a nitrogen stream in a reactor, and TiCl 4 is added dropwise, after which the resulting solution is added with a saturated potassium carbonate aqueous solution, stirred, and extracted with CH 2 Cl 2 , thus obtaining an organic layer which is then dried over MgSO 4 , dewatered under reduced pressure, and purified using silica gel chromatography, yielding a brown solid compound of Chemical Formula B.
  • the compound of Chemical Formula 1 is prepared from the compound of Chemical Formula B as below.
  • the reagents or the reaction solvents used in the above reaction are not particularly limited thereto.
  • the organic electroluminescent device of the present invention may be manufactured using a typical method of manufacturing an organic electroluminescent device and materials therefor, with the exception that the above compounds are used as a luminescent material.
  • an organic electroluminescent device using the compound of Chemical Formula 1 is provided.
  • the organic electroluminescent device is selected from among an organic light-emitting device (OLED), an organic solar cell (OSC), e-paper, an organic photoconductor (OPC), and an organic thin-film transistor (OTFT).
  • OLED organic light-emitting device
  • OSC organic solar cell
  • OPC organic photoconductor
  • OTFT organic thin-film transistor
  • the OLED may be configured such that an organic layer is disposed between an anode as a first electrode and a cathode as a second electrode, and the compound of the invention may be used as a luminescent material.
  • the OLED of the invention may be manufactured by depositing a metal, a conductive metal oxide or alloys thereof on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation to form an anode, forming an organic layer comprising a hole injection layer, a hole transport layer, an emissive layer, a hole blocking layer and an electron transport layer on the anode, and depositing a material for a cathode on the organic layer.
  • PVD physical vapor deposition
  • the OLED may be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate.
  • the organic layer may have a multilayer structure comprising a hole injection layer, a hole transport layer, an emissive layer, a hole blocking layer and an electron transport layer. Also, the organic layer may be manufactured to have a lesser number of layers by not using a deposition process but by using a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing or heat transfer, using a variety of polymer materials.
  • a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing or heat transfer, using a variety of polymer materials.
  • the anode material may be a material having a high work function so as to enable the efficient injection of holes into the organic layer.
  • Specific examples of the anode material useful in the invention include, but are not limited to, metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), titanium oxide (TiO), or indium zinc oxide (IZO); a combination of a metal and an oxide such as ZnO:Al or SnO 2 :Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole, and polyaniline, etc.
  • metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof
  • metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), titanium oxide (TiO), or indium zinc oxide
  • the cathode material may be a material having a low work function so as to facilitate the injection of electrons into the organic layer.
  • Specific examples of the cathode material useful in the invention include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gallium, aluminum, silver, tin and lead, and alloys thereof; a multilayer structure material such as LiAl and LiF/Al or LiO 2 /Al, etc.
  • the hole injection material may be a material able to efficiently receive holes from the anode at a low voltage, and the HOMO (Highest Occupied Molecular Orbital) level of the hole injection material may fall in the range between the work function of the anode material and the HOMO of the organic layer.
  • HOMO Highest Occupied Molecular Orbital
  • a material having good surface adhesion to the anode, and the ability to relieve surface roughness of the anode is particularly useful.
  • the hole injection material include, but are not limited to, organic materials such as metal porphyrine, oligothiophene, arylamine and so on, organic materials such as hexaazatriphenylene hexanitrile and so on, organic materials such as quinacridone and so on, organic materials such as perylene, and conductive polymers such as anthraquinone, polyaniline, polythiophene and so on.
  • the hole transport material may be a material having high hole mobility so that holes may be transported to the emissive layer from the anode or the hole injection layer.
  • a material having HOMO and LUMO levels greater than the bandgap of the emissive layer is also useful.
  • a material having high thermal stability in a chemical structure include organic materials such as arylamine and so on, conductive polymers, and block copolymers having both conjugated and non-conjugated portions.
  • the hole material is mainly exemplified by TPD (N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-benzidine), NPB (N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine), b-NPB (N,N'-bis(naphthalen-2-yl)-N,N'-bis(phenyl)-benzidine), PAPB (N,N'-bis(phenanthren-9-yl)-N,N'-bis(phenyl)-benzidine), a-TNB (N,N,N',N'-tetra-naphthalen-2-yl-benzidine), or a,b-TNB (N,N'-di(naphthalenyl)-N,N'-di(naphthalen-2-yl)-benzidine), having a diamine structure.
  • TPD N,N'-bis(3-methylphenyl
  • N-diaryl structure of anthracene or bianthracene for example, TPA (9,10-bis[phenyl(m-tolyl)-amino]anthracene), TTPA (9,10-bis[N,N-di-(p-tolyl)-amino]anthracene), BA-NPB (N 10 ,N 10' -diphenyl-N 10 ,N 10' -dinaphthalenyl-9,9'-bianthracene-10,10'-diamine), BA-TAD (N 10 ,N 10 ,N 10' ,N 10' -tetra-phenyl-9,9'-bianthracene-10,10'-diamine), BA-TTB [N 10 ,N 10 ,N 10' ,N 10' -tetra-tolyl-9,9'-bianthracene-10,10'-diamine] may be used as a green dopant.
  • the emission wavelengths of MT-01, MT-02, and MT-03 disclosed in Japanese Patent No. 4215837 are respectively 441 nm, 439 nm, and 436 nm, which are evaluated to be too short.
  • the emission wavelength and efficiency should be adjusted using Ar 1 , Ar 2 , R 1 and R 2 of Chemical Formula 1.
  • the hole blocking material may be a material having a HOMO level greater than that of the emissive layer.
  • Useful is a material having high thermal stability in a chemical structure. Specific examples thereof include, but are not limited to, TPBi (2,2',2"-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole)) and BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), which are mainly utilized; CBP (4,4'-bis(carbazol-9-yl)biphenyl), PBD (2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole) and PTCBI (bisbenzimidazo[2,1-a:1',2-b']anthra[2,1,9-def:6,5,10-d'e'f']diisoguinoline-10,21-dione),
  • the electron transport material may be a material having high electron mobility so that electrons may be transported to the emissive layer from the cathode. Also useful is a material having high thermal stability in a chemical structure. Specific examples thereof include, but are not limited to, aluminum 8-hydroxyquinolinate complexes; Alq 3 complexes; organic radical compounds; hydroxyflavon-metal complexes, etc.
  • the luminescent material may be a material having high quantum efficiency so that holes and electrons transported from the hole transport layer and the electron transport layer are combined thus emitting light in the visible range.
  • blue luminescent materials such as ADN (9,10-di(naphth-2-yl)anthracene), MADN (2-methyl-9,10-bis(naphthalen-2-yl)anthracene), DPVBi (4,4'-bis(2,2'-diphenylvinyl)-1,1'-biphenyl), BAlq (bis(2-methyl-8-quinolinolate)-4-(phenylphenolato)aluminium) and so on, green luminescent materials such as Alq 3 and other anthracenes, pyrene, fluorene, spirofluorene, carbazole, benzoxazole, benzothiazole, benzimidazole compounds, polymeric poly(p-phenylene vinylene), polyspiro, polyfluoren
  • the blue luminescent material is required to have, first, an emission wavelength of 445 ⁇ 470 nm. If the emission wavelength is too short, the bandgap (Eg) may increase, undesirably increasing the driving voltage or accumulating a large number of layers. Second, emission efficiency of 6 ⁇ 7 cd/A or more is currently required. The measurement thereof may vary depending on the type of method of manufacturing the device, and performance is compared using a standard material. Third, thermal stability is required, and a glass transition temperature (Tg) should be 120°C or more. Tg is related to the lifetime because it is connected with thermal stability of a compound structure.
  • HOMO should be 5.7 ⁇ 6.0 eV
  • the bandgap (Eg) should be 2.9 eV or more. If HOMO is 6.0 eV or more, its difference from the hole transport layer (HTL; 5.6 ⁇ 5.7 eV) may increase, thus increasing the driving voltage.
  • the present inventors made an effort to solve problems such as green wavelengths of N-diaryl structures (TPD, TPA, TTPA, BA-NPB, BA-TAD, BA-TTB) of conventional anthracene or bianthracene and too short wavelengths of MT-01, MT-02, and MT-03 in JP 4215837, and they synthesized compounds of Chemical Formula 1 and compared them with 9,10-di-(2-naphthyl) anthracene (ADN) as a control in terms of emission efficiency and wavelength. Consequently, the compounds of the invention can be confirmed to exhibit superior emission efficiency and desired wavelength.
  • the OLED of the invention may be of a front-side emission type, a back-side emission type, or a double-sided emission type depending on the type of material used.
  • the compound of the invention may also function in organic electroluminescent devices, including organic solar cells, lighting OLEDs, flexible OLEDs, organic photoconductors, organic transistors, etc., according to a principle similar to that applied to the OLED.
  • N-phenyl-1-naphthylamine (5 mmol) was dissolved in dichloromethane under a nitrogen stream, after which the temperature of the solution was maintained at -5°C and then TiCl 4 (TiCl 4 /CH 2 Cl 2 1:1 solution, 1.7 mmol) was added dropwise for 5 min, followed by carrying out the reaction at -5°C for 1 h and then at 0°C for 8 h.
  • the mixture obtained in the previous step was slowly added dropwise to the KI solution. After 15 min, a NaOH aqueous solution (130 g/250 ml) was added dropwise little by little.
  • reaction solution was cooled, stirred with 300 ml of CH 2 Cl 2 , and extracted with CH 2 Cl 2 thus obtaining an organic layer, which was then dried over MgSO 4 , dewatered under reduced pressure, and purified using silica gel chromatography, giving white crystals at a yield of 40%.
  • reaction solution was cooled and extracted with CH 2 Cl 2 .
  • the resulting organic layer was then dried over MgSO 4 , dewatered under reduced pressure, and purified using silica gel chromatography, giving 0.72 g of the title compound at a yield of 60%.
  • reaction solution was cooled and extracted with CH 2 Cl 2 , thus obtaining an organic layer, which was then dried over MgSO 4 , dewatered under reduced pressure, and purified using silica gel chromatography, giving 0.34 g of the title compound at a yield of 45%.
  • reaction solution was cooled and extracted with CH 2 Cl 2 , thus obtaining an organic layer, which was then dried over MgSO 4 , dewatered under reduced pressure, and purified using silica gel chromatography, giving 0.69 g of a product at a yield of 72%.
  • 1,4-dibromobenzene (21.2 mmol), naphthalene-1-boronic acid (31.8 mmol), and Pd(PPh 3 ) 4 (1.06 mmol) were placed in a three-neck reactor, and dissolved in 50 ml of THF under a nitrogen stream.
  • reaction solution was cooled and extracted with CH 2 Cl 2 , thus obtaining an organic layer, which was then dried over MgSO 4 , dewatered under reduced pressure, and purified using silica gel chromatography, giving 3.6 g of the title compound at a yield of 60%.
  • reaction solution was cooled and extracted with CH 2 Cl 2 , thus obtaining an organic layer, which was then dried over MgSO 4 , dewatered under reduced pressure, and purified using silica gel chromatography, giving 3.6 g of the title compound at a yield of 60%.
  • reaction solution was cooled and extracted with CH 2 Cl 2 , thus obtaining an organic layer, which was then dried over MgSO 4 , dewatered under reduced pressure, and purified using silica gel chromatography, giving 3 g of the title compound at a yield of 45%.
  • reaction solution was cooled and extracted with CH 2 Cl 2 , thus obtaining an organic layer, which was then dried over MgSO 4 , dewatered under reduced pressure, and purified using silica gel chromatography, giving 5 g of the title compound at a yield of 70%.
  • 1,4-dibromonaphthalene (21.2 mmol), naphthalene-1-boronic acid (31.8 mmol), and Pd(PPh 3 ) 4 (1.06 mmol) were placed in a three-neck reactor, and dissolved in 50 ml of THF under a nitrogen stream.
  • reaction solution was cooled and extracted with CH 2 Cl 2 , thus obtaining an organic layer, which was then dried over MgSO 4 , dewatered under reduced pressure, and purified using silica gel chromatography, giving 3.88 g of the title compound at a yield of 55%.
  • a hole transport layer was made of NPB (N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-benzidine) or JP4215837
  • a luminescent material was an AND (9,10-di(naphth-2-yl)anthracene) host alone or an ADN host and one among dopants A-1 to A-15
  • a hole blocking layer was made of TPBi (2,2',2"-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole)) and an electron transport layer was made of Alq 3 (tris(8-hydroxy-quinolinato)aluminum) or LiF (lithium fluoride).
  • a glass substrate coated with an ITO (indium tin oxide) thin film at a thickness of 1500 ⁇ was placed in secondary distilled water having a detergent available from Fischer dissolved therein and ultrasonically washed. ITO was washed for 30 min and then ultrasonically washed for 10 min using distilled water two times. After completion of the washing with distilled water, the substrate was ultrasonically washed using a solvent such as isopropyl alcohol, acetone, or methanol, dried, and transferred to a plasma cleaning machine. The substrate was cleaned for 5 min using oxygen plasma and then transferred to a vacuum evaporator.
  • ITO indium tin oxide
  • a hole layer NPB at a thickness of 700 ⁇ , an emissive layer at a thickness of 300 ⁇ using the anthracene based ADN compound, a hole blocking layer at a thickness of 200 ⁇ using a TPBi compound, and an electron transport layer at a thickness of 400 ⁇ using an Alq 3 compound were vacuum deposited on the thus-prepared ITO transparent electrode, after which LiF at 5 ⁇ and Al (aluminum) at 1000 ⁇ were sequentially deposited, thus forming a cathode.
  • the rate of deposition of the organic material was maintained at 1 ⁇ /sec, the lithium fluoride at 0.2 ⁇ /sec, and the Al at 3 ⁇ 7 ⁇ /sec.
  • the electroluminescent properties of the manufactured OLED are shown in Table 2 below.
  • An OLED was manufactured in the same manner as in Comparative Example 1, with the exception that JP4215837 was vacuum deposited at a thickness of 700 ⁇ instead of NPB, as the hole transport material.
  • Example 1 ITO / NPB / ADN:A-1 / TPBi / Alq 3 / LiF / Al
  • An OLED was manufactured in the same manner as in Comparative Example 1, with the exception that ADN of the emissive layer was doped with 0.5% of the A-1 compound of Synthesis Example 1.
  • OLEDs were manufactured in the same manner as in Example 1, with the exception that A-2 to A-15 were respectively used instead of A-1.
  • the electroluminescent properties of the OLEDs are shown in Table 2 below.
  • the properties of the OLEDs of Comparative Examples 1 and 2 and Examples 1 to 15 were evaluated. The results are shown in Table 2 below.
  • the unit of current density was mA/cm 2
  • the unit of color coordinates was CIE 1931 (x, y)
  • the efficiency was calculated using luminance and current density and the unit thereof was cd/A
  • the unit of lifetime was h at 1000 nit.
  • the compounds represented by Chemical Formula 1 according to the present invention could be used to form a thin-film layer for luminescence of an OLED, and emitted light in the blue, sky blue and green wavelength ranges, and the color coordinates, the emission efficiency and the lifetime thereof were improved.
  • the examples wherein ADN was doped with the compound of Chemical Formula 1 in which R 2 is a phenyl group, a naphthalenyl group, an anthracene group, a phenanthracene group or a pyrene group could be seen to manifest color coordinates of a variety of wavelengths, superior emission efficiency and improved lifetime, compared to the anthracene compound (AND) of the comparative example.

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PCT/KR2012/009470 2011-11-10 2012-11-09 1,1'-binaphthyl-4,4'-diamine derivatives for luminescence of organic electroluminescent device and organic electroluminescent device using them WO2013070026A1 (en)

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CN106688119B (zh) * 2014-07-09 2019-07-23 保土谷化学工业株式会社 有机电致发光器件

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