WO2011132866A1 - Novel compounds for organic electronic material and organic electroluminescent device using the same - Google Patents

Novel compounds for organic electronic material and organic electroluminescent device using the same Download PDF

Info

Publication number
WO2011132866A1
WO2011132866A1 PCT/KR2011/002294 KR2011002294W WO2011132866A1 WO 2011132866 A1 WO2011132866 A1 WO 2011132866A1 KR 2011002294 W KR2011002294 W KR 2011002294W WO 2011132866 A1 WO2011132866 A1 WO 2011132866A1
Authority
WO
WIPO (PCT)
Prior art keywords
heteroaryl
alkyl
aryl
organic
compounds
Prior art date
Application number
PCT/KR2011/002294
Other languages
French (fr)
Inventor
Hee Choon Ahn
Young Jun Cho
Hyuck Joo Kwon
Bong Ok Kim
Sung Min Kim
Original Assignee
Rohm And Haas Electronic Materials Korea Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rohm And Haas Electronic Materials Korea Ltd. filed Critical Rohm And Haas Electronic Materials Korea Ltd.
Publication of WO2011132866A1 publication Critical patent/WO2011132866A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • 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
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium

Definitions

  • the present invention relates to novel compounds for organic electronic materials and an organic electroluminescent device using the same.
  • electroluminescent (EL) devices are advantageous in that they provide wide view angle, superior contrast and fast response rate as self-emissive display devices.
  • Eastman Kodak first developed an organic EL device using a low-molecular-weight aromatic diamine and aluminum complex as a substance for forming an electroluminescent layer [ Appl. Phys. Lett. 51, 913, 1987].
  • an organic EL device when a charge is applied to an organic layer formed between an electron injection electrode (cathode) and a hole injection electrode (anode), an electron and a hole are paired and exciton is generated. Light is emitted by using electroluminescence (phosphorescence or fluorescence) in a state that the exciton is inactivated.
  • the organic EL device emits polarization of light at voltage of about 10V and high brightness of about 100 ⁇ 10,000cd/m2.
  • the organic EL device has a feature in that light is emitted in a spectrum ranging from blue color to red color by simply selecting a fluorescent material.
  • the organic EL device is advantageous in that it can be formed on a flexible transparent substrate such as plastic, is operable with relatively low voltage (10 V or lower) as compared to plasma display panels or inorganic EL displays, consumes less power, and provides excellent color.
  • the electroluminescent material In an organic EL device, the most important factor that determines its performance including luminescence efficiency and operation life is the electroluminescent material. Some requirements of the electroluminescent material include high electroluminescence quantum yield in solid state, high electron and hole mobility, resistance to decomposition during vacuum deposition, ability to form uniform film and stability.
  • Organic electroluminescent materials are generally classified into high-molecular materials and low-molecular materials.
  • the low-molecular materials include metal complexes and thoroughly organic electroluminescent materials which do not contain metal, from the aspect of molecular structure.
  • Such electroluminescent materials include chelate complexes such as tris(8-quinolinolato)aluminum complexes, coumarin derivatives, tetraphenylbutadiene derivatives, bis(styrylarylene) derivatives and oxadiazole derivatives. From those materials, it is reported that light emission of visible region from blue to red can be obtained.
  • electroluminescent materials for red, green and blue
  • OLED organic light-emitting diode
  • the important issue is to develop red, green and blue electroluminescent materials with high efficiency and long life, in order to enhance the overall feature of the organic electroluminescent (EL) devices.
  • the EL materials are classified into host materials and dopant materials. It is generally known that a device structure having the most excellent EL properties can be fabricated with an EL layer prepared by doping a dopant to a host.
  • the desired properties for the host material are high purity and appropriate molecular weight to enable vapor-deposition in vacuo.
  • glass transition temperature and thermal decomposition temperature should be high enough to ensure thermal stability.
  • the host material should have high electrochemical stability for providing long life. It is to be easy to form an amorphous thin film, with high adhesiveness to other adjacent materials but without interlayer migration.
  • the organic EL device When the organic EL device is fabricated by doping technology, transferring energy from host molecule to dopant in an excited state does not achieve 100% and a host material as well as dopant emits light. In particular, since the host material emits light in a range of wavelength having larger visibility than the dopant in case of a red light emitting device, color purity is deteriorated due to dull light emission of the host material. If the technology is actually applied, it is required to increase luminescence life and improve durability.
  • CBP is most widely known as a host material for a phosphorescent material.
  • High-efficiency OLEDs using a hole blocking layer comprising BCP, BAlq, etc. are reported.
  • High-performance OLEDs using BAlq derivatives as a host were reported by Pioneer (Japan) and others.
  • an object of the present invention is to provide compounds for organic electronic materials having luminescence efficiency and device operation life improved over existing materials and having superior backbone with appropriate color coordinates in order to solve the aforesaid problems.
  • Another object of the present invention is to provide a highly efficient organic electroluminescent device having long operation life by employing the compounds for organic electronic materials as an electroluminescent material.
  • compounds for organic electronic materials represented by Chemical Formula 1 and an organic electroluminescent device using the same.
  • the compounds for organic electronic materials according to the present invention may be used to manufacture an OLED device having very superior operation life and consumption power improved due to increase of power efficiency.
  • X 1 through X 8 independently represent CR' and N;
  • Y represents -Si(R 3 )(R 4 )-, -N(R 3 )-, -S-, -O-, or -Se-;
  • L represents a single bond, (C6-C30)aryl and (C3-C30)heteroaryl;
  • Ar 1 represents (C1-C30)alkyl, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C6-C30)aryl and (C3-C30)heteroaryl;
  • R' and R 1 through R 3 independently represent hydrogen, deuterium, (C1-C30)alkyl, halo(C1-C30)alkyl, halogen, cyano, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C1-C30)alkoxy, (C6-C30)aryloxy, (C3-C30)heteroaryl, (C3-C30)heteroaryl with (C1-C30)alkyl substituent(s), (C3-C30)heteroaryl with (C6-C30)aryl substituent(s), (C6-C30)ar(C1-C30)alkyl, (C6-C30)arylthio, mono- or di(C1-C30)alkylamino, mono- or di(C6
  • the alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl of Ar 1 and the alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl or heteroaryl of R' and R 1 through R 3 may be further substituted by one or more substituent(s) selected from the group consisting of deuterium, (C1-C30)alkyl, halo(C1-C30)alkyl, halogen, cyano, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl,(C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C6-C30)aryl with (C3-C30)heteroaryl substituent(s), (C1-C30)alkoxy, (C6-C30)aryloxy, (C3-C30)heteroary
  • R' may be linked to an adjacent R' via (C3-C30)alkylene or (C3-C30)alkenylene to form a ring;
  • alkyl in the present invention, “alkyl”, “alkoxy” and other substituents containing “alkyl” moiety include both linear and branched species.
  • the "cycloalkyl” includes polycyclic hydrocarbon ring such as adamantyl with or without substituent(s) or (C7-C30)bicycloalkyl with or without substituent(s) as well as a monocyclic hydrocarbon ring.
  • aryl means an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen atom, and may include a 4- to 7-membered, particularly 5- or 6-membered, single ring or fused ring, including a plurality of aryl groups having single bond(s) therebetween.
  • Specific examples include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc., but are not limited thereto.
  • the naphthyl includes 1-naphthyl and 2-naphthyl.
  • the anthryl includes 1-anthryl, 2-anthryl and 9-anthryl, and the fluorenyl includes 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl.
  • the heteroaryl also includes heteroaryl groups having single bond(s) therebetween.
  • the heteroaryl includes a divalent aryl group wherein the heteroatom(s) in the ring may be oxidized or quaternized to form, for example, an N-oxide or a quaternary salt.
  • Specific examples include monocyclic heteroaryl such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., polycyclic heteroaryl such as benzofuranyl, benzothiophenyl, isobenzofuranyl, benzimidazolyl, benzothiazolyl, benzoisothi
  • the “(C1-C30)alkyl” groups described herein may include (C1-C20)alkyl or (C1-C10)alkyl and the "(C6-C30)aryl” groups include (C6-C20)aryl or (C6-C12)aryl.
  • the "(C3-C30)heteroaryl” groups include (C3-C20)heteroaryl or (C3-C12)heteroaryl and the "(C3-C30)cycloalkyl” groups include (C3-C20)cycloalkyl or (C3-C7)cycloalkyl.
  • the "(C2-C30)alkenyl or alkynyl” group include (C2-C20)alkenyl or alkynyl, (C2-C10)alkenyl or alkynyl.
  • the compounds for organic electronic materials according to the present invention may be selected from following structures but are not limited thereto:
  • the may be selected from following structures but is not limited thereto:
  • R' represents hydrogen, (C6-C30)aryl, (C3-C30)heteroaryl, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, or tri(C6-C30)arylsilyl, and the aryl or heteroaryl may be further substituted by one or more selected from the group consisting of (C6-C30)aryl and (C3-C30)heteroaryl.
  • the compounds for organic electronic material according to the present invention may be specifically exemplified by following compounds but the present invention is not limited by the compounds:
  • the compounds for organic electronic materials according to the present invention may be prepared as shown in following Scheme 1.
  • X 1 through X 8 , Y, L and Ar 1 are the same as defined in Chemical Formula 1.
  • an organic electroluminescent device which comprises a first electrode; a second electrode; and one or more organic layer(s) interposed between the first electrode and the second electrode, wherein the organic layer comprises one or more compounds for organic electronic material (s) represented by Chemical Formula 1.
  • the organic layer comprises an electroluminescent layer, in which the compounds for organic electronic material of Chemical Formula 1 are used as a host material.
  • the phosphorescent dopant used in the organic electroluminescent device of the present invention is not particularly limited, but may be selected from the compounds represented by Chemical Formula 2:
  • M 1 is a metal selected from the group consisting of Group 7, Group 8, Group 9, Group 10, Group 11, Group 13, Group 15 and Group 16 metals, and ligands L 101 , L 102 and L 103 are independently selected from the structures:
  • R 201 through R 203 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without halogen substituent(s), (C6-C30)aryl with or without (C1-C30)alkyl substituent(s) or halogen;
  • R 204 through R 219 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without substituent(s), (C1-C30)alkoxy with or without substituent(s), (C3-C30)cycloalkyl with or without substituent(s), (C2-C30)alkenyl with or without substituent(s), (C6-C30)aryl with or without substituent(s), mono- or di(C1-C30)alkylamino with or without substituent(s), mono- or di(C6-C30)arylamino with or without substituent(s), SF 5 , tri(C1-C30)alkylsilyl with or without substituent(s), di(C1-C30)alkyl(C6-C30)arylsilyl with or without substituent(s), tri(C6-C30)arylsilyl with or without substituent(s), cyano or halogen;
  • R 220 through R 223 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without halogen substituent(s) or (C6-C30)aryl with or without (C1-C30)alkyl substituent(s);
  • R 224 and R 225 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s) or halogen, or R 224 and R 225 may be linked via (C3-C12)alkylene or (C3-C12)alkenylene with or without a fused ring to form an alicyclic ring or a mono- or polycyclic aromatic ring;
  • R 226 represents (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s), (C5-C30)heteroaryl with or without substituent(s) or halogen;
  • R 227 through R 229 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s) or halogen;
  • R 231 through R 242 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without halogen substituent(s), (C1-C30)alkoxy, halogen, (C6-C30)aryl with or without substituent(s), cyano or (C5-C30)cycloalkyl with or without substituent(s), or each of them may be linked to an adjacent substituent via alkylene or alkenylene to form a spiro ring or a fused ring, or may be linked to R 207 or R 208 via alkylene or alkenylene to form a saturated or unsaturated fused ring.
  • the phosphorescent dopant compounds of Chemical Formula 2 may be exemplified as the compounds having following structures but are not limited thereto:
  • the organic layer may further include, in addition to the compound for organic electric material represented by Chemical Formula 1, one or more compound(s) selected from the group consisting of arylamine compounds and styrylarylamine compounds, at the same time.
  • the arylamine compounds or styrylarylamine compounds are exemplified in Korean Patent Application No. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but are not limited thereto.
  • the organic layer may further include, in addition to the compounds for organic electronic materials represented by Chemical Formula 1, one or more metal(s) selected from the group consisting of organic metals of Group 1, Group 2, 4th period and 5th period transition metals, lanthanide metals and d-transition elements or complex compound(s).
  • the organic layer may include an electroluminescent layer and a charge generating layer.
  • the organic layer may include, in addition to the compound for organic electric material of Chemical Formula 1, one or more organic electroluminescent layer(s) emitting blue, green or red light at the same time in order to embody a white-emitting organic electroluminescent device.
  • the compound emitting blue, green or red light may be exemplified by the compounds described in Korean Patent Application No. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but are not limited thereto.
  • a layer (hereinafter referred to as "surface layer" selected from a chalcogenide layer, a metal halide layer and a metal oxide layer may be placed on the inner surface of one or both electrode(s) among the pair of electrodes. More specifically, a metal chalcogenide (including oxide) layer of silicon or aluminum may be placed on the anode surface of the electroluminescent medium layer, and a metal halide layer or metal oxide layer may be placed on the cathode surface of the electroluminescent medium layer. Operation stability may be attained therefrom.
  • the metal halide may be, for example, LiF, MgF 2 , CaF 2 , a rare earth metal fluoride, etc.
  • the metal oxide may be, for example, Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
  • the organic electroluminescent device it is also preferable to arrange on at least one surface of the pair of electrodes thus manufactured a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant.
  • a mixed region of an electron transport compound and a reductive dopant or a mixed region of a hole transport compound and an oxidative dopant.
  • the electron transport compound is reduced to an anion, injection and transport of electrons from the mixed region to an electroluminescent medium are facilitated.
  • the hole transport compound is oxidized to a cation, injection and transport of holes from the mixed region to an electroluminescent medium are facilitated.
  • Preferable oxidative dopants include various Lewis acids and acceptor compounds.
  • Preferable reductive dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof. Further, a white-emitting electroluminescent device having two or more electroluminescent layers may be manufactured by employing a reductive dopant layer as a charge generating layer.
  • the compounds for organic electronic material according to the present invention exhibits good luminous efficiency and excellent life property, it may be used to manufacture OLED devices having very superior operation life.
  • the present invention is further described with respect to the compounds for organic electronic materials according to the present invention, processes for preparing the same, and luminescence properties of devices employing the same.
  • the following examples are provided for illustrative purposes only and they are not intended to limit the scope of the present invention.
  • An OLED device was manufactured using the compound for organic electronic materials according to the present invention.
  • a transparent electrode ITO thin film (15 ⁇ / ⁇ ) obtained from a glass for OLED (produced by Samsung Corning) was subjected to ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and stored in isopropanol before use.
  • an ITO substrate was equipped in a substrate folder of a vacuum vapor deposition apparatus, and 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine (2-TNATA) was placed in a cell of the vacuum vapor deposition apparatus, which was then ventilated up to 10 -6 torr of vacuum in the chamber. Then, electric current was applied to the cell to evaporate 2-TNATA, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate.
  • 2-TNATA 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine
  • N , N '-bis( ⁇ -naphthyl)- N , N '-diphenyl-4,4'-diamine (NPB) was placed in another cell of the vacuum vapor deposition apparatus, and electric current was applied to the cell to evaporate NPB, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer.
  • the compound 2 purified by vacuum sublimation at 10 -6 torr was placed in a cell of a vacuum vapor deposition apparatus as a host, and an electroluminescent dopant (Ir(ppy) 3 [tris(2-phenylpyridine) iridium]) was placed in another cell as a dopant.
  • the two materials were evaporated at different rates such that an electroluminescent layer having a thickness of 30 nm was vapor-deposited on the hole transport layer through doping at 4 to 20 wt%.
  • An OLED device was manufactured as in Example 1 except that Compound 8 was used as a host material at one cell of the vacuum vapor deposition apparatus.
  • An OLED device was manufactured as in Example 1 except that Compound 32 was used as a host material at one cell of the vacuum vapor deposition apparatus and Bis(2-methyl-8-quinolinato)(p-phenyl-phenolato)aluminum(III) (BAlq) was used as a hole blocking layer.
  • An OLED device was manufactured as in Example 1 except that 4,4 -bis(carbazol-9-yl)biphenyl (CBP) instead of the compounds for organic electronic material according to the present invention was used as an electroluminescent host material at another cell of the vacuum vapor deposition apparatus and Bis(2-methyl-8-quinolinato)(p-phenyl-phenolato)aluminum(III) (BAlq) was used as a hole blocking layer after forming the hole injection layer and the hole transport layer in the same manner as that of Example 1.
  • CBP 4,4 -bis(carbazol-9-yl)biphenyl
  • BAlq Bis(2-methyl-8-quinolinato)(p-phenyl-phenolato)aluminum(III)
  • the driving voltage and the luminous efficiencies of the OLED comprising the compound for organic electronic materials according to the present invention in the Examples 1-3 or the conventional electroluminescent compound in Comparative Example 1 were measured at 1,000 cd/m 2 , respectively, and the results are shown in Table 2.
  • the compounds for organic electronic material developed in the present invention have a good luminous property. In particular, since they have a superior hole current property, good power efficiency is obtained in highly bright regions.
  • the compounds for organic electronic material according to the present invention exhibits good luminous efficiency and excellent life property, it may be used to manufacture OLED devices having very superior operation life.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Inorganic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

Provided are novel compounds for organic electronic material and an organic electroluminescent device using the same. Since the compound for organic electronic material exhibits good luminous efficiency and excellent life property, it may be used to manufacture OLED devices having very superior operation life and consuming less power due to improved power efficiency.

Description

NOVEL COMPOUNDS FOR ORGANIC ELECTRONIC MATERIAL AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME
The present invention relates to novel compounds for organic electronic materials and an organic electroluminescent device using the same.
Among display devices, electroluminescent (EL) devices are advantageous in that they provide wide view angle, superior contrast and fast response rate as self-emissive display devices. In 1987, Eastman Kodak first developed an organic EL device using a low-molecular-weight aromatic diamine and aluminum complex as a substance for forming an electroluminescent layer [Appl. Phys. Lett. 51, 913, 1987].
In an organic EL device, when a charge is applied to an organic layer formed between an electron injection electrode (cathode) and a hole injection electrode (anode), an electron and a hole are paired and exciton is generated. Light is emitted by using electroluminescence (phosphorescence or fluorescence) in a state that the exciton is inactivated. The organic EL device emits polarization of light at voltage of about 10V and high brightness of about 100~10,000cd/㎡. The organic EL device has a feature in that light is emitted in a spectrum ranging from blue color to red color by simply selecting a fluorescent material. The organic EL device is advantageous in that it can be formed on a flexible transparent substrate such as plastic, is operable with relatively low voltage (10 V or lower) as compared to plasma display panels or inorganic EL displays, consumes less power, and provides excellent color.
In an organic EL device, the most important factor that determines its performance including luminescence efficiency and operation life is the electroluminescent material. Some requirements of the electroluminescent material include high electroluminescence quantum yield in solid state, high electron and hole mobility, resistance to decomposition during vacuum deposition, ability to form uniform film and stability.
Organic electroluminescent materials are generally classified into high-molecular materials and low-molecular materials. The low-molecular materials include metal complexes and thoroughly organic electroluminescent materials which do not contain metal, from the aspect of molecular structure. Such electroluminescent materials include chelate complexes such as tris(8-quinolinolato)aluminum complexes, coumarin derivatives, tetraphenylbutadiene derivatives, bis(styrylarylene) derivatives and oxadiazole derivatives. From those materials, it is reported that light emission of visible region from blue to red can be obtained.
Three electroluminescent materials (for red, green and blue) are employed to realize a full-colored organic light-emitting diode (OLED) display. The important issue is to develop red, green and blue electroluminescent materials with high efficiency and long life, in order to enhance the overall feature of the organic electroluminescent (EL) devices. From the aspect of function, the EL materials are classified into host materials and dopant materials. It is generally known that a device structure having the most excellent EL properties can be fabricated with an EL layer prepared by doping a dopant to a host. Recently, development of organic EL devices with high efficiency and long life comes to the fore as an urgent subject, and particularly urgent is development of a material with far better EL properties as compared to conventional EL materials as considering EL properties required for a medium to large sized OLED panel.
From this point of view, development of host material is one of the most important issues to be settled. The desired properties for the host material (serving as a solvent and energy conveyer in solid state) are high purity and appropriate molecular weight to enable vapor-deposition in vacuo. In addition, glass transition temperature and thermal decomposition temperature should be high enough to ensure thermal stability. Further, the host material should have high electrochemical stability for providing long life. It is to be easy to form an amorphous thin film, with high adhesiveness to other adjacent materials but without interlayer migration.
When the organic EL device is fabricated by doping technology, transferring energy from host molecule to dopant in an excited state does not achieve 100% and a host material as well as dopant emits light. In particular, since the host material emits light in a range of wavelength having larger visibility than the dopant in case of a red light emitting device, color purity is deteriorated due to dull light emission of the host material. If the technology is actually applied, it is required to increase luminescence life and improve durability.
At present, CBP is most widely known as a host material for a phosphorescent material. High-efficiency OLEDs using a hole blocking layer comprising BCP, BAlq, etc. are reported. High-performance OLEDs using BAlq derivatives as a host were reported by Pioneer (Japan) and others.
Figure PCTKR2011002294-appb-I000001
Although these materials provide good electroluminescence characteristics, they are disadvantageous in that degradation may occur during the high-temperature deposition process in vacuum because of low glass transition temperature and poor thermal stability. Since the power efficiency of an OLED is given by (π / voltage) × current efficiency, the power efficiency is inversely proportional to the voltage. High power efficiency is required to reduce the power consumption of an OLED. Actually, OLEDs using phosphorescent materials provide much better current efficiency (cd/A) than those using fluorescent materials. However, when the existing materials such as BAlq, CBP, etc. are used as a host of the phosphorescent material, there is no significant advantage in power efficiency (lm/W) over the OLEDs using fluorescent materials because of high driving voltage. Further, the OLED devices do not have satisfactory operation life. Therefore, development of more stable, higher-performance host materials is required.
Accordingly, an object of the present invention is to provide compounds for organic electronic materials having luminescence efficiency and device operation life improved over existing materials and having superior backbone with appropriate color coordinates in order to solve the aforesaid problems. Another object of the present invention is to provide a highly efficient organic electroluminescent device having long operation life by employing the compounds for organic electronic materials as an electroluminescent material.
Provided are compounds for organic electronic materials represented by Chemical Formula 1 and an organic electroluminescent device using the same. With superior luminescence efficiency and excellent life property, the compounds for organic electronic materials according to the present invention may be used to manufacture an OLED device having very superior operation life and consumption power improved due to increase of power efficiency.
[Chemical Formula 1]
Figure PCTKR2011002294-appb-I000002
wherein
X1 through X8 independently represent CR' and N;
Y represents -Si(R3)(R4)-, -N(R3)-, -S-, -O-, or -Se-;
L represents a single bond, (C6-C30)aryl and (C3-C30)heteroaryl;
Ar1 represents (C1-C30)alkyl, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C6-C30)aryl and (C3-C30)heteroaryl;
R' and R1 through R3 independently represent hydrogen, deuterium, (C1-C30)alkyl, halo(C1-C30)alkyl, halogen, cyano, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C1-C30)alkoxy, (C6-C30)aryloxy, (C3-C30)heteroaryl, (C3-C30)heteroaryl with (C1-C30)alkyl substituent(s), (C3-C30)heteroaryl with (C6-C30)aryl substituent(s), (C6-C30)ar(C1-C30)alkyl, (C6-C30)arylthio, mono- or di(C1-C30)alkylamino, mono- or di(C6-C30)arylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, tri(C6-C30)arylsilyl, nitro or hydroxyl, or R1 and R2 are linked via (C3-C30)alkylene or (C3-C30)alkenylene with or without a fused ring to form an alicyclic ring or a mono- or polycyclic aromatic ring;
the alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl of Ar1 and the alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl or heteroaryl of R' and R1 through R3 may be further substituted by one or more substituent(s) selected from the group consisting of deuterium, (C1-C30)alkyl, halo(C1-C30)alkyl, halogen, cyano, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl,(C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C6-C30)aryl with (C3-C30)heteroaryl substituent(s), (C1-C30)alkoxy, (C6-C30)aryloxy, (C3-C30)heteroaryl, (C3-C30)heteroaryl with (C1-C30)alkyl substituent(s), (C3-C30)heteroaryl with (C6-C30)aryl substituent(s), (C6-C30)ar(C1-C30)alkyl, (C6-C30)arylthio, mono- or di(C1-C30)alkylamino, mono- or di(C6-C30)arylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, tri(C6-C30)arylsilyl, -P(=O)RaRb[Ra and Rb independently represent (C1-C30)alkyl or (C6-C30)aryl], nitro and hydroxyl;
R' may be linked to an adjacent R' via (C3-C30)alkylene or (C3-C30)alkenylene to form a ring; and
the heterocycloalkyl and the heteroaryl may contain one or more heteroatom(s) selected from B, N, O, S, P(=O), Si and P.
In the present invention, "alkyl", "alkoxy" and other substituents containing "alkyl" moiety include both linear and branched species. In the present invention, the "cycloalkyl" includes polycyclic hydrocarbon ring such as adamantyl with or without substituent(s) or (C7-C30)bicycloalkyl with or without substituent(s) as well as a monocyclic hydrocarbon ring.
In the present invention, "aryl" means an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen atom, and may include a 4- to 7-membered, particularly 5- or 6-membered, single ring or fused ring, including a plurality of aryl groups having single bond(s) therebetween. Specific examples include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc., but are not limited thereto. The naphthyl includes 1-naphthyl and 2-naphthyl. The anthryl includes 1-anthryl, 2-anthryl and 9-anthryl, and the fluorenyl includes 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl. In the present invention, "heteroaryl" means an aryl group containing 1 to 4 heteroatom(s) selected from B, N, O, S, P(=O), Si and P as aromatic ring backbone atom(s), other remaining aromatic ring backbone atoms being carbon. It may be 5- or 6-membered monocyclic heteroaryl or polycyclic heteroaryl resulting from condensation with a benzene ring, and may be partially saturated. The heteroaryl also includes heteroaryl groups having single bond(s) therebetween.
The heteroaryl includes a divalent aryl group wherein the heteroatom(s) in the ring may be oxidized or quaternized to form, for example, an N-oxide or a quaternary salt. Specific examples include monocyclic heteroaryl such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., polycyclic heteroaryl such as benzofuranyl, benzothiophenyl, isobenzofuranyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenanthridinyl, benzodioxolyl, etc., an N-oxide thereof (e.g., pyridyl N-oxide, quinolyl N-oxide, etc.), a quaternary salt thereof, etc., but are not limited thereto.
The "(C1-C30)alkyl" groups described herein may include (C1-C20)alkyl or (C1-C10)alkyl and the "(C6-C30)aryl" groups include (C6-C20)aryl or (C6-C12)aryl. The "(C3-C30)heteroaryl" groups include (C3-C20)heteroaryl or (C3-C12)heteroaryl and the "(C3-C30)cycloalkyl" groups include (C3-C20)cycloalkyl or (C3-C7)cycloalkyl. The "(C2-C30)alkenyl or alkynyl" group include (C2-C20)alkenyl or alkynyl, (C2-C10)alkenyl or alkynyl.
The compounds for organic electronic materials according to the present invention may be selected from following structures but are not limited thereto:
Figure PCTKR2011002294-appb-I000003
Figure PCTKR2011002294-appb-I000004
Figure PCTKR2011002294-appb-I000005
Figure PCTKR2011002294-appb-I000006
Figure PCTKR2011002294-appb-I000007
Figure PCTKR2011002294-appb-I000008
Figure PCTKR2011002294-appb-I000009
wherein
the R', L, Ar1 and Y are the same as defined in Chemical Formula 1.
More specifically, the
Figure PCTKR2011002294-appb-I000010
may be selected from following structures but is not limited thereto:
Figure PCTKR2011002294-appb-I000011
Figure PCTKR2011002294-appb-I000012
Figure PCTKR2011002294-appb-I000013
Figure PCTKR2011002294-appb-I000014
Figure PCTKR2011002294-appb-I000015
Also, R' represents hydrogen, (C6-C30)aryl, (C3-C30)heteroaryl, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, or tri(C6-C30)arylsilyl, and the aryl or heteroaryl may be further substituted by one or more selected from the group consisting of (C6-C30)aryl and (C3-C30)heteroaryl.
The compounds for organic electronic material according to the present invention may be specifically exemplified by following compounds but the present invention is not limited by the compounds:
Figure PCTKR2011002294-appb-I000016
Figure PCTKR2011002294-appb-I000017
Figure PCTKR2011002294-appb-I000018
Figure PCTKR2011002294-appb-I000019
Figure PCTKR2011002294-appb-I000020
Figure PCTKR2011002294-appb-I000021
Figure PCTKR2011002294-appb-I000022
Figure PCTKR2011002294-appb-I000023
The compounds for organic electronic materials according to the present invention may be prepared as shown in following Scheme 1.
[Scheme 1]
Figure PCTKR2011002294-appb-I000024
wherein
X1 through X8, Y, L and Ar1 are the same as defined in Chemical Formula 1.
Provided is an organic electroluminescent device, which comprises a first electrode; a second electrode; and one or more organic layer(s) interposed between the first electrode and the second electrode, wherein the organic layer comprises one or more compounds for organic electronic material (s) represented by Chemical Formula 1. The organic layer comprises an electroluminescent layer, in which the compounds for organic electronic material of Chemical Formula 1 are used as a host material.
When the compounds for organic electronic material of Chemical Formula 1 are used as a host, one or more phosphorescent dopant(s) is included. The phosphorescent dopant used in the organic electroluminescent device of the present invention is not particularly limited, but may be selected from the compounds represented by Chemical Formula 2:
[Chemical Formula 2]
M1L101L102L103
M1 is a metal selected from the group consisting of Group 7, Group 8, Group 9, Group 10, Group 11, Group 13, Group 15 and Group 16 metals, and ligands L101, L102 and L103 are independently selected from the structures:
Figure PCTKR2011002294-appb-I000025
Figure PCTKR2011002294-appb-I000026
Figure PCTKR2011002294-appb-I000027
Figure PCTKR2011002294-appb-I000028
wherein
R201 through R203 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without halogen substituent(s), (C6-C30)aryl with or without (C1-C30)alkyl substituent(s) or halogen;
R204 through R219 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without substituent(s), (C1-C30)alkoxy with or without substituent(s), (C3-C30)cycloalkyl with or without substituent(s), (C2-C30)alkenyl with or without substituent(s), (C6-C30)aryl with or without substituent(s), mono- or di(C1-C30)alkylamino with or without substituent(s), mono- or di(C6-C30)arylamino with or without substituent(s), SF5, tri(C1-C30)alkylsilyl with or without substituent(s), di(C1-C30)alkyl(C6-C30)arylsilyl with or without substituent(s), tri(C6-C30)arylsilyl with or without substituent(s), cyano or halogen;
R220 through R223 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without halogen substituent(s) or (C6-C30)aryl with or without (C1-C30)alkyl substituent(s);
R224 and R225 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s) or halogen, or R224 and R225 may be linked via (C3-C12)alkylene or (C3-C12)alkenylene with or without a fused ring to form an alicyclic ring or a mono- or polycyclic aromatic ring;
R226 represents (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s), (C5-C30)heteroaryl with or without substituent(s) or halogen;
R227 through R229 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without substituent(s), (C6-C30)aryl with or without substituent(s) or halogen; and
Q represents
Figure PCTKR2011002294-appb-I000029
,
Figure PCTKR2011002294-appb-I000030
or
Figure PCTKR2011002294-appb-I000031
, wherein R231 through R242 independently represent hydrogen, deuterium, (C1-C30)alkyl with or without halogen substituent(s), (C1-C30)alkoxy, halogen, (C6-C30)aryl with or without substituent(s), cyano or (C5-C30)cycloalkyl with or without substituent(s), or each of them may be linked to an adjacent substituent via alkylene or alkenylene to form a spiro ring or a fused ring, or may be linked to R207 or R208 via alkylene or alkenylene to form a saturated or unsaturated fused ring.
The phosphorescent dopant compounds of Chemical Formula 2 may be exemplified as the compounds having following structures but are not limited thereto:
Figure PCTKR2011002294-appb-I000032
Figure PCTKR2011002294-appb-I000033
Figure PCTKR2011002294-appb-I000034
Figure PCTKR2011002294-appb-I000035
Figure PCTKR2011002294-appb-I000036
Figure PCTKR2011002294-appb-I000037
Figure PCTKR2011002294-appb-I000038
In the organic electronic device of the present invention, the organic layer may further include, in addition to the compound for organic electric material represented by Chemical Formula 1, one or more compound(s) selected from the group consisting of arylamine compounds and styrylarylamine compounds, at the same time. The arylamine compounds or styrylarylamine compounds are exemplified in Korean Patent Application No. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but are not limited thereto.
Further, in the organic electroluminescent device of the present invention, the organic layer may further include, in addition to the compounds for organic electronic materials represented by Chemical Formula 1, one or more metal(s) selected from the group consisting of organic metals of Group 1, Group 2, 4th period and 5th period transition metals, lanthanide metals and d-transition elements or complex compound(s). The organic layer may include an electroluminescent layer and a charge generating layer.
Further, the organic layer may include, in addition to the compound for organic electric material of Chemical Formula 1, one or more organic electroluminescent layer(s) emitting blue, green or red light at the same time in order to embody a white-emitting organic electroluminescent device. The compound emitting blue, green or red light may be exemplified by the compounds described in Korean Patent Application No. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but are not limited thereto.
In the organic electroluminescent device of the present invention, a layer (hereinafter referred to as "surface layer" selected from a chalcogenide layer, a metal halide layer and a metal oxide layer may be placed on the inner surface of one or both electrode(s) among the pair of electrodes. More specifically, a metal chalcogenide (including oxide) layer of silicon or aluminum may be placed on the anode surface of the electroluminescent medium layer, and a metal halide layer or metal oxide layer may be placed on the cathode surface of the electroluminescent medium layer. Operation stability may be attained therefrom.
The chalcogenide may be, for example, SiOx (1 = x = 2), AlOx (1 = x = 1.5), SiON, SiAlON, etc. The metal halide may be, for example, LiF, MgF2, CaF2, a rare earth metal fluoride, etc. The metal oxide may be, for example, Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
In the organic electroluminescent device according to the present invention, it is also preferable to arrange on at least one surface of the pair of electrodes thus manufactured a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant. In that case, since the electron transport compound is reduced to an anion, injection and transport of electrons from the mixed region to an electroluminescent medium are facilitated. In addition, since the hole transport compound is oxidized to a cation, injection and transport of holes from the mixed region to an electroluminescent medium are facilitated. Preferable oxidative dopants include various Lewis acids and acceptor compounds. Preferable reductive dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof. Further, a white-emitting electroluminescent device having two or more electroluminescent layers may be manufactured by employing a reductive dopant layer as a charge generating layer.
Since the compounds for organic electronic material according to the present invention exhibits good luminous efficiency and excellent life property, it may be used to manufacture OLED devices having very superior operation life.
The present invention is further described with respect to the compounds for organic electronic materials according to the present invention, processes for preparing the same, and luminescence properties of devices employing the same. However, the following examples are provided for illustrative purposes only and they are not intended to limit the scope of the present invention.
[Preparation Example 1] Preparation of Compound 32
Figure PCTKR2011002294-appb-I000039
Preparation of Compound 1-1
After 2-bromonitrobenzene (40g, 200mmol), triethylamine (350mL), Pd(PPh3)2Cl2 (7g, 10mmol) and CuI (0.95g, 5mmol) were mixed, acetylene (23.5g, 239mmol) was added thereto. The reaction mixture was stirred at room temperature overnight. After distilling triethylamine under reduced pressure, the mixture was extracted with distilled water and ethylacetate. After drying an organic layer with anhydrous MgSO4 and removing a solvent by a rotary type evaporator, Compound 1-1 (39g, 89%) was obtained via purification by column chromatography using hexane as a developing solvent.
Preparation of Compound 1-2
After dissolving Compound 1-1 (39g, 178mmol) in THF (1.2L) at nitrogen atmosphere, tetrabutylammonium fluoride (280mL, 1M solution in THF, 213mmol) was added thereto. The reaction mixture was stirred at room temperature for 1.5 hours and extracted with distilled water and ethylacetate. After drying an organic layer with anhydrous MgSO4 and removing a solvent by a rotary type evaporator, Compound 1-2 (16.2g, 62%) was obtained via purification by column chromatography using methylene chloride (MC) and hexane as a developing solvent.
Preparation of Compound 1-3
After 2-iodonitrobenzene (22.4g, 130mmol), triethylamine (1.5L), Pd(PPh3)2Cl2 (3.7g, 5.4mmol), CuI (1g, 2.2mmol) and Compound 1-2 (16g, 109mmol) were mixed, the mixture was stirred at room temperature overnight. After dissolving suspension, which is obtained after filtration, in MC and performing silica filtering, Compound 1-3 (26g, 89%) was obtained via recrystallization with ethanol.
Preparation of Compound 1-4
Compound 1-3 (26g, 97mmol), KMnO4 (46g, 291mmol), Adogen 464 (25mL), MC 1 L, H2O (800mL) and acetic acid (30mL) were mixed and stirred at 80℃ for 3 hours. The mixture was extracted with distilled water and MC. After drying an organic layer with anhydrous MgSO4 and performing silica filtering, Compound 1-4 (16g, 55%) was obtained.
Preparation of Compound 1-5
Compound 1-4 (16g, 53mmol), SnCl22H2O (120g, 800mmol), acetic acid (600mL) and 1N HCl (70mL) were added and stirred at 80℃ overnight. After distilling a reaction solvent under reduced pressure, the reaction mixture was dissolved in THF and EA and washed with NaHCO3 solution and brine. After removing moisture with anhydrous MgSO4 and performing distillation under reduced pressure, Compound 1-5 (4.2g, 38%) was obtained via recrystallization with MeOH.
Preparation of Compound 1-6
carbazole (20g, 120mmol), 1,4-dibromobenzene (102g, 360mmol), Cu (11.4, 180mmol), 18-crown-6 (2.6g, 9.6mmol), K2CO3 (50g, 360mmol) and 1,2-dichlorobenzene (600mL) were added and stirred under reflux overnight. After removing a reaction solvent via distillation under reduced pressure, a solvent was removed by distilling liquid, which is obtained via filtering (washed with MC and THF), under reduced pressure. Compound 1-6 (25g, 65%) was obtained via purification by column chromatography using MC and hexane as a developing solvent.
Preparation of Compound 32
Compound 1-5 (4g, 20mmol), Compound 1-6 (19g, 58.8mmol), Cu (3.7g, 58.2mmol), 18-crown-6 (1g, 3.9mmol), K2CO3 (13.5g, 97mmol) and 1,2-dichlorobenzene (100mL) were added and stirred under reflux for 36 hours. After removing a reaction solvent via distillation under reduced pressure, a solvent was removed by distilling liquid, which is obtained via filtering (washed with MC and THF), under reduced pressure. Compound 32 (25g, 65%) was obtained via purification by column chromatography using MC and hexane as a developing solvent.
Compounds for organic electronic material 1 to 32 were prepared according to Preparation Example 1. Table 1 shows 1H NMR and MS/FAB of the prepared compounds for organic electronic material.
Table 1
Comp. 1H NMR(CDCl3, 200 MHz) MS/FAB
found calculated
1 δ= 7.25(2H, m), 7.33(2H, m), 7.45~7.58(11H, m), 7.68(2H, m), 7.79(2H, m), 7.94(2H, m), 8.2(2H, m), 8.3(4H, m), 8.74(2H, m) 587.71 587.24
2 δ= 7.25(2H, m), 7.33(2H, m), 7.41~7.51(9H, m), 7.58(2H, m), 7.68(2H, m), 7.79(6H, m), 7.94(2H, m), 8.23(1H, s), 8.74(2H, m) 588.70 588.23
3 δ= 7.25(2H, m), 7.33(2H, m), 7.41~7.51(9H, m), 7.58(2H, m), 7.68(2H, m), 7.79(2H, m), 7.94(2H, m), 8.28(4H, m), 8.74(2H, m) 589.69 589.23
4 δ= 7.11(1H, m), 7.25(2H, m), 7.33(2H, m), 7.41~7.5(13H, m), 7.94(2H, m), 8.3(2H, m), 8.6(1H, m), 8.74(2H, m) 511.61 511.20
5 δ= 7.25(2H, m), 7.33(2H, m), 7.41~7.51(9H, m), 7.58(2H, m), 7.79(4H, m), 7.94(2H, m), 8.63(1H, s), 8.74(2H, m) 512.60 512.20
6 δ= 7.25(2H, m), 7.33(2H, m), 7.41~7.51(9H, m), 7.58(2H, m), 7.94(2H, m), 8.28(4H, m), 8.74(2H, m) 513.59 513.20
7 δ= 7.25(2H, m), 7.33(2H, m), 7.41~7.51(8H, m), 7.58(2H, m), 7.68(2H, m), 7.79~7.85(6H, m), 7.94(2H, m), 8.74(2H, m) 510.63 510.21
8 δ= 7.25(2H, m), 7.33(2H, m), 7.45~7.5(3H, m), 7.58(2H, m), 7.68(2H, m), 7.79~7.88(6H, m), 7.94(2H, m), 8.04(1H, m), 8.12(2H, m), 8.18(1H, m), 8.74(2H, m), 8.93(2H, m), 9.15(1H, m) 584.71 584.23
9 δ= 3.18(6H, m), 3.65(2H, m), 6.76(2H, m), 7.25(2H, m), 7.33(2H, m), 7.41~7.44(4H, m), 7.51~7.52(8H, m), 7.88(1H, m), 7.94(2H, m), 8.05(2H, m), 8.74(2H, m) 595.73 595.26
10 δ= 7.25~7.33(7H, m), 7.45~7.5(4H, m), 7.58~7.63(7H, m), 7.94(3H, m), 8.12(1H, m), 8.55(1H, m), 8.74(2H, m) 523.63 523.20
11 δ= 7.25~7.33(7H, m), 7.45~7.5(4H, m), 7.58~7.68(7H, m), 7.79(4H, m), 7.94(3H, m), 8.12(1H, m), 8.55(1H, m), 8.74(2H, m) 599.72 599.24
12 δ= 7.25(2H, m), 7.33(2H, m), 7.41~7.52(11H, m), 7.58~7.62(5H, m), 7.69(1H, m), 7.77(1H, m), 7.87(1H, m), 7.94~7.98(4H, m), 8.74(2H, m) 599.72 599.24
13 δ= 7.25~7.33(5H, m), 7.45~7.5(7H, m), 7.58~7.68(7H, m), 7.77~7.79(3H, m), 7.94~8(3H, m), 8.12(1H, m), 8.18(1H, m), 8.74(2H, m) 599.72 599.24
14 δ= 7.25(2H, m), 7.33(2H, m), 7.37~7.46(22H, m), 7.76(1H, m), 7.89~7.96(4H, m), 8.57(1H, m), 8.74(2H, m) 694.90 694.26
15 δ= 1.72(6H, s), 7.25~7.38(10H, m), 7.45~7.58(14H, m), 7.66~7.72(3H, m), 7.83~7.87(2H, m), 7.94~7.97(3H, m), 8.74(2H, m) 732.98 732.30
16 δ= 7.25(2H, m), 7.33(2H, m), 7.45~7.5(9H, m), 7.58(2H, m), 7.68(2H, m), 7.77~7.83(10H, m), 7.94(2H, m), 8.74(2H, m) 634.70 634.22
17 δ= 7.25(2H, m), 7.32~7.38(5H, m), 7.45~7.5(3H, m), 7.58(2H, m), 7.66~7.68(3H, m), 7.79~7.94(7H, m), 8.74(2H, m) 524.61 524.19
18 δ= 7.25(2H, m), 7.33(2H, m), 7.45~7.52(5H, m), 7.58(3H, m), 7.68(2H, m), 7.79(2H, m), 7.94~7.98(3H, m), 8.2(1H, m), 8.41~8.45(2H, m), 8.74(2H, m) 540.68 540.17
19 δ= 7.25(2H, m), 7.33(2H, m), 7.41~7.52(8H, m), 7.58(2H, m), 7.68(2H, m), 7.79(2H, m), 7.86(2H, m), 7.94~8(6H, m), 8.74(2H, m) 616.77 616.20
20 δ= 7.25(2H, m), 7.33(2H, m), 7.45~7.5(6H, m), 7.58~7.68(10H, m), 7.77~7.79(3H, m), 7.94~8(3H, m), 8.16~8.18(2H, m), 8.54(1H, m), 8.74(2H, m) 649.78 649.25
21 δ= 1.72(6H, s), 7.25~7.38(6H, m), 7.45~7.68(9H, m), 7.77~7.79(3H, m), 7.87~7.94(4H, m), 8.74(2H, m) 550.69 550.24
22 δ= 7.25~7.33(7H, m), 7.45~7.5(4H, m), 7.58~7.79(13H, m), 7.94(3H, m), 8.12(1H, m), 8.55(1H, m), 8.74(2H, m) 681.84 681.22
23 δ= 7.25~7.37(9H, m), 7.45~7.58(19H, m), 7.68(1H, m), 7.94(1H, m), 8.53(1H, m), 8.74(1H, m) 616.82 616.23
24 δ= 0.66(6H, s), 7.23~7.25(3H, m), 7.33(1H, m), 7.41(2H, m), 7.51(5H, m), 7.68(2H, m), 7.79(7H, m), 7.94(1H, m), 8.23(1H, s), 8.43(1H, m) 555.74 555.21
25 δ= 7.25(1H, m), 7.33~7.55(19H, m), 7.61(1H, m), 7.68(2H, m), 7.79(6H, m), 7.89~7.94(2H, m), 8.23(1H, s), 8.43(1H, m) 679.88 679.24
26 δ= 7.25(1H, m), 7.33(1H, m), 7.41(2H, m), 7.5~7.52(6H, m), 7.68(2H, m), 7.79(6H, m), 7.94~7.98(2H, m), 8.05(1H, m), 8.23(1H, s), 8.43(1H, m) 529.65 529.16
27 δ= 7.25(1H, m), 7.32~7.41(5H, m), 7.51(4H, m), 7.66~7.7(4H, m), 7.79(6H, m), 7.94(1H, m), 8.23(1H, s), 8.43(1H, m) 513.59 513.18
28 δ= 7.25~7.33(5H, m), 7.45~7.5(7H, m), 7.58~7.68(7H, m), 7.77~7.79(3H, m), 7.94~8(3H, m), 8.12(1H, m), 8.18(1H, m), 8.55(1H, m), 8.74(1H, m) 599.72 599.24
29 δ= 7.25~7.33(3H, m), 7.45~7.5(10H, m), 7.58~7.63(8H, m), 7.77(1H, m), 7.94~8(2H, m), 8.1~8.12(2H, m), 8.18(1H, m), 8.49(1H, m), 8.74(1H, m) 599.72 599.24
30 δ= 7.25(1H, m), 7.33(1H, m), 7.45~7.52(8H, m), 7.58(5H, m), 7.77(1H, m), 7.94~8(3H, m), 8.18~8.2(2H, m), 8.41~8.45(2H, m), 8.74(1H, m) 540.68 540.17
31 δ= 7.25(2H, m), 7.33(2H, m), 7.41~7.51(6H, m), 7.58(3H, m), 7.68(2H, m), 7.79~7.84(6H, m), 7.94(2H, m), 8.16(1H, m), 8.74(2H, m) 562.66 562.22
32 δ= 7.25~7.33(10H, m), 7.5(2H, m), 7.62~7.63(10H, m), 7.94(4H, m), 8.12(2H, m), 8.55(2H, m), 8.74(2H, m) 688.82 688.26
[Example 1] Manufacture of OLED device using compound for organic electronic materials according to the present invention
An OLED device was manufactured using the compound for organic electronic materials according to the present invention. First, a transparent electrode ITO thin film (15 Ω/□) obtained from a glass for OLED (produced by Samsung Corning) was subjected to ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and stored in isopropanol before use.
Then, an ITO substrate was equipped in a substrate folder of a vacuum vapor deposition apparatus, and 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine (2-TNATA) was placed in a cell of the vacuum vapor deposition apparatus, which was then ventilated up to 10-6 torr of vacuum in the chamber. Then, electric current was applied to the cell to evaporate 2-TNATA, 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 (NPB) was placed in another cell of the vacuum vapor deposition apparatus, and electric current was applied to the cell to evaporate NPB, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer.
The compound 2 purified by vacuum sublimation at 10-6torr was placed in a cell of a vacuum vapor deposition apparatus as a host, and an electroluminescent dopant (Ir(ppy)3 [tris(2-phenylpyridine) iridium]) was placed in another cell as a dopant. The two materials were evaporated at different rates such that an electroluminescent layer having a thickness of 30 nm was vapor-deposited on the hole transport layer through doping at 4 to 20 wt%.
Subsequently, tris(8-hydroxyquinoline)-aluminum(III) (Alq) was vapor-deposited with a thickness of 20 nm as an electron transport layer on the electroluminescent layer. Then, after vapor-depositing lithium quinolate (Liq) with a thickness of 1 to 2 nm as an electron injection layer, an Al cathode having a thickness of 150 nm was formed using another vacuum vapor deposition apparatus to manufacture an OLED.
[Example 2]
An OLED device was manufactured as in Example 1 except that Compound 8 was used as a host material at one cell of the vacuum vapor deposition apparatus.
[Example 3]
An OLED device was manufactured as in Example 1 except that Compound 32 was used as a host material at one cell of the vacuum vapor deposition apparatus and Bis(2-methyl-8-quinolinato)(p-phenyl-phenolato)aluminum(III) (BAlq) was used as a hole blocking layer.
[Comparative Example 1] Manufacture of OLED device using conventional electroluminescent materials
An OLED device was manufactured as in Example 1 except that 4,4 -bis(carbazol-9-yl)biphenyl (CBP) instead of the compounds for organic electronic material according to the present invention was used as an electroluminescent host material at another cell of the vacuum vapor deposition apparatus and Bis(2-methyl-8-quinolinato)(p-phenyl-phenolato)aluminum(III) (BAlq) was used as a hole blocking layer after forming the hole injection layer and the hole transport layer in the same manner as that of Example 1.
The driving voltage and the luminous efficiencies of the OLED comprising the compound for organic electronic materials according to the present invention in the Examples 1-3 or the conventional electroluminescent compound in Comparative Example 1 were measured at 1,000 cd/m2, respectively, and the results are shown in Table 2.
Table 2
Host material Dopant material Hole blocking layer @1,000cd/m2 Color
Driving voltage (V) Luminous efficiency(cd/A)
Example 1 Compound 2 Ir(ppy)3 - 7.1 23.4 Green
Example 2 Compound 8 Ir(ppy)3 - 7.4 26.2 Green
Example 3 Compound 32 Ir(ppy)3 BAlq 6.8 30.1 Green
Comparative Example 1 CBP Ir(ppy)3 BAlq 7.5 25.1 Green
As shown in Table 2, the compounds for organic electronic material developed in the present invention have a good luminous property. In particular, since they have a superior hole current property, good power efficiency is obtained in highly bright regions.
Since the compounds for organic electronic material according to the present invention exhibits good luminous efficiency and excellent life property, it may be used to manufacture OLED devices having very superior operation life.

Claims (10)

  1. An compounds for organic electronic material represented by Chemical Formula 1:
    [Chemical Formula 1]
    Figure PCTKR2011002294-appb-I000040
    wherein
    X1 through X8 independently represent CR' and N;
    Y represents -Si(R3)(R4)-, -N(R3)-, -S-, -O-, or -Se-;
    L represents a single bond, (C6-C30)aryl and (C3-C30)heteroaryl;
    Ar1 represents (C1-C30)alkyl, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C6-C30)aryl and (C3-C30)heteroaryl;
    R' and R1 through R3 independently represent hydrogen, deuterium, (C1-C30)alkyl, halo(C1-C30)alkyl, halogen, cyano, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C1-C30)alkoxy, (C6-C30)aryloxy, (C3-C30)heteroaryl, (C3-C30)heteroaryl with (C1-C30)alkyl substituent(s), (C3-C30)heteroaryl with (C6-C30)aryl substituent(s), (C6-C30)ar(C1-C30)alkyl, (C6-C30)arylthio, mono- or di(C1-C30)alkylamino, mono- or di(C6-C30)arylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, tri(C6-C30)arylsilyl, nitro or hydroxyl, or R1 and R2 are linked via (C3-C30)alkylene or (C3-C30)alkenylene with or without a fused ring to form an alicyclic ring or a mono- or polycyclic aromatic ring;
    the alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl of Ar1 and the alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl or heteroaryl of R' and R1 through R3 may be further substituted by one or more substituent(s) selected from the group consisting of deuterium, (C1-C30)alkyl, halo(C1-C30)alkyl, halogen, cyano, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl,(C2-C30)alkenyl, (C2-C30)alkynyl, (C6-C30)aryl, (C6-C30)aryl with (C3-C30)heteroaryl substituent(s), (C1-C30)alkoxy, (C6-C30)aryloxy, (C3-C30)heteroaryl, (C3-C30)heteroaryl with (C1-C30)alkyl substituent(s), (C3-C30)heteroaryl with (C6-C30)aryl substituent(s), (C6-C30)ar(C1-C30)alkyl, (C6-C30)arylthio, mono- or di(C1-C30)alkylamino, mono- or di(C6-C30)arylamino, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, tri(C6-C30)arylsilyl, -P(=O)RaRb[Ra and Rb independently represent (C1-C30)alkyl or (C6-C30)aryl], nitro and hydroxyl;
    R' may be linked to an adjacent R' via (C3-C30)alkylene or (C3-C30)alkenylene to form a ring; and
    the heterocycloalkyl and the heteroaryl may contain one or more heteroatom(s) selected from B, N, O, S, P(=O), Si and P.
  2. The compounds for organic electronic material according to claim 1, which is selected from the following structures:
    Figure PCTKR2011002294-appb-I000042
    Figure PCTKR2011002294-appb-I000043
    Figure PCTKR2011002294-appb-I000044
    Figure PCTKR2011002294-appb-I000045
    Figure PCTKR2011002294-appb-I000046
    Figure PCTKR2011002294-appb-I000047
    wherein
    the R', L, Ar1 and Y are the same as defined in claim 1.
  3. The compounds for organic electronic material according to claim 2, wherein
    Figure PCTKR2011002294-appb-I000048
    is selected from following structures:
    Figure PCTKR2011002294-appb-I000049
    Figure PCTKR2011002294-appb-I000050
    Figure PCTKR2011002294-appb-I000051
    Figure PCTKR2011002294-appb-I000052
    Figure PCTKR2011002294-appb-I000053
  4. The compounds for organic electronic material according to claim 2, wherein R' represents hydrogen, (C6-C30)aryl, (C3-C30)heteroaryl, tri(C1-C30)alkylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, or tri(C6-C30)arylsilyl, and the aryl or heteroaryl is further substituted by one or more selected from the group consisting of (C6-C30)aryl and (C3-C30)heteroaryl.
  5. An organic electroluminescent device comprising the compounds for organic electronic material according to any of claims 1 to 4.
  6. The organic electroluminescent device according to claim 5, which comprises a first electrode; a second electrode; and one or more organic layer(s) interposed between the first electrode and the second electrode, wherein the organic layer comprises one or more compound(s) for organic electronic materials according to any of claims 1 to 4 and one or more phosphorescent dopant(s).
  7. The organic electroluminescent device according to claim 6, wherein the organic layer further comprises one or more amine compound(s) selected from the group consisting of arylamine compounds and styrylarylamine compounds.
  8. The organic electroluminescent device according to claim 6, wherein the organic layer further comprises one or more metal(s) selected from the group consisting of organic metals of Group 1, Group 2, 4th period and 5th period transition metals, lanthanide metals and d-transition elements or complex compound(s).
  9. The organic electroluminescent device according to claim 6, wherein the organic layer comprises an electroluminescent layer and a charge generating layer.
  10. The organic electroluminescent device according to claim 6, which is a white-light emitting organic electroluminescent device wherein the organic layer further comprises one or more organic electroluminescent layer(s) emitting blue, red or green light.
PCT/KR2011/002294 2010-04-20 2011-04-01 Novel compounds for organic electronic material and organic electroluminescent device using the same WO2011132866A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2010-0036167 2010-04-20
KR1020100036167A KR20110116635A (en) 2010-04-20 2010-04-20 Novel organic electroluminescent compounds and organic electroluminescent device using the same

Publications (1)

Publication Number Publication Date
WO2011132866A1 true WO2011132866A1 (en) 2011-10-27

Family

ID=44834345

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2011/002294 WO2011132866A1 (en) 2010-04-20 2011-04-01 Novel compounds for organic electronic material and organic electroluminescent device using the same

Country Status (2)

Country Link
KR (1) KR20110116635A (en)
WO (1) WO2011132866A1 (en)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012087187A (en) * 2010-10-18 2012-05-10 Kaneka Corp Light-emitting material and organic el element
CN103214490A (en) * 2013-03-25 2013-07-24 中国科学院青岛生物能源与过程研究所 Method for preparing novel organic field effect transistor material
US20130193429A1 (en) * 2010-10-13 2013-08-01 Yuichi Sawada Organic electroluminescent element
WO2014070029A1 (en) * 2012-11-05 2014-05-08 Instytut Chemii Organicznej Polskiej Akademii Nauk Strongly fluorescent heterocycles and a method for their synthesis
WO2014126241A1 (en) * 2013-02-18 2014-08-21 国立大学法人京都工芸繊維大学 Light emitting material and organic el element
US20150171338A1 (en) * 2013-12-18 2015-06-18 Samsung Display Co., Ltd. Material for organic electroluminescence device and organic electroluminescence device including the same
US20150171339A1 (en) * 2013-12-18 2015-06-18 Samsung Display Co., Ltd. Material for organic electroluminescence device and organic electroluminescence device using the same
WO2015125679A1 (en) * 2014-02-18 2015-08-27 保土谷化学工業株式会社 Benzofuroindole derivative and organic electroluminescence element
CN105732658A (en) * 2014-12-31 2016-07-06 三星显示有限公司 Compound, organic light-emitting device including the same and flat display apparatus
CN106336360A (en) * 2015-07-07 2017-01-18 三星显示有限公司 Compound and organic light-emitting device and display device including same
US20170077422A1 (en) * 2015-09-14 2017-03-16 Samsung Display Co., Ltd. Condensed cyclic compound and organic light-emitting device including the same
US9666809B2 (en) 2013-12-03 2017-05-30 Samsung Display Co., Ltd. Compound and organic light-emitting device including the same
WO2017177719A1 (en) * 2016-04-15 2017-10-19 京东方科技集团股份有限公司 Organic electroluminescent material and organic electroluminescent device
JP2017208455A (en) * 2016-05-19 2017-11-24 出光興産株式会社 Organic electroluminescent element material, organic electroluminescent element and electronic apparatus
CN108409742A (en) * 2017-02-10 2018-08-17 三星显示有限公司 Heterocyclic compound and organic light emitting apparatus comprising the heterocyclic compound
US10074812B2 (en) 2016-03-18 2018-09-11 Samsung Display Co., Ltd. Compound and organic light-emitting device including the same
US10892422B2 (en) 2013-01-18 2021-01-12 Samsung Electronics Co., Ltd. Compound for organic optoelectronic device, organic light emitting diode including the same, and display including the organic light emitting diode
CN115141209A (en) * 2021-03-29 2022-10-04 烟台显华科技集团股份有限公司 Compound with fused heterocyclic biaryl amine or carbazole parent structure
CN115703790A (en) * 2021-08-13 2023-02-17 上海和辉光电股份有限公司 Electron transport compound and organic electroluminescent device

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101497124B1 (en) 2011-11-28 2015-03-06 덕산네오룩스 주식회사 Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
KR102387855B1 (en) * 2013-11-20 2022-04-18 주식회사 동진쎄미켐 Novel electroluminescent compound and organic electroluminescent device comprising same
KR20150122005A (en) 2014-04-22 2015-10-30 제일모직주식회사 Compound for organic optoelectric device and composition and organic optoelectric device and display device
US10193070B2 (en) * 2014-10-31 2019-01-29 E I Du Pont De Nemours And Company Electroactive materials
KR102603871B1 (en) * 2017-02-10 2023-11-22 삼성디스플레이 주식회사 Heterocyclic compound and organic light-emitting device comprising the same
KR102623053B1 (en) 2018-12-05 2024-01-10 삼성디스플레이 주식회사 Organic electroluminescence device and polycyclic compound for organic electroluminescence device

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB830223A (en) * 1955-12-02 1960-03-09 Ciba Ltd Thianaphtheno-indoles
CA2012626A1 (en) * 1990-03-20 1991-09-20 Kenneth W. Bair Hetero polycyclic biocidal compounds, their synthesis and intermediates therefor, formulations containing them, and their use in medicine
EP1727396A1 (en) * 2004-03-19 2006-11-29 Idemitsu Kosan Co., Ltd. Organic electroluminescent device
JP2009054809A (en) * 2007-08-28 2009-03-12 Mitsui Chemicals Inc Organic transistor
JP2009218335A (en) * 2008-03-10 2009-09-24 Mitsui Chemicals Inc Organic transistor
WO2010047335A1 (en) * 2008-10-21 2010-04-29 国立大学法人京都大学 Benzene compound
KR20100131745A (en) * 2009-06-08 2010-12-16 제일모직주식회사 Composition for organic photoelectric device and organic photoelectric device using the same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB830223A (en) * 1955-12-02 1960-03-09 Ciba Ltd Thianaphtheno-indoles
CA2012626A1 (en) * 1990-03-20 1991-09-20 Kenneth W. Bair Hetero polycyclic biocidal compounds, their synthesis and intermediates therefor, formulations containing them, and their use in medicine
EP1727396A1 (en) * 2004-03-19 2006-11-29 Idemitsu Kosan Co., Ltd. Organic electroluminescent device
JP2009054809A (en) * 2007-08-28 2009-03-12 Mitsui Chemicals Inc Organic transistor
JP2009218335A (en) * 2008-03-10 2009-09-24 Mitsui Chemicals Inc Organic transistor
WO2010047335A1 (en) * 2008-10-21 2010-04-29 国立大学法人京都大学 Benzene compound
KR20100131745A (en) * 2009-06-08 2010-12-16 제일모직주식회사 Composition for organic photoelectric device and organic photoelectric device using the same

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
FREED, M. E. ET AL.: "Antidepressants. II. Derivatives of Polynuclear Indoles", JOURNAL OF MEDICINAL CHEMISTRY, vol. 5, 1964, pages 628 - 632 *
JIN, Y ET AL.: "New Conjugated Polymer Based on Dihydroindoloindole for LEDs", BULLETIN OF THE KOREAN CHEMICAL SOCIETY, vol. 27, 2006, pages 1043 - 1047, XP008163221 *
KARNIK, A. V. ET AL.: "Facile syntheis of novel fluorescence active 12H- benzo[e]indolo[3,2-b]benzofuran and its derivatives", INDIAN JOURNAL OF CHEMISTRY, SECTION B: ORGANIC CHEMISTRY INCLUDING MEDICINAL CHEMISTRY, vol. 43B, 2004, pages 1345 - 1348 *
MOCHIDA, K. ET AL.: "Palladium-Catalyzed Intramolecular Coupling of 2-[(2- Pyrrolyl)silyl]aryl Triflates through 1,2-Silicon Migration", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 131, 2009, pages 8350 - 8351 *
NING, M. ET AL.: "Biological activities of a novel selective oestrogen receptor modulator derived from raloxifene (Y134)", BRITISH JOURNAL OF PHARMACOLOGY, vol. 150, 2007, pages 19 - 28 *
SCHROEDER, D. C. ET AL.: "Benzofuro[3,2-b]indoles", JOURNAL OF ORGANIC CHEMISTRY, vol. 27, 1962, pages 586 - 591, XP002093643 *
SHIMIZU, M. ET AL.: "Modular Approach to Silicon-Bridged Biaryls: Palladium- Catalyzed Intramolecular Coupling of 2-(Arylsilyl)aryl Triflates", ANGEWANDTE CHEMIE INTERNATIONAL EDITION, vol. 47, 2008, pages 9760 - 9764 *

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130193429A1 (en) * 2010-10-13 2013-08-01 Yuichi Sawada Organic electroluminescent element
US9312496B2 (en) * 2010-10-13 2016-04-12 Nippon Steel & Sumikin Chemical Co., Ltd. Organic electroluminescent element
JP2012087187A (en) * 2010-10-18 2012-05-10 Kaneka Corp Light-emitting material and organic el element
WO2014070029A1 (en) * 2012-11-05 2014-05-08 Instytut Chemii Organicznej Polskiej Akademii Nauk Strongly fluorescent heterocycles and a method for their synthesis
US9988385B2 (en) 2012-11-05 2018-06-05 Instytut Chemii Organicznej Polskiej Akademii Nauk Strongly fluorescent heterocycles and a method for their synthesis
US10892422B2 (en) 2013-01-18 2021-01-12 Samsung Electronics Co., Ltd. Compound for organic optoelectronic device, organic light emitting diode including the same, and display including the organic light emitting diode
JPWO2014126241A1 (en) * 2013-02-18 2017-02-02 国立大学法人京都工芸繊維大学 Luminescent material and organic EL device
WO2014126241A1 (en) * 2013-02-18 2014-08-21 国立大学法人京都工芸繊維大学 Light emitting material and organic el element
CN103214490A (en) * 2013-03-25 2013-07-24 中国科学院青岛生物能源与过程研究所 Method for preparing novel organic field effect transistor material
US9666809B2 (en) 2013-12-03 2017-05-30 Samsung Display Co., Ltd. Compound and organic light-emitting device including the same
US20150171339A1 (en) * 2013-12-18 2015-06-18 Samsung Display Co., Ltd. Material for organic electroluminescence device and organic electroluminescence device using the same
US20150171338A1 (en) * 2013-12-18 2015-06-18 Samsung Display Co., Ltd. Material for organic electroluminescence device and organic electroluminescence device including the same
JPWO2015125679A1 (en) * 2014-02-18 2017-03-30 保土谷化学工業株式会社 Benzofurindole derivatives and organic electroluminescence devices
WO2015125679A1 (en) * 2014-02-18 2015-08-27 保土谷化学工業株式会社 Benzofuroindole derivative and organic electroluminescence element
CN105732658A (en) * 2014-12-31 2016-07-06 三星显示有限公司 Compound, organic light-emitting device including the same and flat display apparatus
CN106336360A (en) * 2015-07-07 2017-01-18 三星显示有限公司 Compound and organic light-emitting device and display device including same
CN106336360B (en) * 2015-07-07 2021-01-29 三星显示有限公司 Compound, and organic light emitting device and display device including the same
US20170077422A1 (en) * 2015-09-14 2017-03-16 Samsung Display Co., Ltd. Condensed cyclic compound and organic light-emitting device including the same
US10074812B2 (en) 2016-03-18 2018-09-11 Samsung Display Co., Ltd. Compound and organic light-emitting device including the same
US10886475B2 (en) 2016-04-15 2021-01-05 Boe Technology Group Co., Ltd. Organic electroluminescent materials and organic electroluminescent devices
WO2017177719A1 (en) * 2016-04-15 2017-10-19 京东方科技集团股份有限公司 Organic electroluminescent material and organic electroluminescent device
JP2017208455A (en) * 2016-05-19 2017-11-24 出光興産株式会社 Organic electroluminescent element material, organic electroluminescent element and electronic apparatus
CN108409742A (en) * 2017-02-10 2018-08-17 三星显示有限公司 Heterocyclic compound and organic light emitting apparatus comprising the heterocyclic compound
CN115141209A (en) * 2021-03-29 2022-10-04 烟台显华科技集团股份有限公司 Compound with fused heterocyclic biaryl amine or carbazole parent structure
CN115703790A (en) * 2021-08-13 2023-02-17 上海和辉光电股份有限公司 Electron transport compound and organic electroluminescent device

Also Published As

Publication number Publication date
KR20110116635A (en) 2011-10-26

Similar Documents

Publication Publication Date Title
WO2011132866A1 (en) Novel compounds for organic electronic material and organic electroluminescent device using the same
WO2011126224A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2012050371A1 (en) Novel compounds for organic electronic material and organic electroluminescent device using the same
WO2011071255A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011019156A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011136520A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2010126270A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011136484A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011055911A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2010151006A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2010151011A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011099718A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2018105986A1 (en) Organic electroluminescent material and organic electroluminescent device comprising the same
WO2013157886A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2010110553A2 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2010114253A2 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011126225A1 (en) Novel compounds for organic electronic material and organic electroluminescent device using the same
WO2011055912A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2010126234A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2010114256A2 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2014061963A1 (en) Organic electroluminescence compounds and organic electroluminescence device comprising the same
WO2012050347A1 (en) Novel compounds for organic electronic material and organic electroluminescent device using the same
WO2011010839A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2011010843A1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
WO2013109030A1 (en) Organic electroluminescent device comprising the organic electroluminescent compounds

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11772155

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11772155

Country of ref document: EP

Kind code of ref document: A1