WO2013180456A1 - Novel organic electroluminescent compounds and organic electroluminescent device comprising the same - Google Patents

Novel organic electroluminescent compounds and organic electroluminescent device comprising the same Download PDF

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WO2013180456A1
WO2013180456A1 PCT/KR2013/004688 KR2013004688W WO2013180456A1 WO 2013180456 A1 WO2013180456 A1 WO 2013180456A1 KR 2013004688 W KR2013004688 W KR 2013004688W WO 2013180456 A1 WO2013180456 A1 WO 2013180456A1
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group
substituted
unsubstituted
alkyl
compound
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Jin-Hee Kim
Hyo-Jung Lee
Young-Gil Kim
Hyo-Nim Shin
Kyung-Joo Lee
Hong-Yoep NA
Young-Jun Cho
Hyuck-Joo Kwon
Bong-Ok Kim
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Rohm And Haas Electronic Materials Korea Ltd.
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Publication of WO2013180456A1 publication Critical patent/WO2013180456A1/en

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    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
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    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • 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
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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    • H10K85/30—Coordination compounds
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    • H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
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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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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—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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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
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    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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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
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom

Definitions

  • the present invention relates to novel organic electroluminescent compounds and an organic electroluminescent device comprising the same.
  • An electroluminescent (EL) device is a self-light-emitting device with the advantage of providing a wider viewing angle, a greater contrast ratio, and a faster response time.
  • An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules and aluminum complexes as material for forming a light-emitting layer [ see Appl. Phys. Lett. 51, 913, 1987].
  • the organic EL device emits a light by the injection of a charge into an organic film formed between an electron injection electrode (cathode) and a hole injection electrode (anode) and by the extinction of an electron-hole pair.
  • the organic EL device has the following advantages: it can be formed onto a flexible transparent substrate, such as plastic; can be driven at a lower voltage, for example, 10 V or less, over a plasma display panel or an inorganic EL display; has relatively low power consumption; and provides good color. Further, the organic EL device provides tricolor light-emission, i.e., green, blue or red light-emission, and thus there is interest from many people as a next generation color display device.
  • the most important factor determining properties, such as luminescent efficiency, lifespan, etc., in an organic EL device is the light-emitting material.
  • the light-emitting material is required to have the following features: high luminescent quantum yield in a solid state, high movement degree of an electron and a hole, non-breakdown in vacuum deposition, formability of a uniform thin film, and stability.
  • the organic EL device is generally composed of a cathode/a hole injection layer (HIL)/a hole transport layer (HTL)/a light-emitting layer (EML)/an electron transport layer (ETL)/an electron injection layer (EIL)/an anode, and green, blue or red light-emitting of the organic EL device can be embodied depending on how to form a light-emitting layer.
  • HIL hole injection layer
  • HTL hole transport layer
  • EML electron transport layer
  • EIL electron injection layer
  • the light-emitting material is classified into a host material and a dopant material in the functional aspect.
  • the light-emitting layer wherein a dopant is doped onto a host, was known.
  • an urgent task is the development of an organic EL device having high efficacy and a long operating lifespan.
  • the development of highly excellent light-emitting material over conventional light-emitting materials is urgent considering EL properties required in medium- and large-sized OLED panels.
  • a blue light-emitting material system by using diphenylvinyl-biphenyl (DPVBi) and a distyryl blue light-emitting material system (Idemitsu Kosan), and blue light-emitting material systems of dinaphthylanthracene and tetra(t-butyl)perylene (Eastman Kodak) were known.
  • DPVBi diphenylvinyl-biphenyl
  • Idemitsu Kosan distyryl blue light-emitting material system
  • Eastman Kodak blue light-emitting material systems of dinaphthylanthracene and tetra(t-butyl)perylene
  • the distyryl blue light-emitting material system of Idemitsu Kosan is effective, since it provides a device having 6 lm/W of power efficiency and 30000 or more hours of operating lifespan.
  • the system shows the reduction of color purity with the passage of driving time of a device, when it is applied to a full color display, it shows only several thousand hours of lifespan.
  • the conventional blue light-emitting materials do not compose a light-emitting layer by using a host-dopant system, and compose a light-emitting layer by using only host compounds or dopant compounds. Thus, it is difficult to commercially use them in terms of color purity and efficiency. Further, credible data for a long lifespan is insufficient.
  • blue light-emission shows better luminescent efficiency, but does not satisfy pure blue color, and thus cannot be applied to high quality displays. Further, it has problems in color purity, efficiency and thermal stability. Thus, it is urgent to develop blue light-emitting materials.
  • Korean Patent Application Laying-Open No. 10-2011-0027033 discloses an organic EL device comprising anthracene derivatives and amine derivatives
  • Korean Patent Application Laying-Open No. 10-2011-0115887 discloses an organic EL device comprising amine-based compounds.
  • organic EL devices comprising the compounds disclosed in the publications as a dopant material are not satisfactory in luminescent efficiency and color purity.
  • the objective of the present invention is to provide an organic electroluminescent compound, in particular dopant materials, having high luminescent efficiency and a long lifespan and showing blue light-emission having high color purity; and an organic electroluminescent device having high efficiency and a long operating lifespan, comprising the organic electroluminescent compound.
  • L 1 and L 2 each independently represent a single bond, a substituted or unsubstituted 5- to 30-membered heteroarylene group, or a substituted or unsubstituted (C6-C30)arylene group;
  • X represents a single bond or CR 11 R 12 ;
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted 5- to 30-membered heteroaryl group, or a substituted or unsubstituted (C6-C30)aryl group;
  • R 1 to R 6 each independently represent hydrogen, deuterium, a halogen, a cyano group, a nitro group, a hydroxyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a saturated or unsaturated ring;
  • R 7 represents hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30-membered heteroaryl group;
  • R 11 and R 12 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a saturated or unsaturated ring;
  • n an integer of 1 or 2; where n is 2, each of R 7 is the same or different; and
  • the organic electroluminescent compounds according to the present invention have high luminescent efficiency and a long lifespan, and show blue light-emission having high color purity, over the conventional dopant materials.
  • an organic electroluminescent device having high efficiency, a long operating lifespan, and enhanced power consumption efficiency can be prepared by using the organic electroluminescent compounds according to the present invention.
  • the present invention relates to an organic electroluminescent compound represented by formula 1 above, an organic electroluminescent material comprising the organic electroluminescent compound, and an organic electroluminescent device comprising the material.
  • L 1 and L 2 each independently represent a single bond, a substituted or unsubstituted 5- to 20-membered heteroarylene group, or a substituted or unsubstituted (C6-C20)arylene group; and more preferably a single bond, a 5- to 20-membered heteroarylene group which is unsubstituted or substituted with a (C1-C6) alkyl group, or an unsubstituted (C6-C20)arylene group.
  • L 1 and L 2 each independently represent a single bond, phenylene, biphenylene, naphthylene, fluorenylene, phenanthrenylene, pyridylene, pyrazinylene, pyrimidinylene or pyridazinylene.
  • X represents a single bond or CR 11 R 12 , in which preferably R 11 and R 12 each independently represent hydrogen or an unsubstituted (C6-C20)aryl group.
  • Ar 1 and Ar 2 each independently represent a substituted or unsubstituted 5- to 20-membered heteroaryl group, or a substituted or unsubstituted (C6-C20)aryl group; and more preferably a 5- to 15-membered heteroaryl group which is unsubstituted or substituted with deuterium, a halogen, a cyano group, a hydroxyl group, a (C1-C6)alkyl group, a halo(C1-C6)alkyl group, a (C1-C6)alkoxy group, a (C6-C12)aryl group, a 5- to 15- membered heteroaryl group, a tri(C1-C6)alkylsilyl group, a tri(C6-C12)arylsilyl group, a di(C1-C6)alkyl(C6-C12)arylsilyl group or a (C1-C6)alkyldi(C
  • R 1 to R 6 each independently represent hydrogen, a halogen, a cyano group, a substituted or unsubstituted (C1-C10)alkyl group, or a substituted or unsubstituted (C6-C12)aryl group; and more preferably hydrogen, a halogen, a cyano group, an unsubstituted (C1-C10)alkyl group, or a (C6-C12)aryl group which is unsubstituted or substituted with a cyano group.
  • R 7 represents hydrogen, or a substituted or unsubstituted (C1-C6)alkyl group; and more preferably hydrogen, or an unsubstituted (C1-C6)alkyl group.
  • (C1-C30)alkyl is meant to be a linear or branched alkyl having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.
  • “(C1-C30) alkoxy” is meant to be a linear or branched alkoxy having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and includes methoxy, ethoxy, propoxy, iso-propoxy, 1-ethylpropoxy, etc.
  • (C3-C30)cycloalkyl is a mono- or polycyclic hydrocarbon having 3 to 30 carbon atoms, in which the number of carbon atoms is preferably 3 to 20, more preferably 3 to 7, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • (C6-C30)aryl(ene) is a monocyclic or fused ring derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, in which the number of carbon atoms is preferably 6 to 20, more preferably 6 to 15, and includes phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.
  • Halogen includes F, Cl, Br and I.
  • saturated or unsaturated ring is a mono- or polycyclic, (C3-C30) alicyclic or aromatic ring, in which the number of carbon atoms is preferably 5 to 20, more preferably 5 to 12.
  • substituted in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e., a substituent.
  • Substituents of the substituted alkyl group, the substituted alkoxy group, the substituted cycloalkyl group, the substituted heterocycloalkyl group, the substituted aryl(ene) group, and the substituted heteroaryl(ene) group in L 1 and L 2 , Ar 1 and Ar 2 , R 1 to R 7, R 11 and R 12 each independently are at least one selected from the group consisting of deuterium; a halogen; a cyano group; a carboxyl group; a nitro group; a hydroxyl group; a (C1-C30)alkyl group; a halo(C1-C30)alkyl group; a (C2-C30)alkenyl group; a (C2-C
  • organic electroluminescent compounds of formula 1 of the present invention include the following compounds:
  • TMS represents trimethylsilyl and TPS represents triphenylsilyl.
  • organic electroluminescent compounds of formula 1 according to the present invention can be prepared according to the methods known in the art, for example, Suzuki reaction, Ullman reaction, etc.
  • organic electroluminescent compounds of formula 1 according to the present invention can be prepared, for example, according to the following reaction scheme 1 or 2.
  • L 1 and L 2 , R 1 to R 7 , Ar 1 and Ar 2 , X and n are as defined in formula 1 above, and Hal represents a halogen.
  • the present invention further provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1 above, and an organic electroluminescent device comprising the material.
  • the material can be comprised of the organic electroluminescent compound according to the present invention alone, or can further include conventional materials generally used in organic electroluminescent materials.
  • the organic electroluminescent device of the present invention may comprise a first electrode, a second electrode, and at least one organic layer between the first and second electrodes, wherein the organic layer comprises at least one organic electroluminescent compound of formula 1 above.
  • the organic layer may comprise a light-emitting layer, and may further comprise at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, and a hole blocking layer.
  • the organic layer preferably the light-emitting layers can include at least one organic electroluminescent compound of formula 1 of the present invention. Further, preferably, the organic layer can include a compound represented by the following formula 2 as a host material:
  • R 1 and R 18 each independently represent hydrogen, deuterium, a halogen, a cyano group, a hydroxyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic, (C3-C30) alicyclic or aromatic ring.
  • the host compounds of formula 2 above include the following compounds:
  • the organic electroluminescent device according to the present invention may further comprise, in addition to the organic electroluminescent compounds represented by formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds in the organic layer.
  • the organic layer may further comprise, in addition to the organic electroluminescent compounds represented by formula 1, at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4 th period, transition metals of the 5 th period, lanthanides, and organic metals of d-transition elements of the Periodic Table, or at least one complex compound comprising the metal.
  • the organic electroluminescent device of the present invention may emit white light by further comprising at least one light-emitting layer which comprises a blue electroluminescent compound, a red electroluminescent compound, or a green electroluminescent compound, besides the organic electroluminescent compound of formula 1 above; and may further include a yellow or orange light-emitting layer, if necessary.
  • a surface layer selected from a chalcogenide layer, a metal halide layer and a metal oxide layer may be placed on an inner surface(s) of one or both electrode(s).
  • a chalcogenide (includes oxides) layer of silicon or aluminum is placed on an anode surface of an electroluminescent medium layer, and a metal halide layer or metal oxide layer is placed on a cathode surface of an electroluminescent medium layer.
  • the surface layer provides operating stability for the organic electroluminescent device.
  • the chalcogenide includes SiO X (1 ⁇ X ⁇ 2), AlO X (1 ⁇ X ⁇ 1.5), SiON, SiAlON, etc.;
  • the metal halide includes LiF, MgF 2 , CaF 2 , a rare earth metal fluoride, etc.; and the metal oxide includes Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
  • a mixed region of an electron transport compound and an reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant may be placed on at least one surface of a pair of electrodes.
  • the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to an electroluminescent medium.
  • the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the electroluminescent medium.
  • the oxidative dopant includes various Lewis acids and acceptor compounds; and the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof.
  • a reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more electroluminescent layers and emitting white light.
  • dry film-forming methods such as vacuum evaporation, sputtering, plasma, ion plating methods, etc.
  • wet film-forming methods such as spin coating, dip coating, flow coating methods, etc.
  • a thin film is formed by dissolving or dispersing the material constituting each layer in suitable solvents, such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
  • suitable solvents such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
  • the solvents are not specifically limited as long as the material constituting each layer is soluble or dispersible in the solvents, which do not cause any problems in forming a layer.
  • An OLED device was produced using the organic electroluminescent compound according to the present invention.
  • a transparent electrode indium tin oxide (ITO) thin film (15 ⁇ /sq) on a glass substrate for an organic light-emitting diode (OLED) device (Samsung Corning, Republic of Korea) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol, and distilled water, sequentially, and then was stored in isopropanol. Then, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • 4,4’,4”-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine was introduced into a cell of the vacuum vapor depositing apparatus, and then the pressure in the chamber of the apparatus was controlled to 10 -6 torr. Thereafter, an electric current was applied to the cell to evaporate the introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate.
  • N,N’-bis( ⁇ -naphthyl)-N,N’-diphenyl-4,4’-diamine was introduced into another cell of the vacuum vapor depositing apparatus, and was evaporated by applying electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer.
  • compound H-70 as a host was introduced into one cell of the vacuum vapor depositing apparatus, and compound D-15 of the present invention as a dopant was introduced into another cell.
  • the two materials were evaporated at different rates and deposited in a doping amount of 3 wt% of the dopant, based on the total weight of the host and dopant, to form a light-emitting layer having a thickness of 30 nm on the hole transport layer.
  • tris(8-hydroxyquinoline)aluminum(III) was introduced into one cell to form an electron transport layer having a thickness of 30 nm on the light-emitting layer.
  • an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer.
  • All the materials used for producing the OLED device were purified by vacuum sublimation at 10 -6 torr prior to use.
  • the produced OLED device showed blue light-emission having a luminance of 1300 cd/m 2 and a current density of 20.0 mA/cm 2 .
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound H-34 as a host and compound D-16 as a dopant in a light-emitting material.
  • the produced OLED device showed blue light-emission having a luminance of 1050 cd/m 2 and a current density of 17.5 mA/cm 2 .
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound H-20 as a host and compound D-77 as a dopant in a light-emitting material.
  • the produced OLED device showed blue light-emission having a luminance of 2550 cd/m 2 and a current density of 43.9 mA/cm 2 .
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound H-54 as a host and compound D-70 as a dopant in a light-emitting material.
  • the produced OLED device showed blue light-emission having a luminance of 620 cd/m 2 , a current density of 15.1 mA/cm 2 , and CIE color space (0.144, 0.085).
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound H-15 as a host and compound D-74 as a dopant in a light-emitting material.
  • the produced OLED device showed blue light-emission having a luminance of 430 cd/m 2 , a current density of 10.7 mA/cm 2 , and CIE color space (0.146, 0.090).
  • a hole injection layer and a hole transport layer were formed, compound H-8 as a luminescent host was introduced into one cell of the vacuum vapor depositing apparatus, and N1,N1,N6,N6-tetraphenylpyrene-1,6-diamine as a dopant was introduced into another cell.
  • the two materials were deposited at a rate of 100:1 to form a light-emitting layer having a thickness of 30 nm on the hole transport layer.
  • An electron transport layer and an electron injection layer were deposited according to the same manner as in Device Example 1, an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer. Thus, an OLED device was produced.
  • the produced OLED device showed blue light-emission having a luminance of 1210 cd/m 2 , a current density of 22.0 mA/cm 2 , and CIE color space (0.145, 0.143).
  • the organic electroluminescent compounds of the present invention have luminescent characteristics superior to the conventional materials as seen from Device Examples 1 to 3. Further, as seen from Device Examples 4 and 5, the organic electroluminescent compounds of the present invention show deep blue over the conventional materials in view of CIE color space.

Abstract

The present invention relates to novel organic electroluminescent compounds and an organic electroluminescent device containing the same. The organic electroluminescent compounds according to the present invention have high luminescent efficiency and a long lifespan, and show blue light-emission having high color purity, and thus an organic electroluminescent device having high efficiency, a long operating lifespan, and enhanced power consumption efficiency can be prepared by using the organic electroluminescent compounds according to the present invention.

Description

NOVEL ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present invention relates to novel organic electroluminescent compounds and an organic electroluminescent device comprising the same.
An electroluminescent (EL) device is a self-light-emitting device with the advantage of providing a wider viewing angle, a greater contrast ratio, and a faster response time. An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules and aluminum complexes as material for forming a light-emitting layer [see Appl. Phys. Lett. 51, 913, 1987].
The organic EL device emits a light by the injection of a charge into an organic film formed between an electron injection electrode (cathode) and a hole injection electrode (anode) and by the extinction of an electron-hole pair. The organic EL device has the following advantages: it can be formed onto a flexible transparent substrate, such as plastic; can be driven at a lower voltage, for example, 10 V or less, over a plasma display panel or an inorganic EL display; has relatively low power consumption; and provides good color. Further, the organic EL device provides tricolor light-emission, i.e., green, blue or red light-emission, and thus there is interest from many people as a next generation color display device.
The most important factor determining properties, such as luminescent efficiency, lifespan, etc., in an organic EL device is the light-emitting material. The light-emitting material is required to have the following features: high luminescent quantum yield in a solid state, high movement degree of an electron and a hole, non-breakdown in vacuum deposition, formability of a uniform thin film, and stability. The organic EL device is generally composed of a cathode/a hole injection layer (HIL)/a hole transport layer (HTL)/a light-emitting layer (EML)/an electron transport layer (ETL)/an electron injection layer (EIL)/an anode, and green, blue or red light-emitting of the organic EL device can be embodied depending on how to form a light-emitting layer.
The light-emitting material is classified into a host material and a dopant material in the functional aspect. Generally, as a structure of the device having the most excellent EL properties, the light-emitting layer, wherein a dopant is doped onto a host, was known. Recently, an urgent task is the development of an organic EL device having high efficacy and a long operating lifespan. In particular, the development of highly excellent light-emitting material over conventional light-emitting materials is urgent considering EL properties required in medium- and large-sized OLED panels.
As conventional blue light-emitting materials, a blue light-emitting material system by using diphenylvinyl-biphenyl (DPVBi) and a distyryl blue light-emitting material system (Idemitsu Kosan), and blue light-emitting material systems of dinaphthylanthracene and tetra(t-butyl)perylene (Eastman Kodak) were known.
Among them, the distyryl blue light-emitting material system of Idemitsu Kosan is effective, since it provides a device having 6 lm/W of power efficiency and 30000 or more hours of operating lifespan. However, since the system shows the reduction of color purity with the passage of driving time of a device, when it is applied to a full color display, it shows only several thousand hours of lifespan.
Further, the conventional blue light-emitting materials do not compose a light-emitting layer by using a host-dopant system, and compose a light-emitting layer by using only host compounds or dopant compounds. Thus, it is difficult to commercially use them in terms of color purity and efficiency. Further, credible data for a long lifespan is insufficient.
In the case that a light-emitting wavelength slightly moves toward a long wavelength, blue light-emission shows better luminescent efficiency, but does not satisfy pure blue color, and thus cannot be applied to high quality displays. Further, it has problems in color purity, efficiency and thermal stability. Thus, it is urgent to develop blue light-emitting materials.
Korean Patent Application Laying-Open No. 10-2011-0027033 discloses an organic EL device comprising anthracene derivatives and amine derivatives, and Korean Patent Application Laying-Open No. 10-2011-0115887 discloses an organic EL device comprising amine-based compounds. However, organic EL devices comprising the compounds disclosed in the publications as a dopant material are not satisfactory in luminescent efficiency and color purity.
The objective of the present invention is to provide an organic electroluminescent compound, in particular dopant materials, having high luminescent efficiency and a long lifespan and showing blue light-emission having high color purity; and an organic electroluminescent device having high efficiency and a long operating lifespan, comprising the organic electroluminescent compound.
The present inventors found that the above objective can be achieved by a compound represented by the following formula 1:
Figure PCTKR2013004688-appb-I000001
wherein
L1 and L2 each independently represent a single bond, a substituted or unsubstituted 5- to 30-membered heteroarylene group, or a substituted or unsubstituted (C6-C30)arylene group;
X represents a single bond or CR11R12;
Ar1 and Ar2 each independently represent a substituted or unsubstituted 5- to 30-membered heteroaryl group, or a substituted or unsubstituted (C6-C30)aryl group;
R1 to R6 each independently represent hydrogen, deuterium, a halogen, a cyano group, a nitro group, a hydroxyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a saturated or unsaturated ring;
R7 represents hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30-membered heteroaryl group;
R11 and R12 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a saturated or unsaturated ring;
n represents an integer of 1 or 2; where n is 2, each of R7 is the same or different; and
the heteroarylene group and the heteroaryl group contain at least one hetero atom selected from the group consisting of B, N, O, S, P(=O), Si and P.
The organic electroluminescent compounds according to the present invention have high luminescent efficiency and a long lifespan, and show blue light-emission having high color purity, over the conventional dopant materials. Thus, an organic electroluminescent device having high efficiency, a long operating lifespan, and enhanced power consumption efficiency can be prepared by using the organic electroluminescent compounds according to the present invention.
Hereinafter, the present invention will be described in detail. However, the following description is intended to explain the invention, and is not meant in any way to restrict the scope of the invention.
The present invention relates to an organic electroluminescent compound represented by formula 1 above, an organic electroluminescent material comprising the organic electroluminescent compound, and an organic electroluminescent device comprising the material.
In the organic electroluminescent compound represented by formula 1 above, preferably, L1 and L2 each independently represent a single bond, a substituted or unsubstituted 5- to 20-membered heteroarylene group, or a substituted or unsubstituted (C6-C20)arylene group; and more preferably a single bond, a 5- to 20-membered heteroarylene group which is unsubstituted or substituted with a (C1-C6) alkyl group, or an unsubstituted (C6-C20)arylene group. Specifically, L1 and L2 each independently represent a single bond, phenylene, biphenylene, naphthylene, fluorenylene, phenanthrenylene, pyridylene, pyrazinylene, pyrimidinylene or pyridazinylene.
X represents a single bond or CR11R12, in which preferably R11 and R12 each independently represent hydrogen or an unsubstituted (C6-C20)aryl group.
Preferably, Ar1 and Ar2 each independently represent a substituted or unsubstituted 5- to 20-membered heteroaryl group, or a substituted or unsubstituted (C6-C20)aryl group; and more preferably a 5- to 15-membered heteroaryl group which is unsubstituted or substituted with deuterium, a halogen, a cyano group, a hydroxyl group, a (C1-C6)alkyl group, a halo(C1-C6)alkyl group, a (C1-C6)alkoxy group, a (C6-C12)aryl group, a 5- to 15- membered heteroaryl group, a tri(C1-C6)alkylsilyl group, a tri(C6-C12)arylsilyl group, a di(C1-C6)alkyl(C6-C12)arylsilyl group or a (C1-C6)alkyldi(C6-C12)arylsilyl group, or a (C6-C15) aryl group which is unsubstituted or substituted with deuterium, a halogen, a cyano group, a hydroxyl group, a (C1-C6)alkyl group, a halo(C1-C6)alkyl group, a (C1-C6)alkoxy group, a (C6-C12)aryl group, a 5- to 15- membered heteroaryl group, a tri(C1-C6)alkylsilyl group, a tri(C6-C12)arylsilyl group, a di(C1-C6)alkyl(C6-C12)arylsilyl group or a (C1-C6)alkyldi(C6-C12)arylsilyl group.
Preferably, R1 to R6 each independently represent hydrogen, a halogen, a cyano group, a substituted or unsubstituted (C1-C10)alkyl group, or a substituted or unsubstituted (C6-C12)aryl group; and more preferably hydrogen, a halogen, a cyano group, an unsubstituted (C1-C10)alkyl group, or a (C6-C12)aryl group which is unsubstituted or substituted with a cyano group.
Preferably, R7 represents hydrogen, or a substituted or unsubstituted (C1-C6)alkyl group; and more preferably hydrogen, or an unsubstituted (C1-C6)alkyl group.
Herein, “(C1-C30)alkyl” is meant to be a linear or branched alkyl having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. “(C1-C30) alkoxy” is meant to be a linear or branched alkoxy having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and includes methoxy, ethoxy, propoxy, iso-propoxy, 1-ethylpropoxy, etc. “(C3-C30)cycloalkyl” is a mono- or polycyclic hydrocarbon having 3 to 30 carbon atoms, in which the number of carbon atoms is preferably 3 to 20, more preferably 3 to 7, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. “3- to 7-membered heterocycloalkyl” is a cycloalkyl having at least one heteroatom selected from the group consisting of B, N, O, S, P(=O), Si and P, preferably O, S and N, and 3 to 7 ring backbone atoms, and includes tetrahydrofurane, pyrrolidine, thiolan, tetrahydropyran, etc. “(C6-C30)aryl(ene)” is a monocyclic or fused ring derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, in which the number of carbon atoms is preferably 6 to 20, more preferably 6 to 15, and includes phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc. “5- to 30-membered heteroaryl(ene)” is an aryl group having at least one, preferably 1 to 4 heteroatom selected from the group consisting of B, N, O, S, P(=O), Si and P, and 5 to 30 ring backbone atoms; is a monocyclic ring, or a fused ring condensed with at least one benzene ring; has preferably 5 to 20, more preferably 5 to 15 ring backbone atoms; may be partially saturated; may be one formed by linking at least one heteroaryl or aryl group to a heteroaryl group via a single bond(s); and includes a monocyclic ring-type heteroaryl including furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., and a fused ring-type heteroaryl including benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, 9H-carbazolyl, 3-carbazolyl, 9-arylcarbazolyl, 2-carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, etc. “Halogen” includes F, Cl, Br and I. Further, “saturated or unsaturated ring” is a mono- or polycyclic, (C3-C30) alicyclic or aromatic ring, in which the number of carbon atoms is preferably 5 to 20, more preferably 5 to 12.
Herein, “substituted” in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e., a substituent. Substituents of the substituted alkyl group, the substituted alkoxy group, the substituted cycloalkyl group, the substituted heterocycloalkyl group, the substituted aryl(ene) group, and the substituted heteroaryl(ene) group in L1 and L2, Ar1 and Ar2, R1 to R7, R11 and R12 each independently are at least one selected from the group consisting of deuterium; a halogen; a cyano group; a carboxyl group; a nitro group; a hydroxyl group; a (C1-C30)alkyl group; a halo(C1-C30)alkyl group; a (C2-C30)alkenyl group; a (C2-C30)alkynyl group; a (C1-C30)alkoxy group; a (C1-C30)alkylthio group; a (C3-C30)cycloalkyl group; a (C3-C30)cycloalkenyl group; a 3- to 7-membered heterocycloalkyl group; a (C6-C30)aryl group which is unsubstituted or substituted with a 5- to 30-membered heteroaryl group; a (C6-C30)aryloxy group; a (C6-C30)arylthio group; a 5- to 30-membered heteroaryl group which is unsubstituted or substituted with a (C6-C30)aryl group; a tri(C1-C30)alkylsilyl group; a tri(C6-C30)arylsilyl group; a di(C1-C30)alkyl(C6-C30)arylsilyl group; a (C1-C30)alkyldi(C6-C30)arylsilyl group; an amino group; a mono- or di(C1-C30)alkylamino group; a mono- or di(C6-C30)arylamino group; a (C1-C30)alkyl(C6-C30)arylamino group; a (C1-C30)alkylcarbonyl group; a (C1-C30)alkoxycarbonyl group; a (C6-C30)arylcarbonyl group; a di(C6-C30)arylboronyl group; a di(C1-C30)alkylboronyl group; a (C1-C30)alkyl(C6-C30)arylboronyl group; a (C6-C30)aryl(C1-C30)alkyl group; and a (C1-C30)alkyl(C6-C30)aryl group; and preferably at least one selected from the group consisting of deuterium; a halogen; a cyano group; (C1-C30)alkyl group; a halo(C1-C30)alkyl group; a (C6-C30)aryl group; a 5- to 30-membered heteroaryl group; a tri(C1-C30)alkylsilyl group; a tri(C6-C30)arylsilyl group; a di(C1-C30)alkyl(C6-C30)arylsilyl group; a (C1-C30)alkyldi(C6-C30)arylsilyl group; an amino group; a mono- or di(C1-C30)alkylamino group; a mono- or di(C6-C30)arylamino group; a (C1-C30)alkyl(C6-C30)arylamino group; a hydroxyl group; and a (C1-C30)alkoxy group.
The organic electroluminescent compounds of formula 1 of the present invention include the following compounds:
Figure PCTKR2013004688-appb-I000002
Figure PCTKR2013004688-appb-I000003
Figure PCTKR2013004688-appb-I000004
Figure PCTKR2013004688-appb-I000005
Figure PCTKR2013004688-appb-I000006
Figure PCTKR2013004688-appb-I000007
Figure PCTKR2013004688-appb-I000008
Figure PCTKR2013004688-appb-I000009
Figure PCTKR2013004688-appb-I000010
Figure PCTKR2013004688-appb-I000011
Figure PCTKR2013004688-appb-I000012
Figure PCTKR2013004688-appb-I000013
Figure PCTKR2013004688-appb-I000014
Figure PCTKR2013004688-appb-I000015
Figure PCTKR2013004688-appb-I000016
Figure PCTKR2013004688-appb-I000017
Figure PCTKR2013004688-appb-I000018
Figure PCTKR2013004688-appb-I000019
Figure PCTKR2013004688-appb-I000020
Figure PCTKR2013004688-appb-I000021
Figure PCTKR2013004688-appb-I000022
Figure PCTKR2013004688-appb-I000023
Figure PCTKR2013004688-appb-I000024
Figure PCTKR2013004688-appb-I000025
Figure PCTKR2013004688-appb-I000026
Figure PCTKR2013004688-appb-I000027
Figure PCTKR2013004688-appb-I000028
Figure PCTKR2013004688-appb-I000029
wherein TMS represents trimethylsilyl and TPS represents triphenylsilyl.
The organic electroluminescent compounds of formula 1 according to the present invention can be prepared according to the methods known in the art, for example, Suzuki reaction, Ullman reaction, etc.
The organic electroluminescent compounds of formula 1 according to the present invention can be prepared, for example, according to the following reaction scheme 1 or 2.
[Reaction Scheme 1]
Figure PCTKR2013004688-appb-I000030
[Reaction Scheme 2]
Figure PCTKR2013004688-appb-I000031
wherein L1 and L2, R1 to R7, Ar1 and Ar2, X and n are as defined in formula 1 above, and Hal represents a halogen.
The present invention further provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1 above, and an organic electroluminescent device comprising the material. The material can be comprised of the organic electroluminescent compound according to the present invention alone, or can further include conventional materials generally used in organic electroluminescent materials. The organic electroluminescent device of the present invention may comprise a first electrode, a second electrode, and at least one organic layer between the first and second electrodes, wherein the organic layer comprises at least one organic electroluminescent compound of formula 1 above.
One of the first electrodes and the second electrodes can be an anode and the other can be a cathode. The organic layer may comprise a light-emitting layer, and may further comprise at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, and a hole blocking layer.
The organic layer, preferably the light-emitting layers can include at least one organic electroluminescent compound of formula 1 of the present invention. Further, preferably, the organic layer can include a compound represented by the following formula 2 as a host material:
Figure PCTKR2013004688-appb-I000032
wherein
R1 and R18 each independently represent hydrogen, deuterium, a halogen, a cyano group, a hydroxyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic, (C3-C30) alicyclic or aromatic ring.
The host compounds of formula 2 above include the following compounds:
Figure PCTKR2013004688-appb-I000033
Figure PCTKR2013004688-appb-I000034
Figure PCTKR2013004688-appb-I000035
Figure PCTKR2013004688-appb-I000036
Figure PCTKR2013004688-appb-I000037
Figure PCTKR2013004688-appb-I000038
Figure PCTKR2013004688-appb-I000039
Figure PCTKR2013004688-appb-I000040
Figure PCTKR2013004688-appb-I000041
Figure PCTKR2013004688-appb-I000042
Figure PCTKR2013004688-appb-I000043
Figure PCTKR2013004688-appb-I000044
Figure PCTKR2013004688-appb-I000045
Figure PCTKR2013004688-appb-I000046
Figure PCTKR2013004688-appb-I000047
Figure PCTKR2013004688-appb-I000048
The organic electroluminescent device according to the present invention may further comprise, in addition to the organic electroluminescent compounds represented by formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds in the organic layer.
In the organic electroluminescent device according to the present invention, the organic layer may further comprise, in addition to the organic electroluminescent compounds represented by formula 1, at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4th period, transition metals of the 5th period, lanthanides, and organic metals of d-transition elements of the Periodic Table, or at least one complex compound comprising the metal.
In addition, the organic electroluminescent device of the present invention may emit white light by further comprising at least one light-emitting layer which comprises a blue electroluminescent compound, a red electroluminescent compound, or a green electroluminescent compound, besides the organic electroluminescent compound of formula 1 above; and may further include a yellow or orange light-emitting layer, if necessary.
Preferably, in the organic electroluminescent device according to the present invention, at least one layer (hereinafter, "a surface layer”) selected from a chalcogenide layer, a metal halide layer and a metal oxide layer may be placed on an inner surface(s) of one or both electrode(s). Specifically, it is preferred that a chalcogenide (includes oxides) layer of silicon or aluminum is placed on an anode surface of an electroluminescent medium layer, and a metal halide layer or metal oxide layer is placed on a cathode surface of an electroluminescent medium layer. The surface layer provides operating stability for the organic electroluminescent device. Preferably, the chalcogenide includes SiOX(1≤X≤2), AlOX(1≤X≤1.5), SiON, SiAlON, etc.; the metal halide includes LiF, MgF2, CaF2, a rare earth metal fluoride, etc.; and the metal oxide includes Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
Preferably, in the organic electroluminescent device according to the present invention, a mixed region of an electron transport compound and an reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant may be placed on at least one surface of a pair of electrodes. In this case, the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to an electroluminescent medium. Further, the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the electroluminescent medium. Preferably, the oxidative dopant includes various Lewis acids and acceptor compounds; and the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof. A reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more electroluminescent layers and emitting white light.
In order to form each layer constituting the organic electroluminescent device according to the present invention, dry film-forming methods, such as vacuum evaporation, sputtering, plasma, ion plating methods, etc., or wet film-forming methods, such as spin coating, dip coating, flow coating methods, etc., can be used.
When using a wet film-forming method, a thin film is formed by dissolving or dispersing the material constituting each layer in suitable solvents, such as ethanol, chloroform, tetrahydrofuran, dioxane, etc. The solvents are not specifically limited as long as the material constituting each layer is soluble or dispersible in the solvents, which do not cause any problems in forming a layer.
Hereinafter, the organic electroluminescent compound of the present invention, the preparation method of the compound, and the luminescent properties of the device comprising the compound will be explained in detail with reference to the following examples:
Example 1: Preparation of compound D-15
Figure PCTKR2013004688-appb-I000049
Preparation of compound 1-1
After adding 3-aminobenzonitrile (50.0 g, 423.0 mmol), iodobenzene (39.0 ml, 352.0 mmol), palladium(II) acetate(Pd(OAc)2) (3.9 g), tri-t-butylphosphine (P(t-Bu)3) (8.5 ml) and Cs2CO3 (228.0 g) to toluene (1000.0 ml), the reaction mixture was stirred for 24 hours at 120°C. After completing the reaction, the reaction mixture was slowly cooled to room temperature and H2O was added thereto. The organic layer was extracted with ethyl acetate (EA), the obtained organic layer was dried with Na2SO4 and then was concentrated, and was separated through column chromatography to obtain compound 1-1 (70.0 g, Yield: 85 %).
Preparation of compound 1-2
After adding compound 1-1 (8.0 g, 41.0 mmol), 1,6-dibromopyrene (30.0 g, 83.0 mmol), Cu (4.8 g) and Cs2CO3 (34.0 g) to 1,2-dichlorobenzene (400.0 ml), the reaction mixture was stirred for 19 hours at 200°C. After stirring, H2O was slowly added to the reaction mixture to complete the reaction, the reaction mixture was cooled to room temperature, and H2O was added thereto. The organic layer was extracted with EA, the obtained organic layer was dried with Na2SO4 and then was concentrated, and was separated through column chromatography to obtain compound 1-2 (12.0 g, Yield: 60 %).
Preparation of compound D-15
Compound 1-2 (5.0 g, 10.0 mmol) and 1,2,3,4-tetrahydroquinoline (1.6 ml) were mixed. According to the same synthesis method as Preparation of compound 1-1, compound D-15 (3.8 g, Yield: 69 %) was obtained.
Example 2: Preparation of compound D-76
Figure PCTKR2013004688-appb-I000050
Preparation of compound 2-1
After adding 4-isobutyrylbenzonitrile (6.2 g, 35.7 mmol) and phenylhydrazine (3.8 g, 35.7 mmol) to acetic acid (120.0 ml), the reaction mixture was stirred for 3 hours at 80°C. After cooling the mixture, 1,2-dichloroethane (120.0 ml) was added to the mixture and sodium triacetoxyborohydride (NaBH(OAc)3) (9.8 g, 46.6 mol) was gradually added thereto. After stirring the mixture for 30 minutes at room temperature, H2O was added thereto. The organic layer was extracted with EA, the obtained organic layer was dried with Na2SO4 and then was concentrated, and was separated through column chromatography to obtain compound 2-1 (5.3 g, Yield: 60 %).
Preparation of compound D-76
Compound 1-2 (5.0 g, 10.0 mmol) and compound 2-1 (2.5 g, 20.0 mmol) were mixed. According to the same synthesis method as Preparation of compound 1-1, compound D-76 (4.5 g, Yield: 70 %) was obtained.
Example 3: Preparation of compound D-16
Figure PCTKR2013004688-appb-I000051
Preparation of compound 3-1
2-Fluoroaniline (20.0 g, 180.0 mmol) and iodobenzene (16.7 ml, 150.0 mmol) were mixed. According to the same synthesis method as Preparation of compound 1-1, compound 3-1 (23.0 g) was obtained.
Preparation of compound 3-2
Compound 3-1 (5.0 g, 26.7 mmol) and 1,6-dibromopyrene (20.0 g, 53.4 mmol) were mixed. According to the same synthesis method as Preparation of compound 1-2, compound 3-2 (2.9 g) was obtained.
Preparation of compound D-16
Compound 3-2 (2.9 g, 6.15 mmol) and 1,2,3,4-tetrahydroquinole (0.92 ml, 7.38 mmol) were mixed. According to the same synthesis method as Preparation of compound 1-1, compound D-16 (1.7 g) was obtained.
Example 4: Preparation of compound D-25
Figure PCTKR2013004688-appb-I000052
Preparation of compound 4-1
After adding 2,4-dibromo-6-fluoroaniline (25.0 g, 92.9 mmol), phenylboronic acid (34.0 g, 278.0 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) (10.0 g, 9.29 mmol) and K2CO3 (64.0 g, 464.0 mmol) to a mixed solution of toluene (300.0 ml), ethanol (EtOH) (100.0 ml) and H2O (100.0 ml) and dissolving the reaction mixture, and the mixture was stirred for 7 hours at 120°C. After completing the reaction by slowly adding H2O, the organic layer was extracted with EA, was dried with Na2SO4, and was separated through column chromatography to obtain compound 4-1 (20.0 g).
Preparation of compound 4-2
Compound 4-1 (30.0 g, 113.9 mmol) and iodobenzene (19.3 g, 94.0 mmol) were mixed. According to the same synthesis method as Preparation of compound 1-1, compound 4-2 (23.0 g, Yield: 72 %) was obtained.
Preparation of compound 4-3
Compound 4-2 (10.0 g, 29.4 mmol) and 1,6-dibromopyrene (21.0 g, 58.0 mmol) were mixed. According to the same synthesis method as Preparation of compound 1-2, compound 4-3 (2.2 g, Yield: 12 %) was obtained.
Preparation of compound D-25
Compound 4-3 (5.0 g, 8.0 mmol) and indoline (1.0 ml, 9.6 mmol) were mixed. According to the same synthesis method as Preparation of compound 1-1, compound D-25 (1.0 g, Yield: 43 %) was obtained.
Example 5: Preparation of compound D-80
Figure PCTKR2013004688-appb-I000053
Compound 4-3 (5.0 g, 8.0 mmol) and 1,2,3,4-tetrahydroquinoline-6-carbonitrile (1.5 g, 9.6 mmol) were mixed. According to the same synthesis method as Preparation of compound 1-1, compound D-80 (1.0 g, Yield: 40 %) was obtained.
Example 6: Preparation of compound D-74
Figure PCTKR2013004688-appb-I000054
Preparation of compound 6-1
Compound A (3.0 g, 8.6 mmol) and 1,6-dibromopyrene (6.2 g, 17.2 mmol) were mixed. According to the same synthesis method as Preparation of compound 1-2, compound 6-1 (4.0 g, Yield: 60 %) was obtained.
Preparation of compound D-74
Compound 6-1 (4.0 g, 6.4 mmol) and 1,2,3,4-tetrahydroquinoline-6-carbonitrile (1.2 g, 7.7 mmol) were mixed. According to the same synthesis method as Preparation of compound 1-1, compound D-74 (2.2 g, Yield: 50 %) was obtained.
Example 7: Preparation of compound D-75
Figure PCTKR2013004688-appb-I000055
Compound 1-2 (6.0 g, 12.6 mmol) and 2-phenyl-1H-indole (3.0 g, 15.2 mmol) were mixed. According to the same synthesis method as Preparation of compound 1-1, compound D-75 (2.0 g, Yield: 50 %) was obtained.
Example 8: Preparation of compound D-77
Figure PCTKR2013004688-appb-I000056
Preparation of compound 8-1
2-methyl-1-phenylpropane-1-one (15.7 ml, 104.0 mmol) and phenylhydrazine (15.0 g, 104.0 mmol) were mixed. According to the same synthesis method as Preparation of compound 2-1, compound 8-1 (12.0 g, Yield: 52 %) was obtained.
Preparation of compound 8-2
Diphenylamine (8.0 g, 47.3 mmol) and 1,6-dibromopyrene (34.0 g, 94.6 mmol) were mixed. According to the same synthesis method as Preparation of compound 1-2, compound 8-2 (10.6 g, Yield: 50 %) was obtained.
Preparation of compound D-77
Compound 8-1 (3.1 g, 13.9 mmol) and compound 8-2 (7.5 g, 16.7 mmol) were mixed. According to the same synthesis method as Preparation of compound 1-1, compound D-77 (12.0 g, Yield: 52 %) was obtained.
Example 9: Preparation of compound D-71
Figure PCTKR2013004688-appb-I000057
Compound 8-1 (3.1 g, 13.9 mmol) and compound 1-2 (6.0 g, 12.7 mmol) were mixed. According to the same synthesis method as Preparation of compound 1-1, compound D-71 (1.5 g, Yield: 20 %) was obtained.
Example 10: Preparation of compound D-70
Figure PCTKR2013004688-appb-I000058
Preparation of compound 10-1
2-methyl-1-phenylpropane-1-one (15.0 g, 101.0 mmol) and p-cyanophenylhydrazine (17.1 g, 101.0 mmol) were mixed. According to the same synthesis method as Preparation of compound 2-1, compound 10-1 (7.5 g, Yield: 30 %) was obtained.
Preparation of compound D-70
Compound 10-1 (2.5 g, 10.1 mmol) and compound 1-2 (5.0 g, 10.6 mmol) were mixed. According to the same synthesis method as Preparation of compound 1-1, compound D-70 (1.25 g, Yield: 20 %) was obtained.
Example 11: Preparation of compound D-91
Figure PCTKR2013004688-appb-I000059
Compound 1-2 (6.3 g, 13.3 mmol) and 1,2,3,4-tetrahydroquinoline-6-carbonitrile (2.0 g, 12.6 mmol) were mixed. According to the same synthesis method as Preparation of compound 1-1, compound D-91 (5.4 g, Yield: 78 %) was obtained.
Example 12: Preparation of compound D-22
Figure PCTKR2013004688-appb-I000060
Preparation of compound 12-1
2-Aminobenzonitrile (50.0 g, 423.0 mmol) and iodobenzene (39 ml, 352.0 mmol) were mixed. According to the same synthesis method as Preparation of compound 1-1, compound 12-1 (70.0 g, Yield: 85 %) was obtained.
Preparation of compound 12-2
Compound 12-1 (8.0 g, 41.0 mmol) and 1,6-dibromopyrene (30.0 g, 83.0 mmol) were mixed. According to the same synthesis method as Preparation of compound 1-2, compound 12-2 (12.0 g, Yield: 60 %) was obtained.
Preparation of compound D-22
Compound 12-2 (9.5 g, 20.1 mmol) and indoline (2.0 g, 16.8 mmol) were mixed. According to the same synthesis method as Preparation of compound 1-1, compound D-22 (4.3 g, Yield: 50 %) was obtained.
The physical properties of the compounds of the present invention, which were prepared in Examples 1 to 12, are provided in the Table 1 below:
Table 1
Figure PCTKR2013004688-appb-I000061
Device Example 1: Production of an OLED device by using
the organic electroluminescent compound according to the present invention
An OLED device was produced using the organic electroluminescent compound according to the present invention. A transparent electrode indium tin oxide (ITO) thin film (15 Ω/sq) on a glass substrate for an organic light-emitting diode (OLED) device (Samsung Corning, Republic of Korea) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol, and distilled water, sequentially, and then was stored in isopropanol. Then, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus. 4,4’,4”-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine was introduced into a cell of the vacuum vapor depositing apparatus, and then the pressure in the chamber of the apparatus was controlled to 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate the introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate. Then, N,N’-bis(α-naphthyl)-N,N’-diphenyl-4,4’-diamine was introduced into another cell of the vacuum vapor depositing apparatus, and was evaporated by applying electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. Thereafter, compound H-70 as a host was introduced into one cell of the vacuum vapor depositing apparatus, and compound D-15 of the present invention as a dopant was introduced into another cell. The two materials were evaporated at different rates and deposited in a doping amount of 3 wt% of the dopant, based on the total weight of the host and dopant, to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. Then, tris(8-hydroxyquinoline)aluminum(III) was introduced into one cell to form an electron transport layer having a thickness of 30 nm on the light-emitting layer. Then, after depositing lithium quinolate as an electron injection layer having a thickness of 2 nm on the electron transport layer, an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer. Thus, an OLED device was produced. All the materials used for producing the OLED device were purified by vacuum sublimation at 10-6 torr prior to use.
The produced OLED device showed blue light-emission having a luminance of 1300 cd/m2 and a current density of 20.0 mA/cm2.
Device Example 2: Production of an OLED device by using
the organic electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except for using compound H-34 as a host and compound D-16 as a dopant in a light-emitting material.
The produced OLED device showed blue light-emission having a luminance of 1050 cd/m2 and a current density of 17.5 mA/cm2.
Device Example 3: Production of an OLED device by using
the organic electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except for using compound H-20 as a host and compound D-77 as a dopant in a light-emitting material.
The produced OLED device showed blue light-emission having a luminance of 2550 cd/m2 and a current density of 43.9 mA/cm2.
Device Example 4: Production of an OLED device by using
the organic electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except for using compound H-54 as a host and compound D-70 as a dopant in a light-emitting material.
The produced OLED device showed blue light-emission having a luminance of 620 cd/m2, a current density of 15.1 mA/cm2, and CIE color space (0.144, 0.085).
Device Example 5: Production of an OLED device by using
the organic electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except for using compound H-15 as a host and compound D-74 as a dopant in a light-emitting material.
The produced OLED device showed blue light-emission having a luminance of 430 cd/m2, a current density of 10.7 mA/cm2, and CIE color space (0.146, 0.090).
Comparative Example 1: Production of an OLED device
by using conventional light-emitting materials
According to the same manner as in Device Example 1, a hole injection layer and a hole transport layer were formed, compound H-8 as a luminescent host was introduced into one cell of the vacuum vapor depositing apparatus, and N1,N1,N6,N6-tetraphenylpyrene-1,6-diamine as a dopant was introduced into another cell. The two materials were deposited at a rate of 100:1 to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. An electron transport layer and an electron injection layer were deposited according to the same manner as in Device Example 1, an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer. Thus, an OLED device was produced.
The produced OLED device showed blue light-emission having a luminance of 1210 cd/m2, a current density of 22.0 mA/cm2, and CIE color space (0.145, 0.143).
The organic electroluminescent compounds of the present invention have luminescent characteristics superior to the conventional materials as seen from Device Examples 1 to 3. Further, as seen from Device Examples 4 and 5, the organic electroluminescent compounds of the present invention show deep blue over the conventional materials in view of CIE color space.

Claims (7)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2013004688-appb-I000062
    wherein
    L1 and L2 each independently represent a single bond, a substituted or unsubstituted 5- to 30-membered heteroarylene group, or a substituted or unsubstituted (C6-C30)arylene group;
    X represents a single bond or CR11R12;
    Ar1 and Ar2 each independently represent a substituted or unsubstituted 5- to 30-membered heteroaryl group, or a substituted or unsubstituted (C6-C30)aryl group;
    R1 to R6 each independently represent hydrogen, deuterium, a halogen, a cyano group, a nitro group, a hydroxyl group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a saturated or unsaturated ring;
    R7 represents hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 3- to 30-membered heteroaryl group;
    R11 and R12 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted 3- to 7-membered heterocycloalkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic, (C3-C30) alicyclic or aromatic ring;
    n represents an integer of 1 or 2; where n is 2, each of R7 is the same or different; and
    the heteroarylene group and the heteroaryl group contain at least one hetero atom selected from the group consisting of B, N, O, S, P(=O), Si and P.
  2. The organic electroluminescent compound according to claim 1, wherein the substituents of the substituted alkyl group, the substituted alkoxy group, the substituted cycloalkyl group, the substituted heterocycloalkyl group, the substituted aryl(ene) group, and the substituted heteroaryl(ene) group in L1 and L2, Ar1 and Ar2, R1 to R7, R11 and R12 each independently are at least one selected from the group consisting of deuterium; a halogen; a cyano group; a carboxyl group; a nitro group; a hydroxyl group; a (C1-C30)alkyl group; a halo(C1-C30)alkyl group; a (C2-C30)alkenyl group; a (C2-C30)alkynyl group; a (C1-C30)alkoxy group; a (C1-C30)alkylthio group; a (C3-C30)cycloalkyl group; a (C3-C30)cycloalkenyl group; a 3- to 7-membered heterocycloalkyl group; a (C6-C30)aryl group which is unsubstituted or substituted with a 5- to 30-membered heteroaryl group; a (C6-C30)aryloxy group; a (C6-C30)arylthio group; a 5- to 30-membered heteroaryl group which is unsubstituted or substituted with a (C6-C30)aryl group; a tri(C1-C30)alkylsilyl group; a tri(C6-C30)arylsilyl group; a di(C1-C30)alkyl(C6-C30)arylsilyl group; a (C1-C30)alkyldi(C6-C30)arylsilyl group; an amino group; a mono- or di(C1-C30)alkylamino group; a mono- or di(C6-C30)arylamino group; a (C1-C30)alkyl(C6-C30)arylamino group; a (C1-C30)alkylcarbonyl group; a (C1-C30)alkoxycarbonyl group; a (C6-C30)arylcarbonyl group; a di(C6-C30)arylboronyl group; a di(C1-C30)alkylboronyl group; a (C1-C30)alkyl(C6-C30)arylboronyl group; a (C6-C30)aryl(C1-C30)alkyl group; and a (C1-C30)alkyl(C6-C30)aryl group.
  3. The organic electroluminescent compound according to claim 1, wherein L1 and L2 each independently represent a single bond, a substituted or unsubstituted 5- to 20-membered heteroarylene group, or a substituted or unsubstituted (C6-C20)arylene group;
    X represents a single bond or CR11R12, in which R11 and R12 each independently represent hydrogen or an unsubstituted (C6-C20)aryl group;
    Ar1 and Ar2 each independently represent a substituted or unsubstituted 5- to 20-membered heteroaryl group, or a substituted or unsubstituted (C6-C20)aryl group;
    R1 to R6 each independently represent hydrogen, a halogen, a cyano group, a substituted or unsubstituted (C1-C10)alkyl group, or a substituted or unsubstituted (C6-C12)aryl group; and
    R7 represents hydrogen, or a substituted or unsubstituted (C1-C6)alkyl group.
  4. The organic electroluminescent compound according to claim 3, wherein L1 and L2 each independently represent a single bond, a 5- to 20-membered heteroarylene group which is unsubstituted or substituted with a (C1-C6) alkyl group, or an unsubstituted (C6-C20)arylene group;
    Ar1 and Ar2 each independently represent a 5- to 15-membered heteroaryl group which is unsubstituted or substituted with deuterium, a halogen, a cyano group, a hydroxyl group, a (C1-C6)alkyl group, a halo(C1-C6)alkyl group, a (C1-C6)alkoxy group, a (C6-C12)aryl group, a 5- to 15- membered heteroaryl group, a tri(C1-C6)alkylsilyl group, a tri(C6-C12)arylsilyl group, a di(C1-C6)alkyl(C6-C12)arylsilyl group or a (C1-C6)alkyldi(C6-C12)arylsilyl group, or a (C6-C15) aryl group which is unsubstituted or substituted with deuterium, a halogen, a cyano group, a hydroxyl group, a (C1-C6)alkyl group, a halo(C1-C6)alkyl group, a (C1-C6)alkoxy group, a (C6-C12)aryl group, a 5- to 15- membered heteroaryl group, a tri(C1-C6)alkylsilyl group, a tri(C6-C12)arylsilyl group, a di(C1-C6)alkyl(C6-C12)arylsilyl group or a (C1-C6)alkyldi(C6-C12)arylsilyl group;
    R1 to R6 each independently represent hydrogen, a halogen, a cyano group, an unsubstituted (C1-C10)alkyl group, or a (C6-C12)aryl group which is unsubstituted or substituted with a cyano group; and
    R7 represents hydrogen, or an unsubstituted (C1-C6)alkyl group.
  5. The organic electroluminescent compound according to claim 4, wherein wherein L1 and L2 each independently represent a single bond, phenylene, biphenylene, naphthylene, fluorenylene, phenanthrenylene, pyridylene, pyrazinylene, pyrimidinylene or pyridazinylene.
  6. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
    Figure PCTKR2013004688-appb-I000063
    Figure PCTKR2013004688-appb-I000064
    Figure PCTKR2013004688-appb-I000065
    Figure PCTKR2013004688-appb-I000066
    Figure PCTKR2013004688-appb-I000067
    Figure PCTKR2013004688-appb-I000068
    Figure PCTKR2013004688-appb-I000069
    Figure PCTKR2013004688-appb-I000070
    Figure PCTKR2013004688-appb-I000071
    Figure PCTKR2013004688-appb-I000072
    Figure PCTKR2013004688-appb-I000073
    Figure PCTKR2013004688-appb-I000074
    Figure PCTKR2013004688-appb-I000075
    Figure PCTKR2013004688-appb-I000076
    Figure PCTKR2013004688-appb-I000077
    Figure PCTKR2013004688-appb-I000078
    Figure PCTKR2013004688-appb-I000079
    Figure PCTKR2013004688-appb-I000080
    Figure PCTKR2013004688-appb-I000081
    Figure PCTKR2013004688-appb-I000082
    Figure PCTKR2013004688-appb-I000083
    Figure PCTKR2013004688-appb-I000084
    Figure PCTKR2013004688-appb-I000085
    Figure PCTKR2013004688-appb-I000086
    Figure PCTKR2013004688-appb-I000087
    Figure PCTKR2013004688-appb-I000088
    Figure PCTKR2013004688-appb-I000089
    Figure PCTKR2013004688-appb-I000090
    wherein TMS represents trimethylsilyl and TPS represents triphenylsilyl.
  7. An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014088352A1 (en) * 2012-12-06 2014-06-12 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compounds and organic electroluminescent device comprising the same
CN108203407A (en) * 2017-12-20 2018-06-26 李现伟 Pyrene class electroluminescent organic material, luminescent device and display
US11581487B2 (en) 2017-04-26 2023-02-14 Oti Lumionics Inc. Patterned conductive coating for surface of an opto-electronic device
US11730012B2 (en) 2019-03-07 2023-08-15 Oti Lumionics Inc. Materials for forming a nucleation-inhibiting coating and devices incorporating same
US11751415B2 (en) 2018-02-02 2023-09-05 Oti Lumionics Inc. Materials for forming a nucleation-inhibiting coating and devices incorporating same

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016060463A2 (en) * 2014-10-14 2016-04-21 주식회사 동진쎄미켐 Novel compound and organic light-emitting element comprising same
CN109415333B (en) * 2016-12-14 2022-07-12 株式会社Lg化学 Heterocyclic compound and organic light-emitting element comprising same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20070105081A (en) * 2006-04-25 2007-10-30 엘지전자 주식회사 Organic electroluminescence devices
JP2008078362A (en) * 2006-09-21 2008-04-03 Toray Ind Inc Light emitting element material and light emitting element
EP1942171A1 (en) * 2005-09-08 2008-07-09 Toray Industries, Inc. Light-emitting device material and light-emitting device
JP2011001475A (en) * 2009-06-19 2011-01-06 Toyo Ink Mfg Co Ltd Material for organic electroluminescent element and application thereof
KR20110002155A (en) * 2009-07-01 2011-01-07 주식회사 엘지화학 New compounds and organic electronic device using the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1942171A1 (en) * 2005-09-08 2008-07-09 Toray Industries, Inc. Light-emitting device material and light-emitting device
KR20070105081A (en) * 2006-04-25 2007-10-30 엘지전자 주식회사 Organic electroluminescence devices
JP2008078362A (en) * 2006-09-21 2008-04-03 Toray Ind Inc Light emitting element material and light emitting element
JP2011001475A (en) * 2009-06-19 2011-01-06 Toyo Ink Mfg Co Ltd Material for organic electroluminescent element and application thereof
KR20110002155A (en) * 2009-07-01 2011-01-07 주식회사 엘지화학 New compounds and organic electronic device using the same

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014088352A1 (en) * 2012-12-06 2014-06-12 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compounds and organic electroluminescent device comprising the same
US11581487B2 (en) 2017-04-26 2023-02-14 Oti Lumionics Inc. Patterned conductive coating for surface of an opto-electronic device
CN108203407A (en) * 2017-12-20 2018-06-26 李现伟 Pyrene class electroluminescent organic material, luminescent device and display
US11751415B2 (en) 2018-02-02 2023-09-05 Oti Lumionics Inc. Materials for forming a nucleation-inhibiting coating and devices incorporating same
US11730012B2 (en) 2019-03-07 2023-08-15 Oti Lumionics Inc. Materials for forming a nucleation-inhibiting coating and devices incorporating same

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