WO2014092431A1 - Novel compound, and organic electroluminescent device comprising same - Google Patents

Novel compound, and organic electroluminescent device comprising same Download PDF

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WO2014092431A1
WO2014092431A1 PCT/KR2013/011402 KR2013011402W WO2014092431A1 WO 2014092431 A1 WO2014092431 A1 WO 2014092431A1 KR 2013011402 W KR2013011402 W KR 2013011402W WO 2014092431 A1 WO2014092431 A1 WO 2014092431A1
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group
formula
aryl
compound
alkyl
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Korean (ko)
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심재의
이인혁
백영미
신진용
박호철
이창준
이은정
김태형
이재훈
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주식회사 두산
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    • 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
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
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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
    • 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
    • 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
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
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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
    • C—CHEMISTRY; METALLURGY
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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
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms

Definitions

  • the present invention relates to a novel compound and an organic electroluminescent device comprising the same.
  • the organic electroluminescent device when a voltage is applied between two electrodes, holes are injected into the organic material layer at the anode, and electrons are injected into the organic material layer at the cathode. When the injected holes and electrons meet, excitons are formed, and when the excitons fall to the ground, they shine.
  • the material included in the organic material layer may be classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, and the like according to its function.
  • the light emitting material may be classified into blue, green, and red light emitting materials according to the light emitting color, and yellow and orange light emitting materials required to realize a better natural color.
  • a host / dopant system may be used as a light emitting material to increase luminous efficiency through an increase in color purity and energy transfer.
  • the dopant material may be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt.
  • a metal complex compound containing heavy atoms such as Ir and Pt.
  • anthracene derivatives are known as fluorescent dopant / host materials used in the light emitting layer.
  • a phosphorescent dopant material used in the light emitting layer metal complex compounds containing Ir such as Firpic, Ir (ppy) 3 , and (acac) Ir (btp) 2 are known, and as a phosphorescent host material, 4,4-dicarbazolybiphenyl (CBP) is known.
  • an object of the present invention is to provide a novel compound and an organic electroluminescent device using the compound which can improve the efficiency, lifespan and stability of the organic electroluminescent device.
  • the present invention provides a compound represented by the following formula (1).
  • X 1 to X 3 are each independently CR 2 or N, wherein at least one is N,
  • R 1 and R 2 are each independently hydrogen, deuterium, halogen, cyano group, nitro group, amino group, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 alkynyl group, C 3 ⁇ C 40 cycloalkyl group, the number of nuclear atoms of 3 to 40 of the heterocycloalkyl of the alkyl group, C 6 ⁇ C 60 aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, C 1 ⁇ alkyloxy group of C 40, C 6 to C 60 aryloxy group, C 1 to C 40 alkylsilyl group, C 6 to C 60 arylsilyl group, C 1 to C 40 alkyl boron group, C 6 to C 60 aryl boron group, C 6 ⁇ C 60 aryl phosphine is selected from the pingi, C 6 ⁇ C 60 aryl phosphine oxide group, and the group consisting of
  • A is selected from the group consisting of hydrogen, a C 6 ⁇ C 60 aryl group and a heteroaryl group of 5 to 60 nuclear atoms,
  • L is selected from the group consisting of a single bond, a C 6 ⁇ C 60 arylene group and a heteroarylene group having 5 to 60 nuclear atoms, n is an integer of 0 to 3,
  • Cy 1 is a compound represented by the following formula (2),
  • Y 1 to Y 4 are each independently CR 5 or N, and one of Y 1 and Y 2 , Y 2 and Y 3, and Y 3 and Y 4 forms a condensed ring represented by the following Formula 3,
  • the dotted line means a site where condensation occurs with the compound of Formula 2, and Y 5 to Y 8 are each independently CR 6 or N,
  • Z 1 and Z 2 are each independently selected from the group consisting of O, S, Se, N (Ar 1 ), C (Ar 2 ) (Ar 3 ) and Si (Ar 4 ) (Ar 5 ), wherein at least One is N (Ar 1 ),
  • R 3 to R 6 are each independently hydrogen, deuterium, halogen, cyano group, nitro group, amino group, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 alkynyl group, C 3 ⁇ C 40 cycloalkyl group, nuclear hetero atoms 3 to 40 heterocycloalkyl group, C 6 ⁇ C 60 aryl group, nuclear atoms 5 to 60 heteroaryl group, C 1 ⁇ C 40 alkyloxy group, C 6 ⁇ C 60 aryloxy group, C 1 ⁇ C 40 alkylsilyl group, C 6 ⁇ C 60 arylsilyl group, C 1 ⁇ C 40 alkyl boron group, C 6 ⁇ C 60 aryl boron group, C 6 ⁇ C 60 aryl phosphine group, C 6 ⁇ C 60 aryl phosphine oxide group and C 6 ⁇ C 60 It is selected from the group consisting of an arylamine group,
  • Ar 1 to Ar 5 are each independently hydrogen, deuterium, halogen, cyano group, nitro group, C 1 ⁇ C 40 alkyl group, C 2 ⁇ C 40 alkenyl group, C 2 ⁇ C 40 alkynyl group, C 3 ⁇ C 40 cycloalkyl group, the number of nuclear atoms of 3 to 40 of the heterocycloalkyl of the alkyl group, C 6 ⁇ C 60 aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, C 1 ⁇ alkyloxy group of C 40, C 6 Aryloxy group of ⁇ C 60 , C 1 ⁇ C 40 alkylsilyl group, C 6 ⁇ C 60 arylsilyl group, C 1 ⁇ C 40 alkyl boron group, C 6 ⁇ C 60 aryl boron group, C 6 An arylphosphine group of ⁇ C 60 , a C 6 ⁇ C 60 arylphosphine oxide group and a C 6 ⁇
  • the aryl group and heteroaryl group of A are each independently deuterium, halogen, cyano group, nitro group, amino group, C 1 ⁇ C 40 alkyl group (preferably C 1 ⁇ C 10 alkyl group), C 2 ⁇ C 40 Alkenyl groups (preferably C 2 to C 10 alkenyl groups), C 2 to C 40 alkynyl groups (preferably C 2 to C 10 alkynyl groups), C 3 to C 40 cycloalkyl groups (preferably A C 3 -C 18 cycloalkyl group), a heterocycloalkyl group having 3 to 40 nuclear atoms (preferably a heterocycloalkyl group having 3 to 18 nuclear atoms), and an aryl group having a C 6 -C 40 (preferably C 6 An aryl group of -C 18 ), a heteroaryl group of 5 to 40 nuclear atoms (preferably a heteroaryl group of 5 to 18 nuclear atoms), an alkyloxy group of C 1 to C 40 (preferably C 1 to) C
  • Alkyl boron group, aryl boron group, aryl phosphine group, aryl phosphine oxide group and arylamine group are each independently deuterium, halogen, cyano group, nitro group, amino group, C 1 ⁇ C 40 alkyl group (preferably C 1 An alkyl group of ⁇ C 10 ), an alkenyl group of C 2 ⁇ C 40 (preferably an alkenyl group of C 2 ⁇ C 10 ), an alkynyl group of C 2 ⁇ C 40 (preferably an alkynyl group of C 2 ⁇ C 10 ) C 3 -C 40 cycloalkyl group (preferably
  • L is connected to any one of Z 1 , Z 2 , R 3 , R 4 and Y 1 to Y 8 of Formula 2 to which Formula 3 is attached.
  • Alkyl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain saturated hydrocarbon of 1 to 40 carbon atoms, non-limiting examples thereof are methyl, ethyl, propyl, isobutyl, sec-butyl , Pentyl, iso-amyl, hexyl and the like.
  • Alkenyl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon double bond.
  • Non-limiting examples thereof include vinyl, allyl, isopropenyl, 2-butenyl and the like.
  • Alkynyl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon triple bond.
  • Non-limiting examples thereof include ethynyl, 2-propynyl and the like.
  • Cycloalkyl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms (saturated cyclic hydrocarbon).
  • Non-limiting examples thereof include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine and the like.
  • Heterocycloalkyl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from a non-aromatic hydrocarbon (saturated cyclic hydrocarbon) having 3 to 40 nuclear atoms, and preferably at least one carbon in the ring, preferably 1 To 3 carbons are substituted with a hetero atom such as N, O or S.
  • Non-limiting examples thereof include morpholine, piperazine and the like.
  • Aryl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from an aromatic hydrocarbon having 6 to 60 carbon atoms alone or in combination of two or more rings.
  • the two or more rings may be attached in a simple or condensed form with each other.
  • Non-limiting examples thereof include phenyl, biphenyl, triphenyl, terphenyl, naphthyl, fluorenyl, phenanthryl, anthracenyl, indenyl and the like.
  • Heteroaryl used in the present invention is a monovalent functional group obtained by removing a hydrogen atom from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms, and at least one carbon in the ring, preferably 1 to 3 Carbons are substituted with heteroatoms such as nitrogen (N), oxygen (O), sulfur (S) or selenium (Se).
  • the heteroaryl may be attached in a form in which two or more rings are simply attached or condensed with each other, and may also include a condensed form with an aryl group.
  • heteroaryls include six-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl; Polycyclics such as phenoxathienyl, indolinzinyl, indolyl, purinyl, quinolyl, benzothiazole, carbazolyl ring; And 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl, and the like.
  • Alkyloxy used in the present invention means a monovalent functional group represented by RO-, wherein R is alkyl having 1 to 40 carbon atoms, and may include a linear, branched, or cyclic structure. Can be. Non-limiting examples of such alkyloxy include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.
  • Aryloxy used in the present invention means a monovalent functional group represented by R'O-, wherein R 'is an aryl having 6 to 60 carbon atoms.
  • R ' is an aryl having 6 to 60 carbon atoms.
  • Non-limiting examples of such aryloxy include phenyloxy, naphthyloxy, diphenyloxy and the like.
  • Alkylsilyl used in the present invention means silyl substituted with alkyl having 1 to 40 carbon atoms
  • arylsilyl means silyl substituted with aryl having 6 to 60 carbon atoms
  • arylamine is substituted with aryl having 6 to 60 carbon atoms. Amine.
  • the condensed ring means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.
  • the present invention is an anode; cathode; And at least one organic material layer interposed between the anode and the cathode, wherein at least one of the at least one organic material layer comprises a compound represented by Chemical Formula 1 Provided is a light emitting device.
  • the organic material layer including the compound represented by Chemical Formula 1 is selected from the group consisting of a hole injection layer, a hole transport layer, and a light emitting layer, and is preferably a light emitting layer.
  • the compound represented by Chemical Formula 1 may be used as a phosphorescent host of the emission layer.
  • novel compound of the present invention forms a basic skeleton by combining an indene derivative including nitrogen (N) and an indole fusion compound, and is represented by Chemical Formula 1.
  • the compound represented by Chemical Formula 1 of the present invention not only has excellent phosphorescence properties, but also has excellent electron and / or hole transporting ability, a hole injection layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron, which is an organic material layer of an organic EL device. It can be used as the material of any one of the injection layer. Preferably it can be used as a material of any one of a hole injection layer, a hole transport layer and a light emitting layer, more preferably a material (especially a phosphorescent host) of the light emitting layer.
  • the compound represented by Chemical Formula 1 of the present invention is a combination of an indene derivative and an indole fusion compound into which various substituents are introduced, and has a bipolar characteristic, so that the balance of holes and electron mobility is controlled.
  • the recombination efficiency of the electrons can be improved, thereby exhibiting excellent phosphorescence characteristics.
  • the compound represented by Formula 1 of the present invention has a wide energy bandgap (sky blue ⁇ red) as the energy level is controlled by introducing various substituents into the basic skeleton consisting of an indene derivative containing nitrogen (N) and an indole fusion compound ) Therefore, when the compound of Formula 1 of the present invention is used in an organic electroluminescent device, the phosphorescence property of the device may be improved, and the hole injection ability and / or hole transport ability, the luminous efficiency, the driving voltage and the lifetime characteristics may be improved. .
  • the compound represented by the general formula (1) of the present invention has a significant increase in molecular weight due to the various substituents introduced in the basic skeleton, thereby improving the glass transition temperature, which is a conventional organic electroluminescent device material (for example, CBP [4,4-dicarbazolybiphenyl]) may have a higher thermal stability.
  • a conventional organic electroluminescent device material for example, CBP [4,4-dicarbazolybiphenyl]
  • the compound according to the present invention can greatly contribute to improving the performance and lifespan of the organic light emitting device, and further, the lifespan of the organic light emitting device can maximize the performance of the full color organic light emitting panel.
  • X 1 to X 3 of the indene derivative containing nitrogen (N) are each independently CR 2 or N, wherein at least one is preferably nitrogen (N), It is more preferable that all are nitrogen (N).
  • the indene derivative containing nitrogen (N) Is preferably selected from the group consisting of the structures represented by S-1 to S-7, and among them, S-7 which is a triazolopyridine derivative is most preferred.
  • S-7 which is a triazolopyridine derivative is most preferred.
  • R 2 is as defined above, and a plurality of R 2 may be the same as or different from each other.
  • R 1 and R 2 are each independently hydrogen, C 6 ⁇ C 60 aryl group (preferably C 6 ⁇ C 25 aryl group), 5 to 5 nuclear atoms Selected from the group consisting of 60 heteroaryl groups (preferably heteroaryl groups having 5 to 32 nuclear atoms) and arylamine groups having C 6 to C 60 (preferably arylamine groups having C 6 to C 20 ) It is preferable, and it is more preferable that it is hydrogen.
  • R 1 and R 2 and A bonded to the indene derivative may be each independently selected from the group consisting of hydrogen or a structure (substituent) represented by A1 to A70.
  • Cy 1 is preferably selected from the group consisting of compounds represented by the following Formulas 2a to 2f.
  • Z 1 , Z 2, and R 3 to R 6 are the same as defined above.
  • the plurality of R 5 may be the same or different from each other, a plurality of R 6 may be the same or different from each other.
  • L connecting the selected compound is a single bond or phenylene.
  • Z 1 and Z 2 are preferably both N (Ar 1 ), and are bonded to Ar 1 and Z 2 of N (Ar 1 ) bonded to Z 1 .
  • N 1 of Ar (Ar 1) which may be the same or different from each other.
  • Ar 1 is hydrogen, C 6 ⁇ C 60 aryl group (preferably C 6 ⁇ C 18 aryl group) and the number of nuclear atoms 5 It is preferably selected from the group consisting of a heteroaryl group of 60 to 60 (preferably a heteroaryl group having 5 to 18 nuclear atoms).
  • the linking position (bonding position) of L and the compound represented by Formula 2 is not particularly limited, but is connected to any one of Z 1 and Z 2 of Formula 2 to which Formula 3 is bound. It is desirable to be.
  • the compound represented by the formula (1) of the present invention is preferably a compound represented by the following formula (4) or formula (5).
  • A, L, Cy 1 , R 1 and n are as defined above, and a plurality of R 1 are the same as or different from each other.
  • Such a compound represented by Formula 1 of the present invention may be specifically exemplified by the following compounds (1 to 70), but is not limited thereto.
  • Such a compound represented by Formula 1 of the present invention can be synthesized in various ways with reference to the synthesis process of the following examples.
  • the present invention provides an organic electroluminescent device comprising a compound represented by the formula (1).
  • the organic electroluminescent device comprises an anode, a cathode and at least one organic layer interposed between the anode and the cathode, at least one of the at least one organic layer It is characterized by including a compound represented by the formula (1).
  • the organic material layer including the compound represented by Chemical Formula 1 may be any one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
  • the organic material layer including the compound of Formula 1 may be a hole injection layer, a hole transport layer or a light emitting layer, more preferably a light emitting layer.
  • the light emitting layer of the organic electroluminescent device according to the present invention may contain a host material (preferably a phosphorescent host material), in which case, the compound represented by Chemical Formula 1 may be used as the host material.
  • a host material preferably a phosphorescent host material
  • the compound represented by Chemical Formula 1 may be used as the host material.
  • the hole transporting ability is increased to increase the bonding force between the holes and the electrons in the light emitting layer, efficiency (luminescence efficiency and power efficiency), lifetime, luminance, driving voltage, etc.
  • An excellent organic electroluminescent device can be provided.
  • the structure of the organic electroluminescent device according to the present invention is not particularly limited and may be formed of a structure in which a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are sequentially stacked.
  • the electron injection layer may be further stacked on the electron transport layer.
  • the organic electroluminescent device according to the present invention may not only have a structure in which an anode, at least one organic material layer, and a cathode are sequentially stacked, but also have a structure in which an insulating layer or an adhesive layer is inserted at an interface between the electrode and the organic material layer.
  • the material that can be used as the anode included in the organic electroluminescent device according to the present invention is not particularly limited, but non-limiting examples include metals such as vanadium, chromium, copper, zinc, gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO 2 : Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole or polyaniline; And carbon black and the like can be used.
  • metals such as vanadium, chromium, copper, zinc, gold or alloys thereof
  • Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO 2
  • the material that can be used as the cathode included in the organic EL device according to the present invention is not particularly limited, but non-limiting examples include magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, Tin or metals such as lead or alloys thereof; And multilayer structure materials such as LiF / Al or LiO 2 / Al, and the like.
  • the compound represented by Chemical Formula 1 may be any one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, preferably a hole injection layer, a hole transport layer and Except for use in any one of the light emitting layers, more preferably the light emitting layer, it can be made using materials and methods known in the art.
  • the material usable as the substrate included in the organic electroluminescent device according to the present invention is not particularly limited, but non-limiting examples may include silicon wafers, quartz, glass plates, metal plates, plastic films and sheets.
  • Such an organic electroluminescent device of the present invention may be manufactured by a method known in the art, wherein the light emitting layer included in the organic material layer may be manufactured by a vacuum deposition method or a solution coating method.
  • the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.
  • Ar and Ar 'in Schemes 1 and 2 are C 6 ⁇ C 60 aryl group, X is a halogen group.
  • EtOH / MeOH (1: 1, 1.5 L) mixed solvent was added to 180.5 g (2.60 mol) of hydroxylamine hydrochloride. 271 mL (1.56 mol) of N, N-Diisopropylethylamine was added to the reaction solution, and the mixture was stirred for 1 hour. 158 g (0.52 mol) of 1- (3-bromo-pyridine-2-yl) -3-carboethoxy-thiourea synthesized above was added thereto, and the temperature was gradually raised to reflux for 3 hours. The temperature was cooled to room temperature and the resulting solid was filtered off. The filtrate was distilled under reduced pressure and the resulting solid was filtered. The obtained solid product was combined, washed with purified water, EtOH / MeOH mixed solvent, n-hexane, and warmed to obtain 91 g (yield 82%) of the title compound.
  • a glass substrate coated with ITO Indium tin oxide
  • ITO Indium tin oxide
  • a solvent such as isopropyl alcohol, acetone, methanol, etc.
  • UV OZONE cleaner Power sonic 405, Hwasin Tech
  • M-MTDATA 60 nm) / NPB (20 nm) / Compound 8, 32, 40, 51, 64, 69 + 10% (piq) 2 Ir (acac) (30nm) /
  • a red organic electroluminescent device was manufactured by stacking BCP (10 nm) / Alq 3 (30 nm) / LiF (1 nm) / Al (200 nm) in this order.
  • a red organic electroluminescent device was manufactured in the same manner as in Example 1, except that CBP was used instead of compound 8 as a light-emitting host material when forming the light-emitting layer.
  • the red organic electroluminescent devices (Examples 1 to 6) using the compound of the present invention in the light emitting layer have a driving voltage and a red organic electroluminescent device (comparative example) using the conventional CBP in the light emitting layer. It can be seen that the excellent performance in terms of current efficiency.
  • the compound represented by Formula 1 according to the present invention may be applied to an organic material layer, preferably a light emitting layer of the organic electroluminescent device because of excellent thermal stability and phosphorescence properties. That is, when the light emitting layer of the organic electroluminescent device includes the compound represented by Chemical Formula 1 as a phosphorescent host material, the efficiency (light emitting efficiency and power efficiency), lifetime, brightness and driving of the device compared to the case of including a conventional host material The voltage can be improved, and furthermore, the performance and lifetime of the full color organic electroluminescent panel can be greatly improved.

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Abstract

The present invention relates to a novel compound and to an organic electroluminescent device comprising same. The compound according to the present invention is used in an organic layer, and more preferably, in a light-emitting layer of the organic electroluminescent device. Thus, the light-emitting efficiency, the driving voltage, the lifespan, etc. of the organic electroluminescent device may be improved.

Description

신규 화합물 및 이를 포함하는 유기 전계 발광 소자New compound and organic electroluminescent device comprising same
본 발명은 신규 화합물 및 이를 포함하는 유기 전계 발광 소자에 관한 것이다.The present invention relates to a novel compound and an organic electroluminescent device comprising the same.
유기 전계 발광 소자는 두 전극 사이에 전압을 걸어 주면 양극에서는 정공이 유기물층으로 주입되고, 음극에서는 전자가 유기물층으로 주입된다. 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 바닥상태로 떨어질 때 빛이 나게 된다. 상기 유기물층에 포함되는 물질은 그 기능에 따라, 발광 물질, 정공 주입 물질, 정공 수송 물질, 전자 수송 물질, 전자 주입 물질 등으로 분류될 수 있다.In the organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the organic material layer at the anode, and electrons are injected into the organic material layer at the cathode. When the injected holes and electrons meet, excitons are formed, and when the excitons fall to the ground, they shine. The material included in the organic material layer may be classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, and the like according to its function.
상기 발광 물질은 발광색에 따라 청색, 녹색, 적색의 발광 물질과, 보다 나은 천연색을 구현하기 위해 필요한 노란색 및 주황색의 발광 물질로 구분될 수 있다. 또한 색순도의 증가와 에너지 전이를 통해 발광 효율을 증가시키기 위하여 발광 물질로서 호스트/도판트 계를 사용할 수 있다.The light emitting material may be classified into blue, green, and red light emitting materials according to the light emitting color, and yellow and orange light emitting materials required to realize a better natural color. In addition, a host / dopant system may be used as a light emitting material to increase luminous efficiency through an increase in color purity and energy transfer.
도판트 물질은 유기 물질을 사용하는 형광 도판트와 Ir, Pt 등의 중원자(heavy atoms)가 포함된 금속 착체 화합물을 사용하는 인광 도판트로 나눌 수 있다. 이때 인광 도판트는 이론적으로 형광 도판트에 비해 최대 4배의 발광 효율을 향상시킬 수 있기 때문에 인광 도판트 뿐만 아니라 인광 호스트에 대한 연구가 많이 진행되고 있다.The dopant material may be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. In this case, since phosphorescent dopants can theoretically improve luminous efficiency up to 4 times compared to fluorescent dopants, studies on phosphorescent dopants as well as phosphorescent hosts are being conducted.
현재 발광층에 사용되는 형광 도판트/호스트 물질로는 안트라센 유도체들이 알려져 있다. 또한 발광층에 사용되는 인광 도판트 물질로는 Firpic, Ir(ppy)3, (acac)Ir(btp)2 등의 Ir을 포함하는 금속 착체 화합물이 알려져 있고, 인광 호스트 물질로는 4,4-dicarbazolybiphenyl(CBP)가 알려져 있다.At present, anthracene derivatives are known as fluorescent dopant / host materials used in the light emitting layer. In addition, as a phosphorescent dopant material used in the light emitting layer, metal complex compounds containing Ir such as Firpic, Ir (ppy) 3 , and (acac) Ir (btp) 2 are known, and as a phosphorescent host material, 4,4-dicarbazolybiphenyl (CBP) is known.
그러나 기존의 재료들은 유리전이온도가 낮고 열적 안정성이 좋지 않아 유기 전계 발광 소자에서의 수명 측면에서 만족할만한 수준이 되지 못하고 있으며, 발광 특성 측면에서도 여전히 개선이 필요하다.However, existing materials have low glass transition temperature and poor thermal stability, and thus are not satisfactory in terms of lifespan in an organic EL device, and still need improvement in terms of light emission characteristics.
본 발명은 상기한 문제점을 해결하기 위해, 유기 전계 발광 소자의 효율, 수명 및 안정성 등을 향상시킬 수 있는 신규 화합물 및 상기 화합물을 이용한 유기 전계 발광 소자를 제공하는 것을 목적으로 한다.In order to solve the above problems, an object of the present invention is to provide a novel compound and an organic electroluminescent device using the compound which can improve the efficiency, lifespan and stability of the organic electroluminescent device.
상기한 목적을 달성하기 위해, 본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다.In order to achieve the above object, the present invention provides a compound represented by the following formula (1).
[화학식 1][Formula 1]
Figure PCTKR2013011402-appb-I000001
Figure PCTKR2013011402-appb-I000001
상기 화학식 1에서,In Chemical Formula 1,
X1 내지 X3는 각각 독립적으로 CR2 또는 N이고, 이때, 적어도 하나 이상은 N이며,X 1 to X 3 are each independently CR 2 or N, wherein at least one is N,
R1 및 R2는 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1 ~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되고, 인접한 기와 축합 고리를 형성할 수 있으며,R 1 and R 2 are each independently hydrogen, deuterium, halogen, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, the number of nuclear atoms of 3 to 40 of the heterocycloalkyl of the alkyl group, C 6 ~ C 60 aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, C 1 ~ alkyloxy group of C 40, C 6 to C 60 aryloxy group, C 1 to C 40 alkylsilyl group, C 6 to C 60 arylsilyl group, C 1 to C 40 alkyl boron group, C 6 to C 60 aryl boron group, C 6 ~ C 60 aryl phosphine is selected from the pingi, C 6 ~ C 60 aryl phosphine oxide group, and the group consisting of C 6 ~ C 60 aryl amine, the adjacent groups may form a fused ring,
A는 수소, C6~C60의 아릴기 및 핵원자수 5 내지 60의 헤테로아릴기로 이루어진 군에서 선택되고,A is selected from the group consisting of hydrogen, a C 6 ~ C 60 aryl group and a heteroaryl group of 5 to 60 nuclear atoms,
L은 단일결합, C6~C60의 아릴렌기 및 핵원자수 5 내지 60의 헤테로아릴렌기로 이루어진 군에서 선택되며, n은 0 내지 3의 정수이고,L is selected from the group consisting of a single bond, a C 6 ~ C 60 arylene group and a heteroarylene group having 5 to 60 nuclear atoms, n is an integer of 0 to 3,
Cy1은 하기 화학식 2로 표시되는 화합물이며,Cy 1 is a compound represented by the following formula (2),
[화학식 2][Formula 2]
Figure PCTKR2013011402-appb-I000002
Figure PCTKR2013011402-appb-I000002
상기 화학식 2에서,In Chemical Formula 2,
Y1 내지 Y4은 각각 독립적으로 CR5 또는 N이며, Y1 과 Y2, Y2 와 Y3 및 Y3 와 Y4 중 하나는 하기 화학식 3으로 표시되는 축합 고리를 형성하고,Y 1 to Y 4 are each independently CR 5 or N, and one of Y 1 and Y 2 , Y 2 and Y 3, and Y 3 and Y 4 forms a condensed ring represented by the following Formula 3,
[화학식 3][Formula 3]
Figure PCTKR2013011402-appb-I000003
Figure PCTKR2013011402-appb-I000003
상기 화학식 3에서,In Chemical Formula 3,
점선은 상기 화학식 2의 화합물과 축합이 이루어지는 부위를 의미하고, Y5 내지 Y8은 각각 독립적으로 CR6 또는 N이며,The dotted line means a site where condensation occurs with the compound of Formula 2, and Y 5 to Y 8 are each independently CR 6 or N,
Z1 및 Z2는 각각 독립적으로 O, S, Se, N(Ar1), C(Ar2)(Ar3) 및 Si(Ar4)(Ar5)로 이루어진 군에서 선택되고, 이때, 적어도 하나는 N(Ar1)이며,Z 1 and Z 2 are each independently selected from the group consisting of O, S, Se, N (Ar 1 ), C (Ar 2 ) (Ar 3 ) and Si (Ar 4 ) (Ar 5 ), wherein at least One is N (Ar 1 ),
상기 R3 내지 R6은 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1 ~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되고, 인접한 기와 축합 고리를 형성할 수 있으며,R 3 to R 6 are each independently hydrogen, deuterium, halogen, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, nuclear hetero atoms 3 to 40 heterocycloalkyl group, C 6 ~ C 60 aryl group, nuclear atoms 5 to 60 heteroaryl group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group and C 6 ~ C 60 It is selected from the group consisting of an arylamine group, it may form a condensed ring with adjacent groups,
상기 Ar1 내지 Ar5는 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되고,Ar 1 to Ar 5 are each independently hydrogen, deuterium, halogen, cyano group, nitro group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, the number of nuclear atoms of 3 to 40 of the heterocycloalkyl of the alkyl group, C 6 ~ C 60 aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, C 1 ~ alkyloxy group of C 40, C 6 Aryloxy group of ~ C 60 , C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 6 An arylphosphine group of ~ C 60 , a C 6 ~ C 60 arylphosphine oxide group and a C 6 ~ C 60 arylamine group,
상기 A의 아릴기 및 헤테로아릴기는 각각 독립적으로 중수소, 할로겐, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기(바람직하게는 C1~C10의 알킬기), C2~C40의 알케닐기(바람직하게는 C2~C10의 알케닐기), C2~C40의 알키닐기(바람직하게는 C2~C10의 알키닐기), C3~C40의 시클로알킬기(바람직하게는 C3~C18의 시클로알킬기), 핵원자수 3 내지 40의 헤테로시클로알킬기(바람직하게는 핵원자수 3 내지 18의 헤테로시클로알킬기), C6~C40의 아릴기(바람직하게는 C6~C18의 아릴기), 핵원자수 5 내지 40의 헤테로아릴기(바람직하게는 핵원자수 5 내지 18의 헤테로아릴기), C1~C40의 알킬옥시기(바람직하게는 C1~C10의 알킬옥시기), C6~C60의 아릴옥시기(바람직하게는 C6~C18의 아릴옥시기), C1~C40의 알킬실릴기(바람직하게는 C1~C10의 알킬실릴기), C6~C60의 아릴실릴기(바람직하게는 C6~C18의 아릴실릴기), C1~C40의 알킬보론기(바람직하게는 C1~C10의 알킬보론기), C6~C60의 아릴보론기(바람직하게는 C6~C18의 아릴보론기), C6~C60의 아릴포스핀기(바람직하게는 C6~C18의 아릴포스핀기), C6~C60의 아릴포스핀옥사이드기(바람직하게는 C6~C18의 아릴포스핀옥사이드기) 및 C6~C60의 아릴아민기(바람직하게는 C6~C20의 아릴아민기)로 이루어진 군에서 선택된 1종 이상으로 치환될 수 있으며, 이때, 복수개의 치환기들은 서로 동일하거나 상이하고,The aryl group and heteroaryl group of A are each independently deuterium, halogen, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group (preferably C 1 ~ C 10 alkyl group), C 2 ~ C 40 Alkenyl groups (preferably C 2 to C 10 alkenyl groups), C 2 to C 40 alkynyl groups (preferably C 2 to C 10 alkynyl groups), C 3 to C 40 cycloalkyl groups (preferably A C 3 -C 18 cycloalkyl group), a heterocycloalkyl group having 3 to 40 nuclear atoms (preferably a heterocycloalkyl group having 3 to 18 nuclear atoms), and an aryl group having a C 6 -C 40 (preferably C 6 An aryl group of -C 18 ), a heteroaryl group of 5 to 40 nuclear atoms (preferably a heteroaryl group of 5 to 18 nuclear atoms), an alkyloxy group of C 1 to C 40 (preferably C 1 to) C 10 -C 60 alkyloxy group), C 6 -C 60 aryloxy group (preferably C 6 -C 18 aryloxy group), C 1 -C 40 alkylsilyl group (preferably C 1 -C 10 Alkylsilyl group), C 6 ~ C 60 arylsilyl group (preferably C 6 ~ C 18 arylsilyl group), C 1 ~ C 40 alkyl boron group (preferably C 1 ~ C 10 alkyl boron group), C 6 ~ C group 60 arylboronic of (preferably a arylboronic a C 6 ~ C 18), C 6 ~ C 60 aryl phosphine group (preferably a C 6 ~ C 18 aryl phosphine group), C 6 ~ C Group consisting of 60 arylphosphine oxide groups (preferably C 6 to C 18 arylphosphine oxide groups) and C 6 to C 60 arylamine groups (preferably C 6 to C 20 arylamine groups) It may be substituted with one or more selected from, wherein a plurality of substituents are the same or different from each other,
상기 R1 내지 R6 및 Ar1 내지 Ar5의 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 아릴포스핀옥사이드기 및 아릴아민기는 각각 독립적으로 중수소, 할로겐, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기(바람직하게는 C1~C10의 알킬기), C2~C40의 알케닐기(바람직하게는 C2~C10의 알케닐기), C2~C40의 알키닐기(바람직하게는 C2~C10의 알키닐기), C3~C40의 시클로알킬기(바람직하게는 C3~C18의 시클로알킬기), 핵원자수 3 내지 40의 헤테로시클로알킬기(바람직하게는 핵원자수 3 내지 18의 헤테로시클로알킬기), C6~C40의 아릴기(바람직하게는 C6~C18의 아릴기), 핵원자수 5 내지 40의 헤테로아릴기(바람직하게는 핵원자수 5 내지 18의 헤테로아릴기), C1~C40의 알킬옥시기(바람직하게는 C1~C10의 알킬옥시기), C6~C60의 아릴옥시기(바람직하게는 C6~C18의 아릴옥시기), C1~C40의 알킬실릴기(바람직하게는 C1~C10의 알킬실릴기), C6~C60의 아릴실릴기(바람직하게는 C6~C18의 아릴실릴기), C1~C40의 알킬보론기(바람직하게는 C1~C10의 알킬보론기), C6~C60의 아릴보론기(바람직하게는 C6~C18의 아릴보론기), C6~C60의 아릴포스핀기(바람직하게는 C6~C18의 아릴포스핀기), C6~C60의 아릴포스핀옥사이드기(바람직하게는 C6~C18의 아릴포스핀옥사이드기) 및 C6~C60의 아릴아민기(바람직하게는 C6~C20의 아릴아민기)로 이루어진 군에서 선택된 1종 이상으로 치환될 수 있으며, 이때, 복수개의 치환기들은 서로 동일하거나 상이하고,The alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group of R 1 to R 6 and Ar 1 to Ar 5 , Alkyl boron group, aryl boron group, aryl phosphine group, aryl phosphine oxide group and arylamine group are each independently deuterium, halogen, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group (preferably C 1 An alkyl group of ~ C 10 ), an alkenyl group of C 2 ~ C 40 (preferably an alkenyl group of C 2 ~ C 10 ), an alkynyl group of C 2 ~ C 40 (preferably an alkynyl group of C 2 ~ C 10 ) C 3 -C 40 cycloalkyl group (preferably C 3 -C 18 cycloalkyl group), nuclear 3 to 40 heterocycloalkyl group (preferably 3 to 18 heterocycloalkyl group), C 6 ~ C 40 aryl group (preferably a C 6 ~ C 18 aryl group), the number of 5 to 40 heteroaryl group (preferably of atomic nuclei Aryloxy nuclear atoms of 5 to 18 heteroaryl group), C 1 ~ C 40 alkyloxy (preferably alkyloxy group of C 1 ~ C 10), C 6 ~ C 60 (preferably C 6 to C 18 aryloxy group), C 1 to C 40 alkylsilyl group (preferably C 1 to C 10 alkylsilyl group), C 6 to C 60 arylsilyl group (preferably C 6 to Arylsilyl group of C 18 , C 1 ~ C 40 alkyl boron group (preferably C 1 ~ C 10 alkyl boron group), C 6 ~ C 60 aryl boron group (preferably C 6 ~ C 18 Aryl boron group), C 6 ~ C 60 aryl phosphine group (preferably C 6 ~ C 18 aryl phosphine group), C 6 ~ C 60 aryl phosphine oxide group (preferably C 6 ~ C 18 Aryl phosphine oxide group) and C 6 ~ C 60 arylamine group (preferably C 6 ~ C 20 arylamine group) may be substituted with one or more selected from the group consisting of, a plurality of substituents Are the same or different from each other,
상기 L은 상기 화학식 3이 결합된 화학식 2의 Z1, Z2, R3, R4 및 Y1 내지 Y8 중 어느 하나와 연결된다.L is connected to any one of Z 1 , Z 2 , R 3 , R 4 and Y 1 to Y 8 of Formula 2 to which Formula 3 is attached.
본 발명에서 사용되는 알킬은 탄소수 1 내지 40의 직쇄 또는 측쇄의 포화 탄화수소로부터 수소 원자를 제거하여 얻어지는 1가의 작용기를 의미하며, 이의 비제한적인 예로는 메틸, 에틸, 프로필, 이소부틸, sec-부틸, 펜틸, iso-아밀, 헥실 등이 있다.Alkyl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain saturated hydrocarbon of 1 to 40 carbon atoms, non-limiting examples thereof are methyl, ethyl, propyl, isobutyl, sec-butyl , Pentyl, iso-amyl, hexyl and the like.
본 발명에서 사용되는 알케닐(alkenyl)은 탄소-탄소 이중 결합을 1개 이상 가진 탄소수 2 내지 40의 직쇄 또는 측쇄의 불포화 탄화수소로부터 수소 원자를 제거하여 얻어지는 1가의 작용기를 의미한다. 이의 비제한적인 예로는 비닐(vinyl), 알릴(allyl), 이소프로펜일(isopropenyl), 2-부텐일(2-butenyl) 등이 있다.Alkenyl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon double bond. Non-limiting examples thereof include vinyl, allyl, isopropenyl, 2-butenyl and the like.
본 발명에서 사용되는 알키닐(alkynyl)은 탄소-탄소 삼중 결합을 1개 이상 가진 탄소수 2 내지 40의 직쇄 또는 측쇄의 불포화 탄화수소로부터 수소 원자를 제거하여 얻어지는 1가의 작용기를 의미한다. 이의 비제한적인 예로는 에타인일(ethynyl), 2-프로파인일(2-propynyl) 등이 있다.Alkynyl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon triple bond. Non-limiting examples thereof include ethynyl, 2-propynyl and the like.
본 발명에서 사용되는 시클로알킬은 탄소수 3 내지 40의 모노사이클릭 또는 폴리사이클릭 비-방향족 탄화수소(포화 고리형 탄화수소)로부터 수소 원자를 제거하여 얻어지는 1가의 작용기를 의미한다. 이의 비제한적인 예로는 시클로프로필, 시클로펜틸, 시클로헥실, 노르보닐(norbornyl), 아다만틴(adamantine)등이 있다.Cycloalkyl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms (saturated cyclic hydrocarbon). Non-limiting examples thereof include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine and the like.
본 발명에서 사용되는 헤테로시클로알킬은 핵원자수 3 내지 40의 비-방향족 탄화수소(포화 고리형 탄화수소)로부터 수소 원자를 제거하여 얻어지는 1가의 작용기를 의미하며, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 N, O 또는 S와 같은 헤테로 원자로 치환된다. 이의 비제한적인 예로는 모르폴린, 피페라진 등이 있다.Heterocycloalkyl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from a non-aromatic hydrocarbon (saturated cyclic hydrocarbon) having 3 to 40 nuclear atoms, and preferably at least one carbon in the ring, preferably 1 To 3 carbons are substituted with a hetero atom such as N, O or S. Non-limiting examples thereof include morpholine, piperazine and the like.
본 발명에서 사용되는 아릴은 단독 고리 또는 2 이상의 고리가 조합된 탄소수 6 내지 60의 방향족 탄화수소로부터 수소 원자를 제거하여 얻어지는 1가의 작용기를 의미한다. 이때, 2 이상의 고리는 서로 단순 부착되거나 축합된 형태로 부착될 수 있다. 이의 비제한적인 예로는 페닐, 비페닐, 트리페닐, 터페닐(terphenyl), 나프틸, 플루오레닐, 페난트릴, 안트라세닐, 인데닐 등이 있다.Aryl used in the present invention means a monovalent functional group obtained by removing a hydrogen atom from an aromatic hydrocarbon having 6 to 60 carbon atoms alone or in combination of two or more rings. In this case, the two or more rings may be attached in a simple or condensed form with each other. Non-limiting examples thereof include phenyl, biphenyl, triphenyl, terphenyl, naphthyl, fluorenyl, phenanthryl, anthracenyl, indenyl and the like.
본 발명에서 사용되는 헤테로아릴은 핵원자수 5 내지 60의 모노헤테로사이클릭 또는 폴리헤테로사이클릭 방향족 탄화수소로부터 수소 원자를 제거하여 얻어지는 1가의 작용기로서, 고리 중 하나 이상의 탄소, 바람직하게는 1 내지 3개의 탄소가 질소(N), 산소(O), 황(S) 또는 셀레늄(Se)과 같은 헤테로원자로 치환된다. 이때, 헤테로아릴은 2 이상의 고리가 서로 단순 부착되거나 축합된 형태로 부착될 수 있고, 나아가 아릴기와의 축합된 형태도 포함할 수 있다. 이러한 헤테로아릴의 비제한적인 예로는 피리딜, 피라지닐, 피리미디닐, 피리다지닐, 트리아지닐과 같은 6원 모노사이클릭 고리; 페녹사티에닐(phenoxathienyl), 인돌리지닐(indolizinyl), 인돌릴(indolyl), 퓨리닐(purinyl), 퀴놀릴(quinolyl), 벤조티아졸(benzothiazole), 카바졸릴(carbazolyl)과 같은 폴리사이클릭 고리; 및 2-퓨라닐, N-이미다졸릴, 2-이속사졸릴, 2-피리디닐, 2-피리미디닐 등을 들 수 있다.Heteroaryl used in the present invention is a monovalent functional group obtained by removing a hydrogen atom from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms, and at least one carbon in the ring, preferably 1 to 3 Carbons are substituted with heteroatoms such as nitrogen (N), oxygen (O), sulfur (S) or selenium (Se). In this case, the heteroaryl may be attached in a form in which two or more rings are simply attached or condensed with each other, and may also include a condensed form with an aryl group. Non-limiting examples of such heteroaryls include six-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl; Polycyclics such as phenoxathienyl, indolinzinyl, indolyl, purinyl, quinolyl, benzothiazole, carbazolyl ring; And 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl, and the like.
본 발명에서 사용되는 알킬옥시는 RO-로 표시되는 1가의 작용기를 의미하며, 상기 R은 탄소수 1 내지 40개의 알킬로서, 직쇄(linear), 측쇄(branched) 또는 사이클릭(cyclic) 구조를 포함할 수 있다. 이러한 알킬옥시의 비제한적인 예로는 메톡시, 에톡시, n-프로폭시, 1-프로폭시, t-부톡시, n-부톡시, 펜톡시 등을 들 수 있다.Alkyloxy used in the present invention means a monovalent functional group represented by RO-, wherein R is alkyl having 1 to 40 carbon atoms, and may include a linear, branched, or cyclic structure. Can be. Non-limiting examples of such alkyloxy include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.
본 발명에서 사용되는 아릴옥시는 R'O-로 표시되는 1가의 작용기를 의미하며, 상기 R'는 탄소수 6 내지 60의 아릴이다. 이러한 아릴옥시의 비제한적인 예로는 페닐옥시, 나프틸옥시, 디페닐옥시 등이 있다.Aryloxy used in the present invention means a monovalent functional group represented by R'O-, wherein R 'is an aryl having 6 to 60 carbon atoms. Non-limiting examples of such aryloxy include phenyloxy, naphthyloxy, diphenyloxy and the like.
본 발명에서 사용되는 알킬실릴은 탄소수 1 내지 40의 알킬로 치환된 실릴을 의미하며, 아릴실릴은 탄소수 6 내지 60의 아릴로 치환된 실릴을 의미하고, 아릴아민은 탄소수 6 내지 60의 아릴로 치환된 아민을 의미한다.Alkylsilyl used in the present invention means silyl substituted with alkyl having 1 to 40 carbon atoms, arylsilyl means silyl substituted with aryl having 6 to 60 carbon atoms, and arylamine is substituted with aryl having 6 to 60 carbon atoms. Amine.
본 발명에서 사용되는 축합 고리는 축합 지방족 고리, 축합 방향족 고리, 축합 헤테로지방족 고리, 축합 헤테로방향족 고리 또는 이들의 조합된 형태를 의미한다.As used herein, the condensed ring means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.
한편, 본 발명은 양극; 음극; 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하는 유기 전계 발광 소자로서, 상기 1층 이상의 유기물층 중 적어도 하나는 상기 화학식 1로 표시되는 화합물을 포함하는 것을 특징으로 하는 유기 전계 발광 소자를 제공한다.On the other hand, the present invention is an anode; cathode; And at least one organic material layer interposed between the anode and the cathode, wherein at least one of the at least one organic material layer comprises a compound represented by Chemical Formula 1 Provided is a light emitting device.
여기서, 상기 화학식 1로 표시되는 화합물을 포함하는 유기물층은 정공 주입층, 정공 수송층 및 발광층으로 이루어진 군에서 선택되며, 바람직하게는 발광층이다. 이때, 상기 화학식 1로 표시되는 화합물은 상기 발광층의 인광 호스트로 사용될 수 있다.Herein, the organic material layer including the compound represented by Chemical Formula 1 is selected from the group consisting of a hole injection layer, a hole transport layer, and a light emitting layer, and is preferably a light emitting layer. In this case, the compound represented by Chemical Formula 1 may be used as a phosphorescent host of the emission layer.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
1. 신규 화합물1. New Compound
본 발명의 신규 화합물은 질소(N)를 포함하는 인덴 유도체와 인돌기 융합 화합물이 결합되어 기본 골격을 이루는 것으로, 상기 화학식 1로 표시된다.The novel compound of the present invention forms a basic skeleton by combining an indene derivative including nitrogen (N) and an indole fusion compound, and is represented by Chemical Formula 1.
이러한 본 발명의 화학식 1로 표시되는 화합물은 인광 특성이 우수할 뿐만 아니라, 전자 및/또는 정공 수송 능력이 우수하기 때문에 유기 전계 발광 소자의 유기물층인 정공 주입층, 정공 수송층, 발광층, 전자 수송층 및 전자 주입층 중 어느 하나의 재료로 사용될 수 있다. 바람직하게는 정공 주입층, 정공 수송층 및 발광층 중 어느 하나의 재료, 보다 바람직하게는 발광층의 재료(특히, 인광 호스트 )로 사용될 수 있다.Since the compound represented by Chemical Formula 1 of the present invention not only has excellent phosphorescence properties, but also has excellent electron and / or hole transporting ability, a hole injection layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron, which is an organic material layer of an organic EL device. It can be used as the material of any one of the injection layer. Preferably it can be used as a material of any one of a hole injection layer, a hole transport layer and a light emitting layer, more preferably a material (especially a phosphorescent host) of the light emitting layer.
구체적으로, 본 발명의 화학식 1로 표시되는 화합물은 다양한 치환체가 도입되는 인덴 유도체와 인돌기 융합 화합물이 결합된 것으로, 양극성(bipolar) 특성을 가져 정공과 전자 이동도의 균형이 조절되기 때문에 정공과 전자의 재결합 효율이 향상될 수 있고, 이로 인해 우수한 인광 특성을 나타낼 수 있다. 또 본 발명의 화학식 1로 표시되는 화합물은 질소(N)를 포함하는 인덴 유도체와 인돌기 융합 화합물로 이루어진 기본 골격에 여러 치환체가 도입되어 에너지 레벨이 조절됨에 따라 넓은 에너지 밴드갭(sky blue ~ red)을 가질 수 있다. 따라서, 본 발명의 화학식 1의 화합물을 유기 전계 발광 소자에 사용할 경우, 소자의 인광 특성이 개선되고, 정공 주입 능력 및/또는 정공 수송 능력, 발광효율, 구동전압 및 수명 특성 등이 개선될 수 있다.Specifically, the compound represented by Chemical Formula 1 of the present invention is a combination of an indene derivative and an indole fusion compound into which various substituents are introduced, and has a bipolar characteristic, so that the balance of holes and electron mobility is controlled. The recombination efficiency of the electrons can be improved, thereby exhibiting excellent phosphorescence characteristics. In addition, the compound represented by Formula 1 of the present invention has a wide energy bandgap (sky blue ~ red) as the energy level is controlled by introducing various substituents into the basic skeleton consisting of an indene derivative containing nitrogen (N) and an indole fusion compound ) Therefore, when the compound of Formula 1 of the present invention is used in an organic electroluminescent device, the phosphorescence property of the device may be improved, and the hole injection ability and / or hole transport ability, the luminous efficiency, the driving voltage and the lifetime characteristics may be improved. .
또한 본 발명의 화학식 1로 표시되는 화합물은 상기 기본 골격에 도입된 다양한 치환체로 인해 분자량이 유의적으로 증대됨으로써, 유리전이온도가 향상되고, 이로 인해 종래 유기 전계 발광 소자용 재료(예를 들어, CBP [4,4-dicarbazolybiphenyl])보다 높은 열적 안정성을 가질 수 있다.In addition, the compound represented by the general formula (1) of the present invention has a significant increase in molecular weight due to the various substituents introduced in the basic skeleton, thereby improving the glass transition temperature, which is a conventional organic electroluminescent device material (for example, CBP [4,4-dicarbazolybiphenyl]) may have a higher thermal stability.
따라서, 본 발명에 따른 화합물은 유기 전계 발광 소자의 성능 개선 및 수명 향상에 크게 기여할 수 있으며, 나아가 유기 전계 발광 소자의 수명 향상은 풀 칼라 유기 발광 패널의 성능을 극대화시킬 수 있다.Therefore, the compound according to the present invention can greatly contribute to improving the performance and lifespan of the organic light emitting device, and further, the lifespan of the organic light emitting device can maximize the performance of the full color organic light emitting panel.
이러한 본 발명의 화학식 1로 표시되는 화합물에서, 질소(N)를 포함하는 인덴 유도체의 X1 내지 X3는 각각 독립적으로 CR2 또는 N인데, 이때 적어도 하나가 질소(N)인 것이 바람직하며, 모두 질소(N)인 것이 더욱 바람직하다.In the compound represented by Formula 1 of the present invention, X 1 to X 3 of the indene derivative containing nitrogen (N) are each independently CR 2 or N, wherein at least one is preferably nitrogen (N), It is more preferable that all are nitrogen (N).
구체적으로, 질소(N)를 포함하는 인덴 유도체인
Figure PCTKR2013011402-appb-I000004
는 하기 S-1 내지 S-7로 표시되는 구조로 이루어진 군에서 선택되는 것이 바람직하며, 그 중에서도 트리아졸로피리딘 유도체인 S-7이 가장 바람직하다. 상기 S-1 내지 S-7로 표시되는 구조에서 R2는 상기에서 정의한 바와 같으며, 복수개의 R2는 서로 동일하거나 상이할 수 있다.Specifically, the indene derivative containing nitrogen (N)
Figure PCTKR2013011402-appb-I000004
Is preferably selected from the group consisting of the structures represented by S-1 to S-7, and among them, S-7 which is a triazolopyridine derivative is most preferred. In the structures represented by S-1 to S-7, R 2 is as defined above, and a plurality of R 2 may be the same as or different from each other.
Figure PCTKR2013011402-appb-I000005
Figure PCTKR2013011402-appb-I000005
한편 본 발명의 화학식 1로 표시되는 화합물에서, R1 및 R2는 각각 독립적으로 수소, C6~C60의 아릴기(바람직하게는 C6~C25의 아릴기), 핵원자수 5 내지 60의 헤테로아릴기(바람직하게는 핵원자수 5 내지 32의 헤테로아릴기) 및 C6~C60의 아릴아민기(바람직하게는 C6~C20의 아릴아민기)로 이루어진 군에서 선택되는 것이 바람직하며, 수소인 것이 더욱 바람직하다.On the other hand, in the compound represented by the formula (1) of the present invention, R 1 and R 2 are each independently hydrogen, C 6 ~ C 60 aryl group (preferably C 6 ~ C 25 aryl group), 5 to 5 nuclear atoms Selected from the group consisting of 60 heteroaryl groups (preferably heteroaryl groups having 5 to 32 nuclear atoms) and arylamine groups having C 6 to C 60 (preferably arylamine groups having C 6 to C 20 ) It is preferable, and it is more preferable that it is hydrogen.
구체적으로, 상기 R1 및 R2와, 상기 인덴 유도체에 결합되는 A는 각각 독립적으로 수소, 또는 하기 A1 내지 A70으로 표시되는 구조(치환기)로 이루어진 군에서 선택될 수 있다.Specifically, R 1 and R 2 and A bonded to the indene derivative may be each independently selected from the group consisting of hydrogen or a structure (substituent) represented by A1 to A70.
Figure PCTKR2013011402-appb-I000006
Figure PCTKR2013011402-appb-I000006
Figure PCTKR2013011402-appb-I000007
Figure PCTKR2013011402-appb-I000007
상기 A1 내지 A70으로 표시되는 구조에서 *는 상기 인덴 유도체의 탄소(C)와 결합되는 곳을 의미한다.In the structures represented by A1 to A70, * means a place where carbon (C) of the indene derivative is bonded.
본 발명의 화학식 1로 표시되는 화합물에서, Cy1은 하기 화학식 2a 내지 화학식 2f로 표시되는 화합물로 이루어진 군에서 선택되는 것이 바람직하다.In the compound represented by Formula 1 of the present invention, Cy 1 is preferably selected from the group consisting of compounds represented by the following Formulas 2a to 2f.
[화학식 2a][Formula 2a]
Figure PCTKR2013011402-appb-I000008
Figure PCTKR2013011402-appb-I000008
[화학식 2b][Formula 2b]
Figure PCTKR2013011402-appb-I000009
Figure PCTKR2013011402-appb-I000009
[화학식 2c][Formula 2c]
Figure PCTKR2013011402-appb-I000010
Figure PCTKR2013011402-appb-I000010
[화학식 2d][Formula 2d]
Figure PCTKR2013011402-appb-I000011
Figure PCTKR2013011402-appb-I000011
[화학식 2e][Formula 2e]
Figure PCTKR2013011402-appb-I000012
Figure PCTKR2013011402-appb-I000012
[화학식 2f][Formula 2f]
Figure PCTKR2013011402-appb-I000013
Figure PCTKR2013011402-appb-I000013
상기 화학식 2a 내지 화학식 2f에서, Z1, Z2 및 R3 내지 R6은 상기에서 정의한 바와 같다. 이때, 복수개의 R5는 서로 동일하거나 상이할 수 있으며, 복수개의 R6도 서로 동일하거나 상이할 수 있다.In Formulas 2a to 2f, Z 1 , Z 2, and R 3 to R 6 are the same as defined above. In this case, the plurality of R 5 may be the same or different from each other, a plurality of R 6 may be the same or different from each other.
한편 유기 전계 발광 소자의 효율 및 수명 특성을 고려할 때, 본 발명의 화학식 1로 표시되는 화합물에서, 상기 질소(N)를 포함하는 인덴 유도체와 상기 화학식 2a 내지 화학식 2f로 표시되는 화합물로 이루어진 군에서 선택된 화합물을 연결하는 L은 단일결합이거나 페닐렌인 것이 바람직하다. 또한, 상기 화학식 2a 내지 화학식 2f로 표시되는 화합물에서, 상기 Z1 및 Z2는 모두 N(Ar1)인 것이 바람직하며, Z1으로 결합되는 N(Ar1)의 Ar1과 Z2로 결합되는 N(Ar1)의 Ar1은 서로 동일하거나 상이할 수 있다. 구체적으로, Z1 및 Z2가 모두 N(Ar1) 일 때, 상기 Ar1은 수소, C6~C60의 아릴기(바람직하게는 C6~C18의 아릴기) 및 핵원자수 5 내지 60의 헤테로아릴기(바람직하게는 핵원자수 5 내지 18의 헤테로아릴기)로 이루어진 군에서 선택되는 것이 바람직하다.On the other hand, considering the efficiency and life characteristics of the organic electroluminescent device, in the compound represented by the formula (1) of the present invention, in the group consisting of the indene derivative containing the nitrogen (N) and the compound represented by the formula (2a) to formula (2f) It is preferable that L connecting the selected compound is a single bond or phenylene. In addition, in the compounds represented by Formulas 2a to 2f, Z 1 and Z 2 are preferably both N (Ar 1 ), and are bonded to Ar 1 and Z 2 of N (Ar 1 ) bonded to Z 1 . N 1 of Ar (Ar 1) which may be the same or different from each other. Specifically, when Z 1 and Z 2 are both N (Ar 1 ), Ar 1 is hydrogen, C 6 ~ C 60 aryl group (preferably C 6 ~ C 18 aryl group) and the number of nuclear atoms 5 It is preferably selected from the group consisting of a heteroaryl group of 60 to 60 (preferably a heteroaryl group having 5 to 18 nuclear atoms).
본 발명의 화학식 1로 표시되는 화합물에서 L과 상기 화학식 2로 표시되는 화합물의 연결위치(결합위치)는 특별히 한정되지 않으나, 화학식 3이 결합된 화학식 2의 Z1 및 Z2 중 어느 하나와 연결되는 것이 바람직하다.In the compound represented by Formula 1 of the present invention, the linking position (bonding position) of L and the compound represented by Formula 2 is not particularly limited, but is connected to any one of Z 1 and Z 2 of Formula 2 to which Formula 3 is bound. It is desirable to be.
이러한 본 발명의 화학식 1로 표시되는 화합물은 하기 화학식 4 또는 화학식 5로 표시되는 화합물인 것이 바람직하다.The compound represented by the formula (1) of the present invention is preferably a compound represented by the following formula (4) or formula (5).
[화학식 4][Formula 4]
Figure PCTKR2013011402-appb-I000014
Figure PCTKR2013011402-appb-I000014
[화학식 5][Formula 5]
Figure PCTKR2013011402-appb-I000015
Figure PCTKR2013011402-appb-I000015
상기 화학식 4 및 화학식 5에서, A, L, Cy1, R1 및 n은 상기에서 정의한 바와 같으며, 복수개의 R1은 서로 동일하거나 상이하다.In Formulas 4 and 5, A, L, Cy 1 , R 1 and n are as defined above, and a plurality of R 1 are the same as or different from each other.
이와 같은 본 발명의 화학식 1로 표시되는 화합물은 구체적으로 하기 화합물들(1 내지 70)로 예시될 수 있으나, 이에 한정되는 것은 아니다.Such a compound represented by Formula 1 of the present invention may be specifically exemplified by the following compounds (1 to 70), but is not limited thereto.
Figure PCTKR2013011402-appb-I000016
Figure PCTKR2013011402-appb-I000016
Figure PCTKR2013011402-appb-I000017
Figure PCTKR2013011402-appb-I000017
Figure PCTKR2013011402-appb-I000018
Figure PCTKR2013011402-appb-I000018
이와 같은 본 발명의 화학식 1로 표시되는 화합물은 하기 실시예의 합성과정을 참고하여 다양하게 합성할 수 있다.Such a compound represented by Formula 1 of the present invention can be synthesized in various ways with reference to the synthesis process of the following examples.
2. 유기 전계 발광 소자2. Organic electroluminescent device
본 발명은 상기 화학식 1로 표시되는 화합물을 포함하는 유기 전계 발광 소자를 제공한다.The present invention provides an organic electroluminescent device comprising a compound represented by the formula (1).
구체적으로, 본 발명에 따른 유기 전계 발광 소자는 양극(anode), 음극(cathode) 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하며, 상기 1층 이상의 유기물층 중 적어도 하나는 상기 화학식 1로 표시되는 화합물을 포함하는 것을 특징으로 한다.Specifically, the organic electroluminescent device according to the present invention comprises an anode, a cathode and at least one organic layer interposed between the anode and the cathode, at least one of the at least one organic layer It is characterized by including a compound represented by the formula (1).
상기 화학식 1로 표시되는 화합물을 포함하는 유기물층은 정공 주입층, 정공 수송층, 발광층, 전자수송층 및 전자주입층 중 어느 하나 이상일 수 있다. 바람직하게는 상기 화학식 1의 화합물을 포함하는 유기물층이 정공 주입층, 정공 수송층 또는 발광층일 수 있으며, 보다 바람직하게는 발광층일 수 있다.The organic material layer including the compound represented by Chemical Formula 1 may be any one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer. Preferably, the organic material layer including the compound of Formula 1 may be a hole injection layer, a hole transport layer or a light emitting layer, more preferably a light emitting layer.
본 발명에 따른 유기 전계 발광 소자의 발광층은 호스트 재료(바람직하게는, 인광 호스트 재료)를 함유할 수 있는데, 이때, 호스트 재료로 상기 화학식 1로 표시되는 화합물을 사용할 수 있다. 이와 같이 발광층이 상기 화학식 1로 표시되는 화합물을 포함할 경우, 정공 수송 능력이 증가되어 발광층에서 정공과 전자의 결합력이 높아지기 때문에, 효율(발광효율 및 전력효율), 수명, 휘도 및 구동전압 등이 우수한 유기 전계 발광 소자를 제공할 수 있다.The light emitting layer of the organic electroluminescent device according to the present invention may contain a host material (preferably a phosphorescent host material), in which case, the compound represented by Chemical Formula 1 may be used as the host material. As such, when the light emitting layer includes the compound represented by Chemical Formula 1, since the hole transporting ability is increased to increase the bonding force between the holes and the electrons in the light emitting layer, efficiency (luminescence efficiency and power efficiency), lifetime, luminance, driving voltage, etc. An excellent organic electroluminescent device can be provided.
본 발명에 따른 유기 전계 발광 소자의 구조는 특별히 한정되지 않으며, 비제한적인 예로 기판, 양극, 정공주입층, 정공수송층, 발광층, 전자수송층 및 음극이 순차적으로 적층된 구조로 이루어질 수 있다. 여기서, 전자수송층 위에는 전자주입층이 추가로 적층될 수도 있다. 또한, 본 발명에 따른 유기 전계 발광 소자는 양극, 1층 이상의 유기물층 및 음극이 순차적으로 적층된 구조뿐만 아니라, 전극과 유기물층 계면에 절연층 또는 접착층이 삽입된 구조로 이루어질 수도 있다.The structure of the organic electroluminescent device according to the present invention is not particularly limited and may be formed of a structure in which a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are sequentially stacked. Here, the electron injection layer may be further stacked on the electron transport layer. In addition, the organic electroluminescent device according to the present invention may not only have a structure in which an anode, at least one organic material layer, and a cathode are sequentially stacked, but also have a structure in which an insulating layer or an adhesive layer is inserted at an interface between the electrode and the organic material layer.
한편, 본 발명에 따른 유기 전계 발광 소자에 포함되는 양극으로 사용 가능한 물질은 특별히 한정되지 않으나, 비제한적인 예로 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연산화물, 인듐산화물, 인듐 주석 산화물(ITO), 인듐 아연 산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO2:Sb와 같은 금속과 산화물의 조합; 폴리티오펜, 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDT), 폴리피롤 또는 폴리아닐린과 같은 전도성 고분자; 및 카본블랙 등을 사용할 수 있다.On the other hand, the material that can be used as the anode included in the organic electroluminescent device according to the present invention is not particularly limited, but non-limiting examples include metals such as vanadium, chromium, copper, zinc, gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO 2 : Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole or polyaniline; And carbon black and the like can be used.
또, 본 발명에 따른 유기 전계 발광 소자에 포함되는 음극으로 사용 가능한 물질은 특별히 한정되지 않으나, 비제한적인 예로 마그네슘, 칼슘, 나트륨, 칼륨, 타이타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석, 또는 납과 같은 금속 또는 이들의 합금; 및 LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등을 사용할 수 있다.In addition, the material that can be used as the cathode included in the organic EL device according to the present invention is not particularly limited, but non-limiting examples include magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, Tin or metals such as lead or alloys thereof; And multilayer structure materials such as LiF / Al or LiO 2 / Al, and the like.
본 발명에 따른 유기 전계 발광 소자에 포함되는 유기물층은 상기 화학식 1로 표시되는 화합물을 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 중 어느 하나, 바람직하게는 정공 주입층, 정공 수송층 및 발광층 중 어느 하나, 보다 바람직하게는 발광층에 사용하는 것을 제외하고는, 당 기술 분야에 알려져 있는 재료 및 방법을 이용하여 이루어질 수 있다.In the organic material layer included in the organic electroluminescent device according to the present invention, the compound represented by Chemical Formula 1 may be any one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, preferably a hole injection layer, a hole transport layer and Except for use in any one of the light emitting layers, more preferably the light emitting layer, it can be made using materials and methods known in the art.
본 발명에 따른 유기 전계 발광 소자에 포함되는 기판으로 사용 가능한 물질은 특별히 한정되지 않으나, 비제한적인 예로 실리콘 웨이퍼, 석영, 유리판, 금속판, 플라스틱 필름 및 시트 등이 사용될 수 있다. The material usable as the substrate included in the organic electroluminescent device according to the present invention is not particularly limited, but non-limiting examples may include silicon wafers, quartz, glass plates, metal plates, plastic films and sheets.
이와 같은 본 발명의 유기 전계 발광 소자는 당업계에 공지된 방법으로 제조될 수 있으며, 이때, 유기물층에 포함되는 발광층은 진공 증착법이나 용액 도포법으로 제조될 수 있다. 여기서, 용액 도포법의 예로는 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯 프린팅 또는 열 전사법 등이 있으나, 이들에 한정되지 않는다.Such an organic electroluminescent device of the present invention may be manufactured by a method known in the art, wherein the light emitting layer included in the organic material layer may be manufactured by a vacuum deposition method or a solution coating method. Here, examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.
이하 본 발명을 실시예를 통하여 상세히 설명하면 다음과 같다. 단, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following examples are merely to illustrate the present invention and the present invention is not limited by the following examples.
[인덴 유도체 합성][Indene derivative synthesis]
<Scheme 1><Scheme 1>
Figure PCTKR2013011402-appb-I000019
Figure PCTKR2013011402-appb-I000019
<Scheme 2><Scheme 2>
Figure PCTKR2013011402-appb-I000020
Figure PCTKR2013011402-appb-I000020
상기 Scheme 1 및 2에서 Ar 및 Ar'는 C6~C60의 아릴기이고, X는 할로겐기이다.Ar and Ar 'in Schemes 1 and 2 are C 6 ~ C 60 aryl group, X is a halogen group.
[준비예 1] 5-bromo-[1,2,4]triazolopyridin-2-ylamine의 합성Preparation Example 1 Synthesis of 5-bromo- [1,2,4] triazolopyridin-2-ylamine
<단계 1> 1-(3-bromo-pyridine-2-yl)-3-carboethoxy-thiourea의 합성Step 1 Synthesis of 1- (3-bromo-pyridine-2-yl) -3-carboethoxy-thiourea
Figure PCTKR2013011402-appb-I000021
Figure PCTKR2013011402-appb-I000021
2-amino-3-bromopyridine 100g (0.58 mol)에 DCM 1.0 L를 가하였다. 0?로 냉각하고 ethoxycarbonyl isothiocyanate 68.2 mL (0.58 mol)를 15분에 걸쳐 천천히 적가하였다. 반응액을 상온으로 올리고 20시간 교반하였다. 감압증류하여 용매를 적절히 제거하고 여과하였다. 훈풍 건조하여 목적 화합물 158 g (수율 90%)을 얻었다.1.0 L of DCM was added to 100 g (0.58 mol) of 2-amino-3-bromopyridine. After cooling to 0 ?, 68.2 mL (0.58 mol) of ethoxycarbonyl isothiocyanate was slowly added dropwise over 15 minutes. The reaction solution was raised to room temperature and stirred for 20 hours. After distillation under reduced pressure, the solvent was properly removed and filtered. Hot air drying gave 158 g (yield 90%) of the title compound.
<단계 2> 5-bromo-[1,2,4]triazolopyridin-2-ylamine의 합성Step 2 Synthesis of 5-bromo- [1,2,4] triazolopyridin-2-ylamine
Figure PCTKR2013011402-appb-I000022
Figure PCTKR2013011402-appb-I000022
Hydroxylamine hydrochloride 180.5 g (2.60 mol)에 EtOH/MeOH (1:1, 1.5 L) 혼합용매를 가하였다. N,N-Diisopropylethylamine 271 mL (1.56 mol)를 반응액에 가하고 1시간 교반하였다. 상기에서 합성된 1-(3-bromo-pyridine-2-yl)-3-carboethoxy-thiourea 158 g (0.52 mol)을 첨가하고 서서히 온도를 올려주어 3시간 동안 가열환류하였다. 온도를 상온으로 냉각하고 생성된 고체를 여과하였다. 여액을 감압증류하고 생성된 고체를 여과하였다. 얻어진 고체 생성물을 합하여 정제수, EtOH/MeOH 혼합용매 및 n-hexane으로 세척하고 훈풍 건조하여 목적 화합물 91 g (수율 82%)을 얻었다. EtOH / MeOH (1: 1, 1.5 L) mixed solvent was added to 180.5 g (2.60 mol) of hydroxylamine hydrochloride. 271 mL (1.56 mol) of N, N-Diisopropylethylamine was added to the reaction solution, and the mixture was stirred for 1 hour. 158 g (0.52 mol) of 1- (3-bromo-pyridine-2-yl) -3-carboethoxy-thiourea synthesized above was added thereto, and the temperature was gradually raised to reflux for 3 hours. The temperature was cooled to room temperature and the resulting solid was filtered off. The filtrate was distilled under reduced pressure and the resulting solid was filtered. The obtained solid product was combined, washed with purified water, EtOH / MeOH mixed solvent, n-hexane, and warmed to obtain 91 g (yield 82%) of the title compound.
[준비예 2] 8-([1,1'-biphenyl]-4-yl)-[1,2,4]triazolo[1,5-a]pyridin-2-amine의 합성Preparation Example 2 Synthesis of 8-([1,1'-biphenyl] -4-yl)-[1,2,4] triazolo [1,5-a] pyridin-2-amine
Figure PCTKR2013011402-appb-I000023
Figure PCTKR2013011402-appb-I000023
4-biphenylboronic acid 20 g (100 mmol)과 5-bromo-[1,2,4]triazolopyridin-2-ylamine 23.7 g (111 mmol)에 toluene 500 mL를 가하였다. Pd(PPh3)4 5.8 g (5 mmol), Na2CO3 32 g (303 mmol)을 첨가 후 120?에서 8시간 가열환류하였다. 상온으로 온도를 냉각하고 반응액에 정제수 300 mL를 첨가하였다. 1시간 교반 후 반응액에 생성된 고체를 감압여과하고 E.A 100 mL로 세척하였다. 얻어진 고체를 훈풍 건조하여 목적 화합물 20.8 g (수율 72%)을 얻었다.500 mL of toluene was added to 20 g (100 mmol) of 4-biphenylboronic acid and 23.7 g (111 mmol) of 5-bromo- [1,2,4] triazolopyridin-2-ylamine. 5.8 g (5 mmol) of Pd (PPh 3 ) 4 and 32 g (303 mmol) of Na 2 CO 3 were added and heated to reflux at 120 ° C. for 8 hours. Cooled to room temperature and 300 mL of purified water was added to the reaction solution. After stirring for 1 hour, the resulting solid was filtered under reduced pressure and washed with EA 100 mL. The obtained solid was warmed and dried to obtain 20.8 g (yield 72%) of the title compound.
[준비예 3] 8-([1,1'-biphenyl]-4-yl)-2-bromo-[1,2,4]triazolo[1,5-a]pyridine의 합성Preparation Example 3 Synthesis of 8-([1,1'-biphenyl] -4-yl) -2-bromo- [1,2,4] triazolo [1,5-a] pyridine
Figure PCTKR2013011402-appb-I000024
Figure PCTKR2013011402-appb-I000024
8-([1,1'-biphenyl]-4-yl)-[1,2,4]triazolo[1,5-a]pyridin-2-amine 15 g (52.4 mmol), CuBr2 3.5 g (15.7 mmol), HBr 100 mL와 정제수 100 mL를 혼합하였다. 0?로 냉각하고 NaNO2 10.8 g (157 mmol)을 정제수 50 mL에 용해시켜 천천히 적가하였다. 반응액을 상온에서 12시간 교반하였다. 반응액에 탄산나트륨수용액 100 mL 가하고 1 시간 교반 후 생성된 고체를 여과하였다. 얻어진 고체를 E.A 150 mL로 재결정하여 목적 화합물 16.0 g (수율 87%)을 얻었다. 8-([1,1'-biphenyl] -4-yl)-[1,2,4] triazolo [1,5-a] pyridin-2-amine 15 g (52.4 mmol), CuBr 2 3.5 g (15.7 mmol), 100 mL of HBr and 100 mL of purified water were mixed. After cooling to 0? 10.8 g (157 mmol) of NaNO 2 was dissolved in 50 mL of purified water and slowly added dropwise. The reaction solution was stirred at room temperature for 12 hours. 100 mL of aqueous sodium carbonate solution was added to the reaction solution, and the resulting solid was filtered after stirring for 1 hour. The obtained solid was recrystallized with 150 mL of EA to obtain 16.0 g (yield 87%) of the title compound.
[준비예 4] 8-([1,1'-biphenyl]-4-yl)-2-(4-chlorophenyl)-[1,2,4]triazolo[1,5-a]pyridine의 합성Preparation Example 4 Synthesis of 8-([1,1'-biphenyl] -4-yl) -2- (4-chlorophenyl)-[1,2,4] triazolo [1,5-a] pyridine
Figure PCTKR2013011402-appb-I000025
Figure PCTKR2013011402-appb-I000025
8-([1,1'-biphenyl]-4-yl)-2-bromo-[1,2,4]triazolo[1,5-a]pyridine 15 g (42.8 mmol)과 4-chlorophenylboronic acid 7.4 g (47.1 mmol)에 toluene 300 mL를 가하였다. Pd(PPh3)4 2.5 g (2.1 mmol), K2CO3 17.8 g (128 mmol)을 첨가 후 120?에서 3시간 가열환류하였다. 상온으로 온도를 냉각하고 반응액에 염화암모늄 수용액 500 mL로 반응을 종결시켰다. 혼합액을 E.A 500 mL로 추출한 후, 증류수로 세척하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류하고 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 13.9 g (수율 85%)을 얻었다.8-([1,1'-biphenyl] -4-yl) -2-bromo- [1,2,4] triazolo [1,5-a] pyridine 15 g (42.8 mmol) and 4-chlorophenylboronic acid 7.4 g 300 mL of toluene was added to (47.1 mmol). 2.5 g (2.1 mmol) of Pd (PPh 3 ) 4 and 17.8 g (128 mmol) of K 2 CO 3 were added and heated to reflux at 120 ° C. for 3 hours. The temperature was cooled to room temperature, and the reaction was terminated with 500 mL of aqueous ammonium chloride solution. The mixture was extracted with 500 mL of EA and washed with distilled water. The obtained organic layer was dried over anhydrous MgSO 4 , distilled under reduced pressure and purified by silica gel column chromatography to obtain 13.9 g (yield 85%) of the title compound.
[준비예 5] 8-([1,1'-biphenyl]-4-yl)-2-(3-chlorophenyl)-[1,2,4]triazolo[1,5-a]pyridine의 합성Preparation Example 5 Synthesis of 8-([1,1'-biphenyl] -4-yl) -2- (3-chlorophenyl)-[1,2,4] triazolo [1,5-a] pyridine
Figure PCTKR2013011402-appb-I000026
Figure PCTKR2013011402-appb-I000026
4-chlorophenylboronic acid 대신 3-chlorophenylboronic acid을 사용하는 것을 제외하고는 [준비예 4]과 동일한 과정을 수행하여 목적 화합물 13.1 g (수율 80%)을 얻었다.Except for using 3-chlorophenylboronic acid instead of 4-chlorophenylboronic acid was carried out the same procedure as in [Preparation Example 4] to obtain 13.1 g (yield 80%) of the target compound.
[준비예 6] 2-(4-chlorophenyl)-8-(4-(naphthalen-1-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine의 합성Preparation Example 6 Synthesis of 2- (4-chlorophenyl) -8- (4- (naphthalen-1-yl) phenyl)-[1,2,4] triazolo [1,5-a] pyridine
Figure PCTKR2013011402-appb-I000027
Figure PCTKR2013011402-appb-I000027
8-([1,1'-biphenyl]-4-yl)-2-bromo-[1,2,4]triazolo[1,5-a]pyridine 대신 2-bromo-8-(4-(naphthalen-1-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine을 사용하는 것을 제외하고는 [준비예 4]과 동일한 과정을 수행하여 목적 화합물 12.2 g (수율 72%)을 얻었다.8-([1,1'-biphenyl] -4-yl) -2-bromo- [1,2,4] triazolo [1,5-a] pyridine instead of 2-bromo-8- (4- (naphthalen- Except for using 1-yl) phenyl)-[1,2,4] triazolo [1,5-a] pyridine, the same procedure as in [Preparation 4] was carried out to obtain 12.2 g of the target compound (yield 72%) Got.
[준비예 7] 8-([1,1':3',1''-terphenyl]-5'-yl)-2-(4-chlorophenyl)-[1,2,4]triazolo[1,5-a]pyridine의 합성Preparation Example 7 8-([1,1 ': 3', 1 ''-terphenyl] -5'-yl) -2- (4-chlorophenyl)-[1,2,4] triazolo [1,5 -a] Synthesis of pyridine
Figure PCTKR2013011402-appb-I000028
Figure PCTKR2013011402-appb-I000028
8-([1,1'-biphenyl]-4-yl)-2-bromo-[1,2,4]triazolo[1,5-a]pyridine 대신 8-([1,1':3',1''-terphenyl]-5'-yl)-2-bromo-[1,2,4]triazolo[1,5-a]pyridine을 사용하는 것을 제외하고는 [준비예 4]과 동일한 과정을 수행하여 목적 화합물 10.3 g (수율 70%)을 얻었다.8-([1,1 ': 3', instead of 8-([1,1'-biphenyl] -4-yl) -2-bromo- [1,2,4] triazolo [1,5-a] pyridine Perform the same procedure as in [Preparation 4], except that 1 ''-terphenyl] -5'-yl) -2-bromo- [1,2,4] triazolo [1,5-a] pyridine is used. 10.3 g (yield 70%) of the title compound were obtained.
[준비예 8] 8-(4-(naphthalen-1-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridin-2-amine의 합성Preparation Example 8 Synthesis of 8- (4- (naphthalen-1-yl) phenyl)-[1,2,4] triazolo [1,5-a] pyridin-2-amine
Figure PCTKR2013011402-appb-I000029
Figure PCTKR2013011402-appb-I000029
4-biphenylboronic acid 대신 (4-(naphthalen-1-yl)phenyl)boronic acid을 사용하는 것을 제외하고는 [준비예 2]과 동일한 과정을 수행하여 목적 화합물 23.1 g (수율 73%)을 얻었다.23.1 g (yield 73%) of the title compound was obtained in the same manner as in [Preparation Example 2], except that (4- (naphthalen-1-yl) phenyl) boronic acid was used instead of 4-biphenylboronic acid.
[준비예 9] 2-bromo-8-(4-(naphthalen-1-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine 의 합성Preparation Example 9 Synthesis of 2-bromo-8- (4- (naphthalen-1-yl) phenyl)-[1,2,4] triazolo [1,5-a] pyridine
Figure PCTKR2013011402-appb-I000030
Figure PCTKR2013011402-appb-I000030
8-([1,1'-biphenyl]-4-yl)-[1,2,4]triazolo[1,5-a]pyridine-2-amine 대신 8-(4-(naphthalen-1-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridin-2-amine을 사용하는 것을 제외하고는 [준비예 3]과 동일한 과정을 수행하여 목적 화합물 15.7 g (수율 88%)을 얻었다.8- (4- (naphthalen-1-yl) instead of 8-([1,1'-biphenyl] -4-yl)-[1,2,4] triazolo [1,5-a] pyridine-2-amine Except for using phenyl)-[1,2,4] triazolo [1,5-a] pyridin-2-amine, the same procedure as in [Preparation Example 3] was performed, to obtain 15.7 g of the target compound (yield 88%). Got.
[준비예 10] 8-(3-phenylpyrrolo[3,2-a]carbazol-10(3H)-yl)-[1,2,4]triazolo[1,5-a]pyridin-2-amine의 합성Preparation Example 10 Synthesis of 8- (3-phenylpyrrolo [3,2-a] carbazol-10 (3H) -yl)-[1,2,4] triazolo [1,5-a] pyridin-2-amine
Figure PCTKR2013011402-appb-I000031
Figure PCTKR2013011402-appb-I000031
5-bromo-[1,2,4]triazolopyridin-2-ylamine 20 g (93.9 mmol)과 3-phenyl-3,10-dihydropyrrolo[3,2-a]carbazole 29.1 g (103 mmol)에 dioxane 300 mL와 정제수 100 mL를 가하였다. PdCl2dppf 3.4 g (4.7 mmol), K2CO3 38.9 g (282 mmol)을 첨가 후 120?에서 12시간 가열환류하였다. 상온으로 온도를 냉각하고 반응액에 염화암모늄 수용액 500 mL로 반응을 종결시켰다. 혼합액을 E.A 500 mL로 추출한 후, 증류수로 세척하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류하고 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 28.0 g (수율 72%)을 얻었다.300 mL of dioxane in 20 g (93.9 mmol) of 5-bromo- [1,2,4] triazolopyridin-2-ylamine and 29.1 g (103 mmol) of 3-phenyl-3,10-dihydropyrrolo [3,2-a] carbazole And 100 mL of purified water were added. 3.4 g (4.7 mmol) of PdCl 2 dppf and 38.9 g (282 mmol) of K 2 CO 3 were added and heated to reflux at 120 ° C. for 12 hours. The temperature was cooled to room temperature, and the reaction was terminated with 500 mL of aqueous ammonium chloride solution. The mixture was extracted with 500 mL of EA and washed with distilled water. The obtained organic layer was dried over anhydrous MgSO 4 , distilled under reduced pressure and purified by silica gel column chromatography to obtain 28.0 g (yield 72%) of the title compound.
[준비예 11] 10-(2-bromo-[1,2,4]triazolo[1,5-a]pyridin-8-yl)-3-phenyl-3,10-dihydropyrrolo[3,2-a]carbazole 의 합성Preparation Example 11 10- (2-bromo- [1,2,4] triazolo [1,5-a] pyridin-8-yl) -3-phenyl-3,10-dihydropyrrolo [3,2-a] Synthesis of carbazole
Figure PCTKR2013011402-appb-I000032
Figure PCTKR2013011402-appb-I000032
8-([1,1'-biphenyl]-4-yl)-[1,2,4]triazolo[1,5-a]pyridin-2-amine 대신 8-(3-phenylpyrrolo[3,2-a]carbazol-10(3H)-yl)-[1,2,4]triazolo[1,5-a]pyridin-2-amine을 사용한 것을 제외하고는 [준비예 3]과 동일한 과정을 수행하여 목적 화합물 14.9 g (수율 86%)을 얻었다.8- (3-phenylpyrrolo [3,2-a instead of 8-([1,1'-biphenyl] -4-yl)-[1,2,4] triazolo [1,5-a] pyridin-2-amine Except for using] carbazol-10 (3H) -yl)-[1,2,4] triazolo [1,5-a] pyridin-2-amine, the same procedure as in [Preparation Example 3] was performed. 14.9 g (yield 86%) were obtained.
[합성예 1] 화합물 8의 합성Synthesis Example 1 Synthesis of Compound 8
Figure PCTKR2013011402-appb-I000033
Figure PCTKR2013011402-appb-I000033
3-phenyl-3,10-dihydropyrrolo[3,2-a]carbazole 12 g (42.5 mmol)과 준비예 3에서 합성한 8-([1,1'-biphenyl]-4-yl)-2-bromo-[1,2,4]triazolo[1,5-a]pyridine 16.4 g (46.8 mmol)에 1,4-dioxane 250 mL를 가하였다. Pd2(dba)3 1.9 g (2.1 mmol), BINAP 1.3 g (2.1 mmol), Cs2CO3 27.7 g (85 mmol)을 첨가 후 120?에서 24시간 가열환류하였다. 상온으로 온도를 냉각하고 반응액에 염화암모늄 수용액 500 mL로 반응을 종결시켰다. 혼합액을 E.A 500 mL로 추출한 후, 증류수로 세척하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류하고 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 11.2 g (수율 48%)을 얻었다.12-g (42.5 mmol) of 3-phenyl-3,10-dihydropyrrolo [3,2-a] carbazole and 8-([1,1'-biphenyl] -4-yl) -2-bromo synthesized in Preparation Example 3 250 mL of 1,4-dioxane was added to 16.4 g (46.8 mmol) of-[1,2,4] triazolo [1,5-a] pyridine. 1.9 g (2.1 mmol) of Pd 2 (dba) 3 , 1.3 g (2.1 mmol) of BINAP, and 27.7 g (85 mmol) of Cs 2 CO 3 were added and heated to reflux at 120 ° C. for 24 hours. The temperature was cooled to room temperature, and the reaction was terminated with 500 mL of aqueous ammonium chloride solution. The mixture was extracted with 500 mL of EA and washed with distilled water. The obtained organic layer was dried over anhydrous MgSO 4, distilled under reduced pressure, and purified by silica gel column chromatography to obtain 11.2 g (yield 48%) of the title compound.
[합성예 2] 화합물 32의 합성Synthesis Example 2 Synthesis of Compound 32
Figure PCTKR2013011402-appb-I000034
Figure PCTKR2013011402-appb-I000034
3-phenyl-3,10-dihydropyrrolo[3,2-a]carbazole 10 g (35.4 mmol)과 2-(4-chlorophenyl)-8-(4-(naphthalen-1-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine 16.8 g (39.0 mmol)에 toluene 200 mL를 가하였다. Pd(OAc)2 0.4 g (1.8 mmol), P(t-Bu)3 0.34 g (1.8 mmol), NaOt-Bu 10.2 g (106 mmol)을 첨가 후 120?에서 24시간 가열환류하였다. 상온으로 온도를 냉각하고 반응액에 염화암모늄 수용액 500 mL로 반응을 종결시켰다. 혼합액을 E.A 500 mL로 추출한 후, 증류수로 세척하였다. 얻어진 유기층을 무수 MgSO4로 건조하고, 감압증류하고 실리카겔 컬럼크로마토그래피로 정제하여 목적 화합물 13.9 g (수율 58%)을 얻었다. 10 g (35.4 mmol) of 3-phenyl-3,10-dihydropyrrolo [3,2-a] carbazole and 2- (4-chlorophenyl) -8- (4- (naphthalen-1-yl) phenyl)-[1, 200 mL of toluene was added to 16.8 g (39.0 mmol) of 2,4] triazolo [1,5-a] pyridine. 0.4 g (1.8 mmol) of Pd (OAc) 2 , 0.34 g (1.8 mmol) of P (t-Bu) 3 , and 10.2 g (106 mmol) of NaOt-Bu were heated and refluxed at 120 ° C. for 24 hours. The temperature was cooled to room temperature, and the reaction was terminated with 500 mL of aqueous ammonium chloride solution. The mixture was extracted with 500 mL of EA and washed with distilled water. The obtained organic layer was dried over anhydrous MgSO 4, distilled under reduced pressure, and purified by silica gel column chromatography to obtain 13.9 g (yield 58%) of the title compound.
[합성예 3] 화합물 40의 합성Synthesis Example 3 Synthesis of Compound 40
Figure PCTKR2013011402-appb-I000035
Figure PCTKR2013011402-appb-I000035
2-(4-chlorophenyl)-8-(4-(naphthalen-1-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine 대신 8-([1,1':3',1''-terphenyl]-5'-yl)-2-(4-chlorophenyl)-[1,2,4]triazolo[1,5-a]pyridine을 사용한 것을 제외하고는 [합성예 2]과 동일한 과정을 수행하여 목적 화합물 11 g (수율 55%)을 얻었다.2- (4-chlorophenyl) -8- (4- (naphthalen-1-yl) phenyl)-[1,2,4] triazolo [1,5-a] pyridine instead of 8-([1,1 ': 3 Synthesis Example 2, except that ', 1' '-terphenyl] -5'-yl) -2- (4-chlorophenyl)-[1,2,4] triazolo [1,5-a] pyridine was used 11 g (yield 55%) of the title compound was obtained by the same process as the procedure above.
[합성예 4] 화합물 51의 합성Synthesis Example 4 Synthesis of Compound 51
Figure PCTKR2013011402-appb-I000036
Figure PCTKR2013011402-appb-I000036
2-(4-chlorophenyl)-8-(4-(naphthalen-1-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine 대신 상기 준비예 5에서 합성한 8-([1,1'-biphenyl]-4-yl)-2-(3-chlorophenyl)-[1,2,4]triazolo[1,5-a]pyridine을 사용한 것을 제외하고는 [합성예 2]과 동일한 과정을 수행하여 목적 화합물 10.7 g (수율 60%)을 얻었다.2- (4-chlorophenyl) -8- (4- (naphthalen-1-yl) phenyl)-[1,2,4] triazolo [1,5-a] pyridine instead of 8- ( [Synthesis Example 2], except that [1,1'-biphenyl] -4-yl) -2- (3-chlorophenyl)-[1,2,4] triazolo [1,5-a] pyridine was used The same procedure was followed to obtain 10.7 g (yield 60%) of the title compound.
[합성예 5] 화합물 64의 합성Synthesis Example 5 Synthesis of Compound 64
Figure PCTKR2013011402-appb-I000037
Figure PCTKR2013011402-appb-I000037
3-phenyl-3,10-dihydropyrrolo[3,2-a]carbazole 대신 1-phenyl-1,6-dihydropyrrolo[3,2-c]carbazole을 사용한 것을 제외하고는 [합성예 1]과 동일한 과정을 수행하여 목적 화합물 11.8 g (수율 55%)을 얻었다.The same procedure as in [Synthesis Example 1] was performed except that 1-phenyl-1,6-dihydropyrrolo [3,2-c] carbazole was used instead of 3-phenyl-3,10-dihydropyrrolo [3,2-a] carbazole. This gave 11.8 g (yield 55%) of the title compound.
[합성예 6] 화합물 69의 합성Synthesis Example 6 Synthesis of Compound 69
Figure PCTKR2013011402-appb-I000038
Figure PCTKR2013011402-appb-I000038
반응물로 10-(2-bromo-[1,2,4]triazolo[1,5-a]pyridin-8-yl)-3-phenyl-3,10-dihydropyrrolo[3,2-a]carbazole과 9H-carbazole을 사용한 것을 제외하고는 [합성예 2]와 동일한 과정을 수행하여 목적 화합물 5.5 g (수율 42%)을 얻었다.As a reactant, 10- (2-bromo- [1,2,4] triazolo [1,5-a] pyridin-8-yl) -3-phenyl-3,10-dihydropyrrolo [3,2-a] carbazole and 9H 5.5 g (yield 42%) of the title compound was obtained in the same manner as in Synthesis Example 2, except that -carbazole was used.
[실시예 1 내지 6] 적색 유기 전계 발광 소자의 제작Examples 1 to 6 Fabrication of Red Organic Electroluminescent Devices
합성예 1 내지 6에서 합성한 화합물 8, 32, 40, 51, 64, 69를 통상적으로 알려진 방법으로 고순도 승화정제를 한 후 아래의 과정에 따라 적색 유기 전계 발광 소자를 제작하였다.Compounds 8, 32, 40, 51, 64, and 69 synthesized in Synthesis Examples 1 to 6 were subjected to high purity sublimation purification by a conventionally known method, and then a red organic electroluminescent device was manufactured according to the following procedure.
먼저, ITO (Indium tin oxide)가 1500Å 두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝나면 이소프로필 알코올, 아세톤, 메탄올 등의 용제로 초음파 세척을 하고 건조시킨 후 UV OZONE 세정기 (Power sonic 405, 화신테크)로 이송시킨 다음 UV를 이용하여 상기 기판을 5분간 세정하고 진공 증착기로 기판을 이송하였다.First, a glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 Å was washed with distilled water ultrasonic waves. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried and transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech), and then the substrate is cleaned for 5 minutes by UV and vacuum evaporator The substrate was transferred to.
이렇게 준비된 ITO 투명 전극 위에 m-MTDATA (60 nm)/NPB (20 nm)/화합물 8, 32, 40, 51, 64, 69 각각의 화합물 + 10 % (piq)2Ir(acac) (30nm)/BCP (10 nm)/Alq3 (30 nm)/LiF (1 nm)/Al (200 nm) 순으로 적층하여 적색 유기 전계 발광 소자를 제작하였다.M-MTDATA (60 nm) / NPB (20 nm) / Compound 8, 32, 40, 51, 64, 69 + 10% (piq) 2 Ir (acac) (30nm) / A red organic electroluminescent device was manufactured by stacking BCP (10 nm) / Alq 3 (30 nm) / LiF (1 nm) / Al (200 nm) in this order.
[비교예] 적색 유기 전계 발광 소자의 제작Comparative Example Fabrication of Red Organic Electroluminescent Device
발광층 형성시 발광 호스트 물질로서 화합물 8 대신 CBP를 사용하는 것을 제외하고는 상기 실시예 1과 동일한 과정으로 적색 유기 전계 발광 소자를 제작하였다.A red organic electroluminescent device was manufactured in the same manner as in Example 1, except that CBP was used instead of compound 8 as a light-emitting host material when forming the light-emitting layer.
상기 실시예 1 내지 6 및 비교예에서 사용된 m-MTDATA, NPB, (piq)2Ir(acac), BCP 및 CBP의 구조는 하기와 같다.The structures of m-MTDATA, NPB, (piq) 2 Ir (acac), BCP and CBP used in Examples 1 to 6 and Comparative Examples are as follows.
Figure PCTKR2013011402-appb-I000039
Figure PCTKR2013011402-appb-I000039
[평가예][Evaluation example]
실시예 1 내지 6 및 비교예에서 제작한 각각의 유기 전계 발광 소자에 대하여 전류밀도 10 mA/㎠에서의 구동전압, 전류효율 및 발광 피크를 측정하고, 그 결과를 하기 표 1에 나타내었다.The driving voltage, current efficiency, and emission peak at the current density of 10 mA / cm 2 were measured for each organic electroluminescent device manufactured in Examples 1 to 6 and Comparative Examples, and the results are shown in Table 1 below.
표 1
샘플 호스트 구동전압 (V) 전류효율(cd/A)
실시예 1 화합물 8 4.65 13.5
실시예 2 화합물 32 4.57 13.3
실시예 3 화합물 40 4.60 12.5
실시예 4 화합물 51 4.65 13.0
실시예 5 화합물 64 4.70 12.6
실시예 6 화합물 69 4.66 13.1
비교예 CBP 5.25 8.2
Table 1
Sample Host Drive voltage (V) Current efficiency (cd / A)
Example 1 Compound 8 4.65 13.5
Example 2 Compound 32 4.57 13.3
Example 3 Compound 40 4.60 12.5
Example 4 Compound 51 4.65 13.0
Example 5 Compound 64 4.70 12.6
Example 6 Compound 69 4.66 13.1
Comparative example CBP 5.25 8.2
상기 표1에 나타낸 바와 같이, 본 발명의 화합물을 발광층에 사용한 적색 유기 전계 발광 소자(실시예 1 내지 6)는 종래의 CBP를 발광층에 사용한 적색 유기 전계 발광 소자(비교예)에 비해 구동전압 및 전류효율 면에서 우수한 성능을 나타내는 것을 알 수 있다.As shown in Table 1, the red organic electroluminescent devices (Examples 1 to 6) using the compound of the present invention in the light emitting layer have a driving voltage and a red organic electroluminescent device (comparative example) using the conventional CBP in the light emitting layer. It can be seen that the excellent performance in terms of current efficiency.
본 발명에 따른 화학식 1로 표시되는 화합물은 열적 안정성 및 인광 특성이 우수하기 때문에 유기 전계 발광 소자의 유기물층, 바람직하게는 발광층에 적용될 수 있다. 즉, 유기 전계 발광 소자의 발광층이 상기 화학식 1로 표시되는 화합물을 인광 호스트 물질로 포함할 경우, 종래의 호스트 물질을 포함한 경우에 비해 소자의 효율(발광 효율 및 전력 효율), 수명, 휘도 및 구동전압이 향상될 수 있고, 나아가 풀 칼라 유기 전계 발광 패널의 성능 및 수명이 크게 향상될 수 있다.The compound represented by Formula 1 according to the present invention may be applied to an organic material layer, preferably a light emitting layer of the organic electroluminescent device because of excellent thermal stability and phosphorescence properties. That is, when the light emitting layer of the organic electroluminescent device includes the compound represented by Chemical Formula 1 as a phosphorescent host material, the efficiency (light emitting efficiency and power efficiency), lifetime, brightness and driving of the device compared to the case of including a conventional host material The voltage can be improved, and furthermore, the performance and lifetime of the full color organic electroluminescent panel can be greatly improved.

Claims (11)

  1. 하기 화학식 1로 표시되는 화합물:Compound represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2013011402-appb-I000040
    Figure PCTKR2013011402-appb-I000040
    상기 화학식 1에서,In Chemical Formula 1,
    X1 내지 X3는 각각 독립적으로 CR2 또는 N이고, 이때, 적어도 하나 이상은 N이며,X 1 to X 3 are each independently CR 2 or N, wherein at least one is N,
    R1 및 R2는 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되고, 인접한 기와 축합 고리를 형성할 수 있으며,R 1 and R 2 are each independently hydrogen, deuterium, halogen, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, the number of nuclear atoms of 3 to 40 of the heterocycloalkyl of the alkyl group, C 6 ~ C 60 aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, C 1 ~ alkyloxy group of C 40, C 6 to C 60 aryloxy group, C 1 to C 40 alkylsilyl group, C 6 to C 60 arylsilyl group, C 1 to C 40 alkyl boron group, C 6 to C 60 aryl boron group, C 6 ~ C 60 aryl phosphine is selected from the pingi, C 6 ~ C 60 aryl phosphine oxide group, and the group consisting of C 6 ~ C 60 aryl amine, the adjacent groups may form a fused ring,
    A는 수소, C6~C60의 아릴기 및 핵원자수 5 내지 60의 헤테로아릴기로 이루어진 군에서 선택되고,A is selected from the group consisting of hydrogen, a C 6 ~ C 60 aryl group and a heteroaryl group of 5 to 60 nuclear atoms,
    L은 단일결합, C6~C60의 아릴렌기 및 핵원자수 5 내지 60의 헤테로아릴렌기로 이루어진 군에서 선택되며,L is selected from the group consisting of a single bond, a C 6 ~ C 60 arylene group and a heteroarylene group having 5 to 60 nuclear atoms,
    n은 0 내지 3의 정수이고,n is an integer from 0 to 3,
    Cy1은 하기 화학식 2로 표시되는 화합물이며,Cy 1 is a compound represented by the following formula (2),
    [화학식 2][Formula 2]
    Figure PCTKR2013011402-appb-I000041
    Figure PCTKR2013011402-appb-I000041
    상기 화학식 2에서,In Chemical Formula 2,
    Y1 내지 Y4은 각각 독립적으로 CR5 또는 N이며, Y1 과 Y2, Y2 와 Y3 및 Y3 와 Y4 중 하나는 하기 화학식 3으로 표시되는 축합 고리를 형성하고,Y 1 to Y 4 are each independently CR 5 or N, and one of Y 1 and Y 2 , Y 2 and Y 3, and Y 3 and Y 4 forms a condensed ring represented by the following Formula 3,
    [화학식 3][Formula 3]
    Figure PCTKR2013011402-appb-I000042
    Figure PCTKR2013011402-appb-I000042
    상기 화학식 3에서,In Chemical Formula 3,
    점선은 상기 화학식 2의 화합물과 축합이 이루어지는 부위를 의미하고, Y5 내지 Y8은 각각 독립적으로 CR6 또는 N이며,The dotted line means a site where condensation occurs with the compound of Formula 2, and Y 5 to Y 8 are each independently CR 6 or N,
    Z1 및 Z2는 각각 독립적으로 O, S, Se, N(Ar1), C(Ar2)(Ar3) 및 Si(Ar4)(Ar5)로 이루어진 군에서 선택되고, 이때, 적어도 하나는 N(Ar1)이며,Z 1 and Z 2 are each independently selected from the group consisting of O, S, Se, N (Ar 1 ), C (Ar 2 ) (Ar 3 ) and Si (Ar 4 ) (Ar 5 ), wherein at least One is N (Ar 1 ),
    상기 R3 내지 R6은 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되고, 인접한 기와 축합 고리를 형성할 수 있으며,R 3 to R 6 are each independently hydrogen, deuterium, halogen, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, nuclear hetero atoms 3 to 40 heterocycloalkyl group, C 6 ~ C 60 aryl group, nuclear atoms 5 to 60 heteroaryl group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group and C 6 ~ C 60 It is selected from the group consisting of an arylamine group, it may form a condensed ring with adjacent groups,
    상기 Ar1 내지 Ar5는 각각 독립적으로 수소, 중수소, 할로겐, 시아노기, 니트로기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되고,Ar 1 to Ar 5 are each independently hydrogen, deuterium, halogen, cyano group, nitro group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, the number of nuclear atoms of 3 to 40 of the heterocycloalkyl of the alkyl group, C 6 ~ C 60 aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, C 1 ~ alkyloxy group of C 40, C 6 Aryloxy group of ~ C 60 , C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 6 An arylphosphine group of ~ C 60 , a C 6 ~ C 60 arylphosphine oxide group and a C 6 ~ C 60 arylamine group,
    상기 A의 아릴기 및 헤테로아릴기는 각각 독립적으로 중수소, 할로겐, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상으로 치환될 수 있으며,The aryl group and heteroaryl group of A are each independently deuterium, halogen, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 alkenyl group, C 2 ~ C 40 alkynyl group, C 3 ~ C 40 cycloalkyl group, nuclear hetero atoms 3 to 40 heterocycloalkyl group, C 6 ~ C 40 aryl group, nuclear atoms 5 to 40 heteroaryl group, C 1 ~ C 40 alkyloxy group, C 6 ~ C 60 aryloxy group, C 1 ~ C 40 alkylsilyl group, C 6 ~ C 60 arylsilyl group, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl boron group, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~ C 60 aryl group, and the amine may be substituted with at least one member selected from the group consisting of a,
    상기 R1 내지 R6 및 Ar1 내지 Ar5의 알킬기, 알케닐기, 알키닐기, 시클로알킬기, 헤테로시클로알킬기, 아릴기, 헤테로아릴기, 알킬옥시기, 아릴옥시기, 알킬실릴기, 아릴실릴기, 알킬보론기, 아릴보론기, 아릴포스핀기, 아릴포스핀옥사이드기 및 아릴아민기는 각각 독립적으로 중수소, 할로겐, 시아노기, 니트로기, 아미노기, C1~C40의 알킬기, C2~C40의 알케닐기, C2~C40의 알키닐기, C3~C40의 시클로알킬기, 핵원자수 3 내지 40의 헤테로시클로알킬기, C6~C40의 아릴기, 핵원자수 5 내지 40의 헤테로아릴기, C1~C40의 알킬옥시기, C6~C60의 아릴옥시기, C1~C40의 알킬실릴기, C6~C60의 아릴실릴기, C1~C40의 알킬보론기, C6~C60의 아릴보론기, C6~C60의 아릴포스핀기, C6~C60의 아릴포스핀옥사이드기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택된 1종 이상으로 치환될 수 있으며,The alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group of R 1 to R 6 and Ar 1 to Ar 5 , Alkyl boron group, aryl boron group, aryl phosphine group, aryl phosphine oxide group and arylamine group are each independently deuterium, halogen, cyano group, nitro group, amino group, C 1 ~ C 40 alkyl group, C 2 ~ C 40 Alkenyl group, C 2 to C 40 alkynyl group, C 3 to C 40 cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C 6 to C 40 aryl group, nuclear atom 5 to 40 hetero aryl group, C 1 ~ C 40 of the alkyloxy group, C 6 ~ C 60 of the aryloxy group, C 1 ~ C 40 alkyl silyl group, the group C 6 ~ C 60 aryl silyl, C 1 ~ C 40 alkyl boron group, C 6 ~ C 60 aryl group of boron, C 6 ~ C 60 aryl phosphine group, C 6 ~ C 60 aryl phosphine oxide group, and a C 6 ~ from the group consisting of an arylamine C in 60 Selected, and may be substituted with one or more,
    상기 L은 상기 화학식 3이 결합된 화학식 2의 Z1, Z2, R3, R4 및 Y1 내지 Y8 중 어느 하나와 연결된다.L is connected to any one of Z 1 , Z 2 , R 3 , R 4 and Y 1 to Y 8 of Formula 2 to which Formula 3 is attached.
  2. 제1항에 있어서,The method of claim 1,
    상기 화학식 1의
    Figure PCTKR2013011402-appb-I000043
    는 하기 S-1 내지 S-7로 표시되는 구조로 이루어진 군에서 선택되는 것을 특징으로 하는 화합물.    Of Formula 1
    Figure PCTKR2013011402-appb-I000043
    Is selected from the group consisting of the structures represented by S-1 to S-7.
    Figure PCTKR2013011402-appb-I000044
    Figure PCTKR2013011402-appb-I000044
    상기 S-1 내지 S-7로 표시되는 구조에서,In the structure represented by S-1 to S-7,
    R2는 제1항에서 정의한 바와 같으며, 복수개의 R2는 서로 동일하거나 상이하다.R 2 is as defined in claim 1, and a plurality of R 2 are the same as or different from each other.
  3. 제1항에 있어서,The method of claim 1,
    상기 R1 및 R2는 각각 독립적으로 수소, C6~C60의 아릴기, 핵원자수 5 내지 60의 헤테로아릴기 및 C6~C60의 아릴아민기로 이루어진 군에서 선택되는 것을 특징으로 하는 화합물.R 1 and R 2 are each independently selected from the group consisting of hydrogen, a C 6 ~ C 60 aryl group, a heteroaryl group of 5 to 60 nuclear atoms, and an arylamine group of C 6 ~ C 60 compound.
  4. 제1항에 있어서,The method of claim 1,
    상기 R1, R2 및 A는 각각 독립적으로 수소, 또는 하기 A1 내지 A70으로 표시되는 구조로 이루어진 군에서 선택되는 것을 특징으로 하는 화합물.The R 1 , R 2 and A are each independently hydrogen or a compound, characterized in that selected from the group consisting of the structure represented by A1 to A70.
    Figure PCTKR2013011402-appb-I000045
    Figure PCTKR2013011402-appb-I000045
    Figure PCTKR2013011402-appb-I000046
    Figure PCTKR2013011402-appb-I000046
  5. 제1항에 있어서,The method of claim 1,
    상기 화학식 2로 표시되는 화합물은 하기 화학식 2a 내지 화학식 2f로 표시되는 화합물로 이루어진 군에서 선택되는 것을 특징으로 하는 화합물.Compound represented by the formula (2) is a compound characterized in that it is selected from the group consisting of the compound represented by the formula
    [화학식 2a][Formula 2a]
    Figure PCTKR2013011402-appb-I000047
    Figure PCTKR2013011402-appb-I000047
    [화학식 2b][Formula 2b]
    Figure PCTKR2013011402-appb-I000048
    Figure PCTKR2013011402-appb-I000048
    [화학식 2c][Formula 2c]
    Figure PCTKR2013011402-appb-I000049
    Figure PCTKR2013011402-appb-I000049
    [화학식 2d][Formula 2d]
    Figure PCTKR2013011402-appb-I000050
    Figure PCTKR2013011402-appb-I000050
    [화학식 2e][Formula 2e]
    Figure PCTKR2013011402-appb-I000051
    Figure PCTKR2013011402-appb-I000051
    [화학식 2f][Formula 2f]
    Figure PCTKR2013011402-appb-I000052
    Figure PCTKR2013011402-appb-I000052
    상기 화학식 2a 내지 화학식 2f에서,In Chemical Formulas 2a to 2f,
    Z1, Z2 및 R3 내지 R6은 제1항에서 정의한 바와 같으며, 복수개의 R5는 서로 동일하거나 상이하며, 복수개의 R6도 서로 동일하거나 상이하다.Z 1 , Z 2 and R 3 to R 6 are as defined in claim 1, and a plurality of R 5 are the same as or different from each other, and a plurality of R 6 are also the same or different from each other.
  6. 제5항에 있어서,The method of claim 5,
    상기 화학식 1의 L은 단일결합이거나 페닐렌이며,L in Formula 1 is a single bond or phenylene,
    상기 Z1 및 Z2는 모두 N(Ar1)이고, 이때, Ar1은 서로 동일하거나 상이하며,Z 1 and Z 2 are both N (Ar 1 ), wherein Ar 1 is the same as or different from each other,
    상기 Ar1은 수소, C6~C60의 아릴기 및 핵원자수 5 내지 60의 헤테로아릴기로 이루어진 군에서 선택되는 것을 특징으로 하는 화합물.Ar 1 is hydrogen, a C 6 ~ C 60 A aryl group, and a compound characterized in that it is selected from the group consisting of 5 to 60 nuclear atoms.
  7. 제1항에 있어서,The method of claim 1,
    상기 L은 상기 화학식 3이 결합된 화학식 2의 Z1 및 Z2 중 어느 하나와 연결되는 것을 특징으로 하는 화합물.Wherein L is a compound characterized in that it is connected to any one of Z 1 and Z 2 of the formula (2) bonded to the formula (3).
  8. 제1항에 있어서,The method of claim 1,
    상기 화학식 1로 표시되는 화합물은 하기 화학식 4 또는 화학식 5로 표시되는 화합물인 것을 특징으로 하는 화합물:Compound represented by the formula (1) is a compound characterized in that the compound represented by the following formula (4) or (5):
    [화학식 4][Formula 4]
    Figure PCTKR2013011402-appb-I000053
    Figure PCTKR2013011402-appb-I000053
    [화학식 5][Formula 5]
    Figure PCTKR2013011402-appb-I000054
    Figure PCTKR2013011402-appb-I000054
    상기 화학식 4 및 화학식 5에서,In Chemical Formulas 4 and 5,
    A, L, Cy1, R1 및 n은 제1항에서 정의한 바와 같으며, 복수개의 R1은 서로 동일하거나 상이하다.A, L, Cy 1 , R 1 and n are as defined in claim 1 , and a plurality of R 1 are the same as or different from each other.
  9. 양극; 음극; 및 상기 양극과 음극 사이에 개재(介在)된 1층 이상의 유기물층을 포함하는 유기 전계 발광 소자로서,anode; cathode; And one or more organic material layers interposed between the anode and the cathode.
    상기 1층 이상의 유기물층 중 적어도 하나는 제1항 내지 제8항 중 어느 한 항에 따른 화합물을 포함하는 것을 특징으로 하는 유기 전계 발광 소자.At least one of the at least one organic layer is an organic electroluminescent device, characterized in that it comprises a compound according to any one of claims 1 to 8.
  10. 제9항에 있어서,The method of claim 9,
    상기 화합물을 포함하는 유기물층은 정공 주입층, 정공 수송층 및 발광층으로 이루어진 군에서 선택되는 것을 특징으로 하는 유기 전계 발광 소자.The organic material layer containing the compound is an organic electroluminescent device, characterized in that selected from the group consisting of a hole injection layer, a hole transport layer and a light emitting layer.
  11. 제9항에 있어서,The method of claim 9,
    상기 화합물을 포함하는 유기물층은 발광층이고,The organic material layer containing the compound is a light emitting layer,
    상기 화합물은 상기 발광층의 인광 호스트인 것을 특징으로 하는 유기 전계 발광 소자.The compound is an organic electroluminescent device, characterized in that the phosphorescent host of the light emitting layer.
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