WO2021261856A1 - Heterocyclic compound and organic light-emitting device comprising same - Google Patents

Heterocyclic compound and organic light-emitting device comprising same Download PDF

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WO2021261856A1
WO2021261856A1 PCT/KR2021/007746 KR2021007746W WO2021261856A1 WO 2021261856 A1 WO2021261856 A1 WO 2021261856A1 KR 2021007746 W KR2021007746 W KR 2021007746W WO 2021261856 A1 WO2021261856 A1 WO 2021261856A1
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substituted
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허동욱
홍성길
한미연
윤정민
윤희경
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주식회사 엘지화학
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Priority to CN202180035677.7A priority Critical patent/CN115667249A/en
Publication of WO2021261856A1 publication Critical patent/WO2021261856A1/en

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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
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
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    • 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
    • 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]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers

Definitions

  • the present specification relates to a heterocyclic compound and an organic light emitting device including the same.
  • the organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to the organic light emitting device having such a structure, electrons and holes injected from the two electrodes combine in the organic thin film to form a pair, and then disappear and emit light.
  • the organic thin film may be composed of a single layer or multiple layers, if necessary.
  • hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials, etc. can be divided into
  • the hole injection material or the hole transport material an organic material having a p-type property, that is, an organic material that is easily oxidized and has an electrochemically stable state during oxidation is mainly used.
  • an electron injection material or an electron transport material an organic material having an n-type property, that is, an organic material that is easily reduced and has an electrochemically stable state during reduction is mainly used.
  • the light emitting layer material a material having both p-type and n-type properties, that is, a material having a stable form in both oxidation and reduction states, is preferable, and excitons generated by recombination of holes and electrons in the light emitting layer are formed.
  • a material with high luminous efficiency that converts it into light when it is formed is preferable.
  • the present specification provides a heterocyclic compound and an organic light emitting device including the same.
  • An exemplary embodiment of the present specification provides a heterocyclic compound represented by the following formula (1).
  • Z is O or S
  • R1 and R2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
  • R3 to R6 are each independently hydrogen, or combine with each other to form a hydrocarbon ring
  • L is a direct bond; a substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,
  • a is an integer of 1 to 3, and when a is 2 or more, L of 2 or more are the same as or different from each other,
  • b is an integer of 1 to 4, and when b is 2 or more, the structures in parentheses are the same as or different from each other,
  • Ar1 is any one selected from the group consisting of
  • c is an integer of 1 to 5, and when c is 2 or more, 2 or more G15 are the same as or different from each other,
  • d is an integer of 1 to 4, and when d is 2 or more, 2 or more G16 are the same as or different from each other,
  • X1 to X4 are the same as or different from each other, and each independently represents N or CR10, provided that at least two of X1 to X4 are N;
  • R10 and G1 to G16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • Another embodiment of the present specification is a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the heterocyclic compound.
  • the heterocyclic compound according to an exemplary embodiment of the present specification may be used as a material for an organic material layer of an organic light emitting device, and by using the same, it is possible to improve efficiency, low driving voltage and/or lifespan characteristics in an organic light emitting device.
  • 1 to 4 illustrate an organic light emitting diode according to an exemplary embodiment of the present specification.
  • the present specification provides a heterocyclic compound represented by the following formula (1).
  • Z is O or S
  • R1 and R2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
  • R3 to R6 are each independently hydrogen, or combine with each other to form a hydrocarbon ring
  • L is a direct bond; a substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,
  • a is an integer of 1 to 3, and when a is 2 or more, L of 2 or more are the same as or different from each other,
  • b is an integer of 1 to 4, and when b is 2 or more, the structures in parentheses are the same as or different from each other,
  • Ar1 is any one selected from the group consisting of
  • c is an integer of 1 to 5, and when c is 2 or more, 2 or more G15 are the same as or different from each other,
  • d is an integer of 1 to 4, and when d is 2 or more, 2 or more G16 are the same as or different from each other,
  • X1 to X4 are the same as or different from each other, and each independently represents N or CR10, provided that at least two of X1 to X4 are N;
  • R10 and G1 to G16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • the compound represented by Formula 1 of the present invention is polarized by including only one substituent in the xanthene group, thioxanthene group, benzoxanthene group, or benzothioxanthene group in which Z is O or S. As a result, the dipole moment is improved and the lifespan is improved.
  • the compound represented by Formula 1 of the present invention includes a polycyclic aryl group as R1 and R2; or a heterocyclic group to enhance polarization.
  • the compound exhibits the effect of improving the electron transfer characteristics by substituting Ar1 on one side of the xanthene group, thereby improving the efficiency of the organic light emitting device.
  • substitution means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, a position where the substituent is substitutable, is substituted. , two or more substituents may be the same as or different from each other.
  • substituted or unsubstituted refers to deuterium; halogen group; cyano group (-CN); ester group; imid; amine group; alkoxy group; an alkyl group; cycloalkyl group; aryl group; And it means that it is substituted with one or two or more substituents selected from the group consisting of a heterocyclic group, is substituted with a substituent to which two or more of the above-exemplified substituents are connected, or does not have any substituents.
  • a substituent in which two or more substituents are connected may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected.
  • the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30.
  • Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl,
  • the aryl group is not particularly limited, but preferably has 6 to 50 carbon atoms, such as 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.
  • the aryl group is a monocyclic aryl group
  • the number of carbon atoms is not particularly limited, but preferably 6 to 30 carbon atoms.
  • the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, and the like, but is not limited thereto.
  • the aryl group is a polycyclic aryl group
  • the number of carbon atoms is not particularly limited. It is preferable that it is C10-30.
  • the polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthrene group, a triphenylene group, a pyrene group, a phenalenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, a fluoranthene group, etc.
  • the present invention is not limited thereto.
  • the fluorenyl group may be substituted, and adjacent groups may combine with each other to form a ring.
  • the heterocyclic group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, S and P, and the like.
  • the number of carbon atoms is not particularly limited, but preferably has 1 to 50 carbon atoms, further preferably 2 to 30 carbon atoms, and the heterocyclic group may be monocyclic or polycyclic.
  • the heterocyclic group may be an aromatic ring, an aliphatic ring, or a ring condensed therewith.
  • heterocyclic group examples include a thiophene group, a furanyl group, a pyrrole group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazinyl group, Triazolyl group, acridyl group, pyridazinyl group, pyrazinyl group, quinolyl group, quinazolyl group, quinoxalyl group, phthalazinyl group, pyridopyrimidyl group, pyridopyrazinyl group, pyrazinopyrazinyl group group, isoquinolyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazoly
  • the description of the above-mentioned heterocyclic group may be cited except that the divalent heterocyclic group is divalent.
  • the halogen group may be fluorine, chlorine, bromine or iodine.
  • the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., but are limited thereto it is not
  • the hydrocarbon ring may be an aromatic, aliphatic, or a condensed ring of an aromatic and an aliphatic group, and may be selected from examples of the cycloalkyl group or the aryl group.
  • the alkoxy group may be a straight chain, branched chain or cyclic chain. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C30. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n -hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy and the like may be used, but is not limited thereto.
  • the amine group is -NH 2 ; an alkylamine group; N-alkylarylamine group; arylamine group; N-aryl heteroarylamine group; It may be selected from the group consisting of an N-alkylheteroarylamine group and a heteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 0 to 30.
  • the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, and a 9-methyl-anthracenylamine group.
  • diphenylamine group diphenylamine group, N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group, N-phenylnaphthylamine group, N-bi Phenylnaphthylamine group, N-naphthylfluorenylamine group, N-phenylphenanthrenylamine group, N-biphenylphenanthrenylamine group, N-phenylfluorenylamine group, N-phenylterphenylamine group, N-phenanthrenylfluorenylamine group, N-biphenylfluorenylamine group, and the like, but is not limited thereto.
  • the N-alkylarylamine group refers to an amine group in which an alkyl group and an aryl group are substituted with N of the amine group.
  • the N-arylheteroarylamine group refers to an amine group in which an aryl group and a heteroaryl group are substituted with N of the amine group.
  • the N-alkylheteroarylamine group refers to an amine group in which an alkyl group and a heteroaryl group are substituted with N of the amine group.
  • the alkyl group in the alkylamine group, the N-arylalkylamine group, and the N-alkylheteroarylamine group is the same as the example of the alkyl group described above.
  • L is a direct bond; a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; or a substituted or unsubstituted C 2 to C 30 divalent heterocyclic group.
  • L is a direct bond; a substituted or unsubstituted monocyclic arylene group having 6 to 30 carbon atoms; a substituted or unsubstituted polycyclic arylene group having 10 to 30 carbon atoms; or a substituted or unsubstituted C 2 to C 30 divalent heterocyclic group.
  • L is a direct bond; a substituted or unsubstituted monocyclic arylene group having 6 to 30 carbon atoms; a substituted or unsubstituted polycyclic arylene group having 10 to 30 carbon atoms; or a substituted or unsubstituted divalent N-containing heterocyclic group having 2 to 30 carbon atoms.
  • L is a direct bond; a substituted or unsubstituted phenylene group; a substituted or unsubstituted biphenylene group; a substituted or unsubstituted naphthylene group; or a substituted or unsubstituted divalent pyridine group.
  • L is a direct bond; an arylene group unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a cyano group, an alkyl group, and an aryl group; or direct bonding; It is a divalent heterocyclic group unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a cyano group, an alkyl group and an aryl group.
  • L is a direct bond; an arylene group having 6 to 30 carbon atoms that is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a cyano group, an alkyl group and an aryl group; or a divalent heterocyclic group having 2 to 30 carbon atoms which is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a cyano group, an alkyl group and an aryl group.
  • L is a direct bond; a phenylene group unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a cyano group, an alkyl group and an aryl group; a biphenylene group unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a cyano group, an alkyl group and an aryl group; a naphthylene group unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a cyano group, an alkyl group and an aryl group; or a divalent pyridine group unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a cyano group, an alkyl group, and an aryl group.
  • L is a direct bond; an arylene group unsubstituted or substituted with deuterium, a cyano group, an alkyl group, or an aryl group; It is a divalent heterocyclic group unsubstituted or substituted with deuterium, a cyano group, an alkyl group, or an aryl group.
  • L is a direct bond; a phenylene group unsubstituted or substituted with deuterium, a cyano group, an alkyl group, or an aryl group; a biphenylene group unsubstituted or substituted with deuterium, a cyano group, an alkyl group, or an aryl group; a naphthylene group unsubstituted or substituted with deuterium, a cyano group, an alkyl group, or an aryl group; or a divalent pyridine group unsubstituted or substituted with deuterium, a cyano group, an alkyl group, or an aryl group.
  • L is a direct bond; a phenylene group unsubstituted or substituted with a cyano group or an alkyl group; a biphenylene group unsubstituted or substituted with a cyano group or an alkyl group; a naphthylene group unsubstituted or substituted with a cyano group or an alkyl group; or a divalent pyridine group unsubstituted or substituted with a cyano group or an alkyl group.
  • L is a direct bond; phenylene group; a biphenylene group unsubstituted or substituted with a cyano group; naphthylene group; or a divalent pyridine group.
  • R1 and R2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.
  • R1 and R2 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic aryl group having 6 to 30 carbon atoms; a substituted or unsubstituted polycyclic aryl group having 10 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.
  • R1 and R2 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic aryl group having 6 to 30 carbon atoms; a substituted or unsubstituted polycyclic aryl group having 10 to 30 carbon atoms; or a substituted or unsubstituted C 2 to C 30 N-containing heterocyclic group.
  • R1 and R2 are the same as or different from each other, and each independently a monocyclic aryl group having 6 to 30 carbon atoms; a polycyclic aryl group having 10 to 30 carbon atoms; or an N-containing heterocyclic group having 2 to 30 carbon atoms.
  • R1 and R2 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group; a substituted or unsubstituted naphthyl group; Or a substituted or unsubstituted pyridine group.
  • R1 and R2 are the same as or different from each other, and each independently a phenyl group; naphthyl group; or a pyridine group.
  • Ar1 is any one of the following structures.
  • c is an integer of 1 to 5, and when c is 2 or more, 2 or more G15 are the same as or different from each other,
  • d is an integer of 1 to 4, and when d is 2 or more, 2 or more G16 are the same as or different from each other,
  • X1 to X4 are the same as or different from each other, and each independently represents N or CR10, provided that at least two of X1 to X4 are N;
  • R10 and G1 to G16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • Ar1 is any one of the following structures.
  • two of X1 to X4 are N, the other two are CR10, and R10 is hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • two of X1 to X4 are N, the other two are CR10, and R10 is hydrogen.
  • X2 and X3 are N
  • X1 and X4 are CR10
  • R10 is hydrogen
  • heavy hydrogen a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • X2 and X3 are N
  • X1 and X4 are CR10
  • R10 is hydrogen
  • G1 to G16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  • G1 to G16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted C 1 to C 20 alkyl group; a substituted or unsubstituted C6-C30 aryl group; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.
  • G1 to G16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted aryl group.
  • G1 to G16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or a substituted or unsubstituted C6-C30 aryl group.
  • G1 to G16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or an aryl group unsubstituted or substituted with deuterium, a cyano group, an alkyl group, an aryl group, or a heterocyclic group.
  • G1 to G16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; a substituted or unsubstituted naphthyl group; a substituted or unsubstituted fluoranthene group; a substituted or unsubstituted dibenzothiophene group; Or a substituted or unsubstituted dibenzofuran group.
  • G1 to G16 are the same as or different from each other, and each independently hydrogen; or a substituted or unsubstituted phenyl group.
  • G1 to G16 are the same as or different from each other, and each independently hydrogen; or a phenyl group unsubstituted or substituted with a cyano group or a pyridine group.
  • b is an integer of 1 to 3.
  • b is 1.
  • Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-4.
  • Chemical Formula 1 is represented by Chemical Formula 1-1.
  • Chemical Formula 1 is represented by Chemical Formula 1-2.
  • Chemical Formula 1 is represented by Chemical Formula 1-3.
  • Chemical Formula 1 is represented by Chemical Formula 1-4.
  • Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-5 to 1-7.
  • R1 to R6, L, a, b, and Ar1 are the same as defined in Formula 1 above.
  • Chemical Formula 1 is represented by Chemical Formula 1-5.
  • Chemical Formula 1 is represented by Chemical Formula 1-6.
  • Chemical Formula 1 is represented by Chemical Formula 1-7.
  • the heterocyclic compound of Formula 1 has any one of the following structures.
  • the core structure of Chemical Formula 1 according to an exemplary embodiment of the present specification may be prepared as shown in the following reaction scheme, the substituents may be combined by methods known in the art, and the type, position or number of the substituents may be determined in the art. It can be changed according to the known technique.
  • A is Cl or Br.
  • An exemplary embodiment of the present specification includes a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one organic material layer of the organic material layer provides an organic light-emitting device including the above-described heterocyclic compound.
  • the organic light emitting device of the present specification is prepared by manufacturing methods and materials known in the art, except that at least one layer of the organic material layer contains the heterocyclic compound of the present specification, that is, the heterocyclic compound represented by Formula 1 above. can be manufactured.
  • the organic light emitting device of the present specification may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate.
  • a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation
  • a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to It can be manufactured by forming a first electrode, forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and then depositing a material that can be used as a second electrode thereon.
  • an organic light emitting device may be manufactured by sequentially depositing the second electrode material, the organic material layer, and the first electrode material on the substrate.
  • the heterocyclic compound represented by Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device.
  • the solution application method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.
  • the organic material layers may be formed of the same material or different materials.
  • the organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a layer that simultaneously injects and transports holes, an electron suppression layer, a light emitting layer and an electron transport layer, an electron injection layer, a layer that simultaneously injects and transports electrons, etc.
  • the present invention is not limited thereto and may have a single-layer structure.
  • the organic layer is formed using a variety of polymer materials in a smaller number by a solvent process rather than a vapor deposition method, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer method. It can be made in layers.
  • the organic material layer includes an electron injection layer, an electron transport layer, or a layer that simultaneously injects and transports electrons, and the electron injection layer, the electron transport layer, or a layer that simultaneously injects and transports electrons and the heterocyclic compound.
  • the organic material layer includes a hole blocking layer, and the hole blocking layer includes the heterocyclic compound.
  • the organic material layer may further include one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.
  • the first electrode is an anode
  • the second electrode is a cathode
  • the first electrode is a cathode
  • the second electrode is an anode
  • the structure of the organic light emitting diode of the present specification may have the structure shown in FIGS. 1 to 4 , but is not limited thereto.
  • 1 illustrates a structure of an organic light emitting diode 10 in which a first electrode 2 , a light emitting layer 3 , and a second electrode 4 are sequentially stacked on a substrate 1 .
  • 1 is an exemplary structure of an organic light emitting device according to an exemplary embodiment of the present specification, and may further include another organic material layer.
  • 2 shows a first electrode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron transport layer 7, an electron injection layer 8 and a second electrode ( 4)
  • the structure of the organic light emitting device stacked in this order is exemplified. 2 is an exemplary structure according to an embodiment of the present specification, and may further include another organic material layer.
  • 3 shows a first electrode 2, a hole injection layer 5, a first hole transport layer 6-1, a second hole transport layer 6-2, a light emitting layer 3, an electron injection and
  • the structure of the organic light emitting device in which the transport layer 9 and the second electrode 4 are sequentially stacked is illustrated.
  • 3 is an exemplary structure according to an embodiment of the present specification, and may further include another organic material layer.
  • 4 shows a first electrode 2, a hole injection layer 5, a first hole transport layer 6-1, a second hole transport layer 6-2, a light emitting layer 3, and a hole blocking layer on the substrate 1 (10).
  • the structure of the organic light emitting device in which the electron injection and transport layer 9 and the second electrode 4 are sequentially stacked is illustrated. 4 is an exemplary structure according to an embodiment of the present specification, and may further include another organic material layer.
  • the organic light emitting device may have, for example, the following stacked structure in addition to the structure specified in the drawings, but is not limited thereto.
  • the hole transport layer may have a multilayer structure.
  • it may be composed of a first hole transport layer and a second hole transport layer comprising different materials.
  • the anode is an electrode for injecting holes, and as the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer.
  • the anode material that can be used in the present invention 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 Tin Oxide), and indium zinc oxide (IZO, Indium Zinc Oxide); combinations of metals and oxides such as ZnO:Al or SnO 2 :Sb; and conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto. .
  • the cathode is an electrode for injecting electrons
  • the cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer.
  • the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and a multi-layered material such as LiF/Al or LiO2/Al, but is not limited thereto.
  • the hole injection layer is a layer that facilitates injection of holes from the anode to the light emitting layer.
  • the hole injection material holes can be well injected from the anode at a low voltage, and the highest occupied (HOMO) of the hole injection material is The molecular orbital) is preferably between the work function of the positive electrode material and the HOMO of the surrounding organic material layer.
  • the hole injection material include metal porphyrine, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material.
  • Organic materials carbazole-based organic materials, fluorene-based organic materials, anthraquinone, polyaniline and polythiophene-based conductive polymers, etc., but are not limited thereto.
  • a compound including a substituted or unsubstituted carbazole and a substituted or unsubstituted fluorene may be used, but is not limited thereto.
  • the hole injection layer may have a thickness of 1 nm to 150 nm.
  • the thickness of the hole injection layer is 1 nm or more, there is an advantage in that the hole injection characteristics can be prevented from being deteriorated, and when it is 150 nm or less, the thickness of the hole injection layer is too thick, so that the driving voltage is increased to improve hole movement There are advantages to avoiding this.
  • the hole transport layer may serve to facilitate hole transport.
  • the hole transport material a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer is suitable, and a material having high hole mobility is suitable.
  • the hole transport material include an arylamine-based organic material, a carbazole-based organic material, a quinoxaline-based organic material, a fluorene-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together. is not limited to Specifically, the hole transport material includes, but is not limited to, a quinoxazoline-based compound and an arylamine-based compound.
  • a hole buffer layer may be additionally provided between the hole injection layer and the hole transport layer, and a hole injection or transport material known in the art may be included.
  • An electron blocking layer may be provided between the hole transport layer and the light emitting layer.
  • the electron-blocking layer the above-described compound or a material known in the art may be used.
  • the light emitting layer may emit red, green, or blue light, and may be made of a phosphorescent material or a fluorescent material.
  • the light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable.
  • Specific examples include 8-hydroxy-quinoline aluminum complex (Alq 3 ), carbazole-based compound, dimerized styryl compound, BAlq, 10-hydroxybenzoquinoline-metal compound, benzoxazole-based compound, benz There are thiazole-based compounds, benzimidazole-based compounds, poly(p-phenylenevinylene) (PPV)-based polymers, spiro compounds, polyfluorene and rubrene, etc., but are limited to these no.
  • the light emitting layer includes a host and a dopant.
  • the host may include the above-mentioned compounds, condensed aromatic ring derivatives, heterocyclic-containing compounds, and the like.
  • condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc.
  • heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
  • phosphorescent material or a fluorescent material such as Alq 3 (tris(8-hydroxyquinolino)aluminum) may be used, but is not limited thereto.
  • a phosphor such as Ir(ppy) 3 (fac tris(2-phenylpyridine)iridium) or a fluorescent material such as Alq3 (tris(8-hydroxyquinolino)aluminum) may be used as the emission dopant.
  • the present invention is not limited thereto.
  • the light emitting layer emits blue light
  • 4,6-F 2 ppy) 2 Irpic, spiro-DPVBi, spiro-6P, distylbenzene (DSB), distrylarylene (DSA), PFO-based polymer , PPV-based, pyrene-based, arylamine-based compounds, etc. may be used, but is not limited thereto.
  • a hole blocking layer may be provided between the electron transport layer and the light emitting layer, and materials known in the art may be used for the hole blocking layer.
  • the electron transport layer may serve to facilitate the transport of electrons.
  • the electron transport material a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high electron mobility is suitable. Specific examples include, but are not limited to, an Al complex of 8-hydroxyquinoline , a complex including Alq 3 , an organic radical compound, an anthracene-based compound, an imidazole-based compound, and a hydroxyflavone-metal complex.
  • the electron transport layer may have a thickness of 1 nm to 50 nm.
  • the thickness of the electron transport layer is 1 nm or more, there is an advantage in that the electron transport characteristics can be prevented from being deteriorated, and if it is 50 nm or less, the thickness of the electron transport layer is too thick to prevent an increase in the driving voltage to improve the movement of electrons.
  • the electron injection layer may serve to facilitate electron injection.
  • the electron injection material has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, prevents the movement of excitons generated in the light emitting layer to the hole injection layer, and , a compound having excellent thin film forming ability is preferable.
  • fluorenone anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, anthracene, imidazole and their derivatives; metal complex compounds; nitrogen-containing 5-membered ring derivatives; and lithium quinolate (LiQ), but is not limited thereto.
  • the organic material layer including the heterocyclic compound of Formula 1 is an electron injection layer, an electron transport layer, or a layer that simultaneously injects and transports electrons, and the electron injection layer, the electron transport layer or the electron injection and The layer that simultaneously transports electrons further includes a metal complex.
  • examples of the metal complex include , but are not limited to, Al complex of 8-hydroxyquinoline (Alq 3 ), LiQ, and a metal complex compound.
  • the metal complex compound examples include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium,
  • the present invention is not limited thereto.
  • the heterocyclic compound of Formula 1 and the metal complex in the electron injection layer, the electron transport layer, or the layer that simultaneously injects and transports electrons may be included in a mass ratio of 0.5:1.5 to 1.5:0.5. .
  • the hole blocking layer is a layer that blocks the holes from reaching the cathode, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP and aluminum complexes, but is not limited thereto.
  • An exemplary embodiment of the present specification is a compound represented by Formula 1; And it provides a composition comprising a metal complex.
  • metal complex included in the composition is the same as described above in the electron injection layer, the electron transport layer, or the layer that simultaneously injects and transports electrons.
  • the heterocyclic compound of Formula 1 and the metal complex in the composition may be included in a mass ratio of 0.5:1.5 to 1.5:0.5.
  • the organic light emitting device according to the present invention may be a top emission type, a back emission type, or a double side emission type depending on the material used.
  • E1-A (20 g, 43.4 mmol) and E1-B (10.5 g, 43.4 mmol) were placed in 400 mL of tetrahydrofuran, stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.3 mmol) was dissolved in 18 mL of water, and after stirring sufficiently, tetrakistriphenyl-phosphinopalladium (1.5 g, 1.3 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • Compound E2 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
  • Compound E3 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
  • Compound E4 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
  • Compound E5 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
  • Compound E6 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
  • Compound E7 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
  • Compound E8 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
  • Compound E9 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
  • Compound E10 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
  • Compound E11 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
  • Compound E12 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
  • Compound E13 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
  • Compound E14 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
  • Compound E15 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
  • a glass substrate coated with indium tin oxide (ITO) to a thickness of 1000 ⁇ was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves.
  • ITO indium tin oxide
  • a product manufactured by Fischer Co. was used as the detergent
  • distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water.
  • ultrasonic washing was performed for 10 minutes by repeating twice with distilled water.
  • ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, and after drying, it was transported to a plasma cleaner.
  • the substrate was transported to a vacuum evaporator.
  • the following HI-A compound was thermally vacuum deposited to a thickness of 600 ⁇ to form a hole injection layer.
  • a first hole transport layer and a second hole transport layer were formed by sequentially vacuum-depositing 50 ⁇ of the HAT compound and 60 ⁇ of the HT-A compound on the hole injection layer.
  • the following BH compound and BD compound were vacuum-deposited in a weight ratio of 25:1 to a thickness of 20 nm on the second hole transport layer to form a light emitting layer.
  • the compound E1 prepared in Preparation Example 1-1 and the following LiQ compound were vacuum deposited in a weight ratio of 1:1 to form an electron injection and transport layer to a thickness of 350 ⁇ .
  • a cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 10 ⁇ and aluminum to a thickness of 1000 ⁇ on the electron injection and transport layer.
  • LiF lithium fluoride
  • the deposition rate of the organic material was maintained at 0.4 ⁇ /sec to 0.9 ⁇ /sec
  • the deposition rate of lithium fluoride of the negative electrode was maintained at 0.3 ⁇ /sec
  • the deposition rate of aluminum was maintained at 2 ⁇ /sec
  • the vacuum degree during deposition was By maintaining 1 ⁇ 10 -7 torr to 5 ⁇ 10 -5 torr, an organic light emitting device was manufactured.
  • Example 1-2 to 1-15 Example 1-2 to 1-15.
  • An organic light emitting diode was manufactured in the same manner as in Example 1-1, except that compounds E2 to E15 of Table 1 were used instead of compound E1 of Example 1-1.
  • An organic light emitting diode was manufactured in the same manner as in Example 1-1, except that compounds ET-A to ET-M shown in Table 1 were used instead of Compound E1 of Example 1-1.
  • the compound represented by Formula 1 according to the present specification may be used in an organic material layer that simultaneously injects and transports electrons of an organic light emitting device.
  • a glass substrate coated with indium tin oxide (ITO) to a thickness of 1000 ⁇ was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves.
  • ITO indium tin oxide
  • a product manufactured by Fischer Co. was used as the detergent
  • distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water.
  • ultrasonic washing was performed for 10 minutes by repeating twice with distilled water.
  • ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, and after drying, it was transported to a plasma cleaner.
  • the substrate was transported to a vacuum evaporator.
  • the following HI-A compound was thermally vacuum deposited to a thickness of 600 ⁇ to form a hole injection layer.
  • a first hole transport layer and a second hole transport layer were formed by sequentially vacuum-depositing 50 ⁇ of the HAT compound and 60 ⁇ of the HT-A compound on the hole injection layer.
  • the following BH compound and BD compound were vacuum-deposited at a weight ratio of 25:1 to a thickness of 20 nm on the second hole transport layer to form a light emitting layer.
  • the compound E1 prepared in Preparation Example 1-1 was vacuum deposited to a thickness of 50 ⁇ to form a hole blocking layer, and ET-N and the following LiQ compound were vacuum deposited in a weight ratio of 1:1 to a thickness of 300 ⁇ .
  • An electron injection and transport layer was formed.
  • a cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 10 ⁇ and aluminum to a thickness of 1000 ⁇ on the electron injection and transport layer.
  • LiF lithium fluoride
  • the deposition rate of the organic material was maintained at 0.4 ⁇ /sec to 0.9 ⁇ /sec
  • the deposition rate of lithium fluoride of the negative electrode was maintained at 0.3 ⁇ /sec
  • the deposition rate of aluminum was maintained at 2 ⁇ /sec
  • the vacuum degree during deposition was By maintaining 1 ⁇ 10 -7 torr to 5 ⁇ 10 -5 torr, an organic light emitting device was manufactured.
  • An organic light emitting device was prepared in the same manner as in Example 2-1, except that compounds E2 to E8, E10 to E12, E14 and E15 described in Table 2 below were used instead of compound E1 of Example 2-1. prepared.
  • Example 2-1 The same method as in Example 2-1, except that compounds ET-A to ET-H and ET-J to ET-L described in Table 2 below were used instead of Compound E1 in Example 2-1 to manufacture an organic light emitting device.
  • Example 2-1 E1 4.35 5.09 (0.140, 0.092) 126
  • Example 2-2 E2 4.44 4.99 (0.140, 0.093) 138
  • Example 2-3 E3 4.26 5.25 (0.140, 0.093) 114
  • Example 2-4 E4 4.39 5.09 (0.141, 0.092) 128
  • Example 2-5 E5 4.26 5.22 (0.140, 0.092)
  • Example 2-6 E6 4.48 4.89 (0.140, 0.093)
  • Example 2-7 E7 4.31 5.12 (0.140, 0.093) 122
  • Examples 2-8 E8 4.40 5.04 (0.141, 0.092) 146
  • Examples 2-9 E10 4.31 5.19 (0.140, 0.093) 121
  • Example 2-10 E11 4.14 5.17 (0.140, 0.093) 117
  • the compound represented by Chemical Formula 1 according to the present specification may be used in the organic material layer for blocking holes of the organic light emitting device.
  • the organic light emitting device to which the heterocyclic compound of Formula 1 according to the present specification is applied is a compound in which both sides of the xanthene group include a substituent It was confirmed that it showed significantly superior characteristics in terms of efficiency and lifespan compared to organic light emitting devices to which .

Abstract

The present specification relates to a heterocyclic compound and an organic light-emitting device comprising same.

Description

헤테로고리 화합물 및 이를 포함하는 유기 발광 소자Heterocyclic compound and organic light emitting device comprising same
본 출원은 본 출원은 2020년 6월 26일에 한국특허청에 제출된 한국 특허 출원 제10-2020-0078172호의 출원일의 이익을 주장하며, 그 내용 전부는 본 명세서에 포함된다.This application claims the benefit of the filing date of Korean Patent Application No. 10-2020-0078172 submitted to the Korean Intellectual Property Office on June 26, 2020, the entire contents of which are incorporated herein by reference.
본 명세서는 헤테로고리 화합물 및 이를 포함하는 유기 발광 소자에 관한 것이다.The present specification relates to a heterocyclic compound and an organic light emitting device including the same.
유기 발광 소자는 2개의 전극 사이에 유기박막을 배치시킨 구조를 가지고 있다. 이와 같은 구조의 유기 발광 소자에 전압이 인가되면, 2개의 전극으로부터 주입된 전자와 전공이 유기박막에서 결합하여 쌍을 이룬 후 소멸하면서 빛을 발하게 된다. 상기 유기박막은 필요에 따라 단층 또는 다층으로 구성될 수 있다.The organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to the organic light emitting device having such a structure, electrons and holes injected from the two electrodes combine in the organic thin film to form a pair, and then disappear and emit light. The organic thin film may be composed of a single layer or multiple layers, if necessary.
유기 발광 소자에서 사용되는 물질로는 순수 유기 물질 또는 유기 물질과 금속이 착물을 이루는 착화합물이 대부분을 차지하고 있으며, 용도에 따라 정공주입 물질, 정공수송 물질, 발광 물질, 전자수송 물질, 전자주입 물질 등으로 구분될 수 있다. 여기서, 정공주입 물질이나 정공수송 물질로는 p-타입의 성질을 가지는 유기물질, 즉 쉽게 산화가 되고 산화시에 전기화학적으로 안정한 상태를 가지는 유기물이 주로 사용되고 있다. 한편, 전자주입 물질이나 전자수송 물질로는 n-타입 성질을 가지는 유기 물질, 즉 쉽게 환원이 되고 환원시에 전기화학적으로 안정한 상태를 가지는 유기물이 주로 사용되고 있다. 발광층 물질로는 p-타입 성질과 n-타입 성질을 동시에 가진 물질, 즉 산화와 환원 상태에서 모두 안정한 형태를 갖는 물질이 바람직하며, 정공 및 전자가 발광층에서 재결합하여 생성되는 엑시톤(exciton)이 형성되었을 때 이를 빛으로 전환하는 발광 효율이 높은 물질이 바람직하다.As materials used in organic light emitting devices, pure organic materials or complex compounds in which organic materials and metals are complexed account for most, and depending on the use, hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials, etc. can be divided into Here, as the hole injection material or the hole transport material, an organic material having a p-type property, that is, an organic material that is easily oxidized and has an electrochemically stable state during oxidation is mainly used. On the other hand, as an electron injection material or an electron transport material, an organic material having an n-type property, that is, an organic material that is easily reduced and has an electrochemically stable state during reduction is mainly used. As the light emitting layer material, a material having both p-type and n-type properties, that is, a material having a stable form in both oxidation and reduction states, is preferable, and excitons generated by recombination of holes and electrons in the light emitting layer are formed. A material with high luminous efficiency that converts it into light when it is formed is preferable.
유기 발광 소자의 성능, 수명 또는 효율을 향상시키기 위하여, 유기박막의 재료의 개발이 지속적으로 요구되고 있다.In order to improve the performance, lifespan or efficiency of an organic light emitting device, the development of a material for an organic thin film is continuously required.
본 명세서는 헤테로고리 화합물 및 이를 포함하는 유기 발광 소자를 제공한다.The present specification provides a heterocyclic compound and an organic light emitting device including the same.
본 명세서의 일 실시상태는 하기 화학식 1로 표시되는 헤테로고리 화합물을 제공한다.An exemplary embodiment of the present specification provides a heterocyclic compound represented by the following formula (1).
[화학식 1][Formula 1]
Figure PCTKR2021007746-appb-img-000001
Figure PCTKR2021007746-appb-img-000001
상기 화학식 1에 있어서,In Formula 1,
Z는 O 또는 S이고,Z is O or S;
R1 및 R2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이며,R1 and R2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
R3 내지 R6는 각각 독립적으로 수소이거나, 서로 결합하여 탄화수소고리를 형성하고,R3 to R6 are each independently hydrogen, or combine with each other to form a hydrocarbon ring,
L은 직접결합; 치환 또는 비치환된 아릴렌기; 또는 치환 또는 비치환된 2가의 헤테로고리기이며,L is a direct bond; a substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,
a는 1 내지 3의 정수이고, a가 2 이상일 경우 2 이상의 L은 서로 같거나 상이하며,a is an integer of 1 to 3, and when a is 2 or more, L of 2 or more are the same as or different from each other,
b는 1 내지 4의 정수이고, b가 2 이상일 경우 괄호 안의 구조는 서로 같거나 상이하며,b is an integer of 1 to 4, and when b is 2 or more, the structures in parentheses are the same as or different from each other,
Ar1은 하기로 구성되는 군으로부터 선택된 어느 하나이고,Ar1 is any one selected from the group consisting of
Figure PCTKR2021007746-appb-img-000002
Figure PCTKR2021007746-appb-img-000002
상기 구조에 있어서,In the structure,
Figure PCTKR2021007746-appb-img-000003
는 L에 연결되는 부분이고,
Figure PCTKR2021007746-appb-img-000003
is a part connected to L,
c는 1 내지 5의 정수이고, c가 2 이상일 경우 2 이상의 G15는 서로 같거나 상이하며,c is an integer of 1 to 5, and when c is 2 or more, 2 or more G15 are the same as or different from each other,
d는 1 내지 4의 정수이고, d가 2 이상일 경우 2 이상의 G16은 서로 같거나 상이하며,d is an integer of 1 to 4, and when d is 2 or more, 2 or more G16 are the same as or different from each other,
X1 내지 X4는 서로 같거나 상이하고, 각각 독립적으로 N 또는 CR10이고, 단 X1 내지 X4 중 2 이상이 N이며,X1 to X4 are the same as or different from each other, and each independently represents N or CR10, provided that at least two of X1 to X4 are N;
R10 및 G1 내지 G16은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다.R10 and G1 to G16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 또 하나의 실시상태는 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 상기 헤테로고리 화합물을 포함하는 것인 유기 발광 소자를 제공한다.Another embodiment of the present specification is a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the heterocyclic compound.
본 명세서의 일 실시상태에 따른 헤테로고리 화합물은 유기 발광 소자의 유기물층의 재료로서 사용될 수 있고, 이를 사용함으로써 유기 발광 소자에서 효율의 향상, 낮은 구동전압 및/또는 수명 특성의 향상이 가능하다.The heterocyclic compound according to an exemplary embodiment of the present specification may be used as a material for an organic material layer of an organic light emitting device, and by using the same, it is possible to improve efficiency, low driving voltage and/or lifespan characteristics in an organic light emitting device.
도 1 내지 도 4는 본 명세서의 일 실시상태에 따른 유기 발광 소자를 도시한 것이다. 1 to 4 illustrate an organic light emitting diode according to an exemplary embodiment of the present specification.
1: 기판1: Substrate
2: 제1 전극2: first electrode
3: 발광층3: light emitting layer
4: 제2 전극4: second electrode
5: 정공주입층5: hole injection layer
6: 정공수송층6: hole transport layer
6-1: 제1 정공수송층6-1: first hole transport layer
6-2: 제2 정공수송층6-2: second hole transport layer
7: 전자수송층7: electron transport layer
8: 전자주입층8: electron injection layer
9: 전자 주입 및 수송층9: Electron injection and transport layer
10: 정공차단층10: hole blocking layer
이하 본 명세서에 대하여 더욱 상세히 설명한다. Hereinafter, the present specification will be described in more detail.
본 명세서는 하기 화학식 1로 표시되는 헤테로고리 화합물을 제공한다. The present specification provides a heterocyclic compound represented by the following formula (1).
[화학식 1][Formula 1]
Figure PCTKR2021007746-appb-img-000004
Figure PCTKR2021007746-appb-img-000004
상기 화학식 1에 있어서,In Formula 1,
Z는 O 또는 S이고,Z is O or S;
R1 및 R2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이며,R1 and R2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
R3 내지 R6는 각각 독립적으로 수소이거나, 서로 결합하여 탄화수소고리를 형성하고,R3 to R6 are each independently hydrogen, or combine with each other to form a hydrocarbon ring,
L은 직접결합; 치환 또는 비치환된 아릴렌기; 또는 치환 또는 비치환된 2가의 헤테로고리기이며,L is a direct bond; a substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,
a는 1 내지 3의 정수이고, a가 2 이상일 경우 2 이상의 L은 서로 같거나 상이하며,a is an integer of 1 to 3, and when a is 2 or more, L of 2 or more are the same as or different from each other,
b는 1 내지 4의 정수이고, b가 2 이상일 경우 괄호 안의 구조는 서로 같거나 상이하며,b is an integer of 1 to 4, and when b is 2 or more, the structures in parentheses are the same as or different from each other,
Ar1은 하기로 구성되는 군으로부터 선택된 어느 하나이고,Ar1 is any one selected from the group consisting of
Figure PCTKR2021007746-appb-img-000005
Figure PCTKR2021007746-appb-img-000005
상기 구조에 있어서,In the structure,
Figure PCTKR2021007746-appb-img-000006
는 L에 연결되는 부분이고,
Figure PCTKR2021007746-appb-img-000006
is a part connected to L,
c는 1 내지 5의 정수이고, c가 2 이상일 경우 2 이상의 G15는 서로 같거나 상이하며,c is an integer of 1 to 5, and when c is 2 or more, 2 or more G15 are the same as or different from each other,
d는 1 내지 4의 정수이고, d가 2 이상일 경우 2 이상의 G16은 서로 같거나 상이하며,d is an integer of 1 to 4, and when d is 2 or more, 2 or more G16 are the same as or different from each other,
X1 내지 X4는 서로 같거나 상이하고, 각각 독립적으로 N 또는 CR10이고, 단 X1 내지 X4 중 2 이상이 N이며,X1 to X4 are the same as or different from each other, and each independently represents N or CR10, provided that at least two of X1 to X4 are N;
R10 및 G1 내지 G16은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다.R10 and G1 to G16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 발명의 화학식 1로 표시되는 화합물은 Z가 O 또는 S인 잔텐기, 싸이오잔텐기, 벤조잔텐기 또는 벤조싸이오잔텐기에서 한쪽만 치환기를 포함함으로써 분극화가 이루어진다. 이에 따라 쌍극자 모멘트가 향상되고, 수명이 향상되는 효과를 나타낸다. The compound represented by Formula 1 of the present invention is polarized by including only one substituent in the xanthene group, thioxanthene group, benzoxanthene group, or benzothioxanthene group in which Z is O or S. As a result, the dipole moment is improved and the lifespan is improved.
또한, 본 발명의 화학식 1로 표시되는 화합물은 R1 및 R2로 다환의 아릴기; 또는 헤테로고리기를 포함하여 분극화를 향상시킨다. 또한, 상기 화합물은 잔텐기의 한쪽에 Ar1을 치환하여 전자이동 특성을 향상시키며, 이에 따라 유기 발광 소자의 효율이 향상되는 효과를 나타낸다.In addition, the compound represented by Formula 1 of the present invention includes a polycyclic aryl group as R1 and R2; or a heterocyclic group to enhance polarization. In addition, the compound exhibits the effect of improving the electron transfer characteristics by substituting Ar1 on one side of the xanthene group, thereby improving the efficiency of the organic light emitting device.
본 명세서에 있어서, 어떤 부분이 어떤 구성요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다.In the present specification, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.
본 명세서에 있어서, 어떤 부재가 다른 부재 "상에" 위치하고 있다고 할 때, 이는 어떤 부재가 다른 부재에 접해 있는 경우뿐 아니라 두 부재 사이에 또 다른 부재가 존재하는 경우도 포함한다.In this specification, when a member is said to be located "on" another member, this includes not only a case in which a member is in contact with another member but also a case in which another member exists between the two members.
본 명세서에 있어서 치환기의 예시들은 아래에서 설명하나, 이에 한정되는 것은 아니다.Examples of substituents in the present specification are described below, but are not limited thereto.
상기 "치환"이라는 용어는 화합물의 탄소 원자에 결합된 수소 원자가 다른 치환기로 바뀌는 것을 의미하며, 치환되는 위치는 수소 원자가 치환되는 위치 즉, 치환기가 치환 가능한 위치라면 한정하지 않으며, 2 이상 치환되는 경우, 2 이상의 치환기는 서로 동일하거나 상이할 수 있다.The term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, a position where the substituent is substitutable, is substituted. , two or more substituents may be the same as or different from each other.
본 명세서에서 "치환 또는 비치환된" 이라는 용어는 중수소; 할로겐기; 시아노기(-CN); 에스테르기; 이미드기; 아민기; 알콕시기; 알킬기; 시클로알킬기; 아릴기; 및 헤테로고리기로 이루어진 군에서 선택된 1 또는 2 이상의 치환기로 치환되었거나 상기 예시된 치환기 중 2 이상의 치환기가 연결된 치환기로 치환되거나, 또는 어떠한 치환기도 갖지 않는 것을 의미한다. 예컨대, "2 이상의 치환기가 연결된 치환기"는 바이페닐기일 수 있다. 즉, 바이페닐기는 아릴기일 수도 있고, 2개의 페닐기가 연결된 치환기로 해석될 수 도 있다.As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; cyano group (-CN); ester group; imid; amine group; alkoxy group; an alkyl group; cycloalkyl group; aryl group; And it means that it is substituted with one or two or more substituents selected from the group consisting of a heterocyclic group, is substituted with a substituent to which two or more of the above-exemplified substituents are connected, or does not have any substituents. For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected.
본 명세서에 있어서, 상기 알킬기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나 1 내지 30인 것이 바람직하다. 구체적인 예로는 메틸, 에틸, 프로필, n-프로필, 이소프로필, 부틸, n-부틸, 이소부틸, tert-부틸, sec-부틸, 1-메틸-부틸, 1-에틸-부틸, 펜틸, n-펜틸, 이소펜틸, 네오펜틸, tert-펜틸, 헥실, n-헥실, 1-메틸펜틸, 2-메틸펜틸, 4-메틸-2-펜틸, 3,3-디메틸부틸, 2-에틸부틸, 헵틸, n-헵틸, 1-메틸헥실, 시클로펜틸메틸, 시클로헥실메틸, 옥틸, n-옥틸, tert-옥틸, 1-메틸헵틸, 2-에틸헥실, 2-프로필펜틸, n-노닐, 2,2-디메틸헵틸, 1-에틸-프로필, 1,1-디메틸-프로필, 이소헥실, 4-메틸헥실, 5-메틸헥실 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, and the like.
본 명세서에 있어서, 아릴기는 특별히 한정되지 않으나, 탄소수 6 내지 50, 예컨대 탄소수 6 내지 30인 것이 바람직하며, 상기 아릴기는 단환식 또는 다환식일 수 있다.In the present specification, the aryl group is not particularly limited, but preferably has 6 to 50 carbon atoms, such as 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.
상기 아릴기가 단환식 아릴기인 경우 탄소수는 특별히 한정되지 않으나, 탄소수 6 내지 30인 것이 바람직하다. 구체적으로 단환식 아릴기로는 페닐기, 바이페닐기, 터페닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다.When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, and the like, but is not limited thereto.
상기 아릴기가 다환식 아릴기인 경우 탄소수는 특별히 한정되지 않으나. 탄소수 10 내지 30인 것이 바람직하다. 구체적으로 다환식 아릴기로는 나프틸기, 안트라세닐기, 페난트렌기, 트리페닐렌기, 피렌기, 페날레닐기, 페릴레닐기, 크라이세닐기, 플루오레닐기, 플루오란텐기 등이 될 수 있으나, 이에 한정되는 것은 아니다. When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it is C10-30. Specifically, the polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthrene group, a triphenylene group, a pyrene group, a phenalenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, a fluoranthene group, etc. The present invention is not limited thereto.
본 명세서에 있어서, 상기 플루오레닐기는 치환될 수 있으며, 인접한 기들이 서로 결합하여 고리를 형성할 수 있다. In the present specification, the fluorenyl group may be substituted, and adjacent groups may combine with each other to form a ring.
상기 플루오레닐기가 치환되는 경우,
Figure PCTKR2021007746-appb-img-000007
,
Figure PCTKR2021007746-appb-img-000008
,
Figure PCTKR2021007746-appb-img-000009
및
Figure PCTKR2021007746-appb-img-000010
등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,
Figure PCTKR2021007746-appb-img-000007
,
Figure PCTKR2021007746-appb-img-000008
,
Figure PCTKR2021007746-appb-img-000009
and
Figure PCTKR2021007746-appb-img-000010
etc. can be However, the present invention is not limited thereto.
본 명세서에 있어서, 상기 아릴렌기는 2가인 것을 제외하고 상술한 아릴기의 설명을 인용할 수 있다.In the present specification, the description of the above-described aryl group may be cited except that the arylene group is divalent.
본 명세서에 있어서, 헤테로고리기는 탄소가 아닌 원자, 이종원자를 1 이상 포함하는 것으로서, 구체적으로 상기 이종 원자는 O, N, S 및 P 등으로 이루어진 군에서 선택되는 원자를 1 이상 포함할 수 있다. 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 50, 나아가 2 내지 30인 것이 바람직하며, 상기 헤테로고리기는 단환식 또는 다환식일 수 있다. 상기 헤테로고리기는 방향족 고리, 지방족 고리 및 이들이 축합된 고리일 수 있다. 상기 헤테로고리기의 예로는 티오펜기, 퓨라닐기, 피롤기, 이미다졸릴기, 티아졸릴기, 옥사졸릴기, 옥사디아졸릴기, 피리딜기, 바이피리딜기, 피리미딜기, 트리아지닐기, 트리아졸릴기, 아크리딜기, 피리다지닐기, 피라지닐기, 퀴놀릴기, 퀴나졸릴기, 퀴녹살릴기, 프탈라지닐기, 피리도 피리미딜기, 피리도 피라지닐기, 피라지노 피라지닐기, 이소퀴놀릴기, 인돌릴기, 카바졸릴기, 벤즈옥사졸릴기, 벤즈이미다졸릴기, 벤조티아졸릴기, 벤조카바졸릴기, 벤조티오펜기, 디벤조티오펜기, 벤조퓨라닐기, 페난쓰롤리닐기(phenanthroline), 이소옥사졸릴기, 티아디아졸릴기, 페노티아지닐기 및 디벤조퓨라닐기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the heterocyclic group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, S and P, and the like. The number of carbon atoms is not particularly limited, but preferably has 1 to 50 carbon atoms, further preferably 2 to 30 carbon atoms, and the heterocyclic group may be monocyclic or polycyclic. The heterocyclic group may be an aromatic ring, an aliphatic ring, or a ring condensed therewith. Examples of the heterocyclic group include a thiophene group, a furanyl group, a pyrrole group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazinyl group, Triazolyl group, acridyl group, pyridazinyl group, pyrazinyl group, quinolyl group, quinazolyl group, quinoxalyl group, phthalazinyl group, pyridopyrimidyl group, pyridopyrazinyl group, pyrazinopyrazinyl group group, isoquinolyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, A phenanthroline group, an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.
본 명세서에 있어서, 상기 2가의 헤테로고리기는 2가인 것을 제외하고 상술한 헤테로고리기의 설명을 인용할 수 있다.In the present specification, the description of the above-mentioned heterocyclic group may be cited except that the divalent heterocyclic group is divalent.
본 명세서에 있어서, 할로겐기는 불소, 염소, 브롬 또는 요오드가 될 수 있다.In the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.
본 명세서에 있어서, 시클로알킬기는 특별히 한정되지 않으나, 탄소수 3 내지 30인 것이 바람직하며, 구체적으로 시클로프로필, 시클로부틸, 시클로펜틸, 3-메틸시클로펜틸, 2,3-디메틸시클로펜틸, 시클로헥실, 3-메틸시클로헥실, 4-메틸시클로헥실, 2,3-디메틸시클로헥실, 3,4,5-트리메틸시클로헥실, 4-tert-부틸시클로헥실, 시클로헵틸, 시클로옥틸 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., but are limited thereto it is not
본 명세서에 있어서, 탄화수소고리는 방향족, 지방족 또는 방향족과 지방족의 축합고리일 수 있으며, 상기 시클로알킬기 또는 아릴기의 예시 중에서 선택될 수 있다.In the present specification, the hydrocarbon ring may be an aromatic, aliphatic, or a condensed ring of an aromatic and an aliphatic group, and may be selected from examples of the cycloalkyl group or the aryl group.
본 명세서에 있어서, 상기 알콕시기는 직쇄, 분지쇄 또는 고리쇄일 수 있다. 알콕시기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 30인 것이 바람직하다. 구체적으로, 메톡시, 에톡시, n-프로폭시, 이소프로폭시, n-부톡시, 이소부톡시, tert-부톡시, sec-부톡시, n-펜틸옥시, 네오펜틸옥시, 이소펜틸옥시, n-헥실옥시, 3,3-디메틸부틸옥시, 2-에틸부틸옥시, n-옥틸옥시, n-노닐옥시, n-데실옥시 등이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C30. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n -hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy and the like may be used, but is not limited thereto.
본 명세서에 있어서, 아민기는 -NH2; 알킬아민기; N-알킬아릴아민기; 아릴아민기; N-아릴헤테로아릴아민기; N-알킬헤테로아릴아민기 및 헤테로아릴아민기로 이루어진 군으로부터 선택될 수 있으며, 탄소수는 특별히 한정되지 않으나, 0 내지 30인 것이 바람직하다. 아민기의 구체적인 예로는 메틸아민기, 디메틸아민기, 에틸아민기, 디에틸아민기, 페닐아민기, 나프틸아민기, 바이페닐아민기, 안트라세닐아민기, 9-메틸-안트라세닐아민기, 디페닐아민기, N-페닐나프틸아민기, 디톨릴아민기, N-페닐톨릴아민기, 트리페닐아민기, N-페닐바이페닐아민기, N-페닐나프틸아민기, N-바이페닐나프틸아민기, N-나프틸플루오레닐아민기, N-페닐페난트레닐아민기, N-바이페닐페난트레닐아민기, N-페닐플루오레닐아민기, N-페닐터페닐아민기, N-페난트레닐플루오레닐아민기, N-바이페닐플루오레닐아민기 등이 있으나, 이에 한정되는 것은 아니다.In the present specification, the amine group is -NH 2 ; an alkylamine group; N-alkylarylamine group; arylamine group; N-aryl heteroarylamine group; It may be selected from the group consisting of an N-alkylheteroarylamine group and a heteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 0 to 30. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, and a 9-methyl-anthracenylamine group. , diphenylamine group, N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group, N-phenylnaphthylamine group, N-bi Phenylnaphthylamine group, N-naphthylfluorenylamine group, N-phenylphenanthrenylamine group, N-biphenylphenanthrenylamine group, N-phenylfluorenylamine group, N-phenylterphenylamine group, N-phenanthrenylfluorenylamine group, N-biphenylfluorenylamine group, and the like, but is not limited thereto.
본 명세서에 있어서, N-알킬아릴아민기는 아민기의 N에 알킬기 및 아릴기가 치환된 아민기를 의미한다.In the present specification, the N-alkylarylamine group refers to an amine group in which an alkyl group and an aryl group are substituted with N of the amine group.
본 명세서에 있어서, N-아릴헤테로아릴아민기는 아민기의 N에 아릴기 및 헤테로아릴기가 치환된 아민기를 의미한다.In the present specification, the N-arylheteroarylamine group refers to an amine group in which an aryl group and a heteroaryl group are substituted with N of the amine group.
본 명세서에 있어서, N-알킬헤테로아릴아민기는 아민기의 N에 알킬기 및 헤테로아릴기가 치환된 아민기를 의미한다.In the present specification, the N-alkylheteroarylamine group refers to an amine group in which an alkyl group and a heteroaryl group are substituted with N of the amine group.
본 명세서에 있어서, 알킬아민기, N-아릴알킬아민기, N-알킬헤테로아릴아민기 중의 알킬기는 전술한 알킬기의 예시와 같다. In the present specification, the alkyl group in the alkylamine group, the N-arylalkylamine group, and the N-alkylheteroarylamine group is the same as the example of the alkyl group described above.
본 명세서의 일 실시상태에 있어서, 상기 L은 직접결합; 치환 또는 비치환된 탄소수 6 내지 30의 아릴렌기; 또는 치환 또는 비치환된 탄소수 2 내지 30의 2가의 헤테로고리기이다.In one embodiment of the present specification, L is a direct bond; a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; or a substituted or unsubstituted C 2 to C 30 divalent heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 L은 직접결합; 치환 또는 비치환된 탄소수 6 내지 30의 단환의 아릴렌기; 치환 또는 비치환된 탄소수 10 내지 30의 다환의 아릴렌기; 또는 치환 또는 비치환된 탄소수 2 내지 30의 2가의 헤테로고리기이다.In one embodiment of the present specification, L is a direct bond; a substituted or unsubstituted monocyclic arylene group having 6 to 30 carbon atoms; a substituted or unsubstituted polycyclic arylene group having 10 to 30 carbon atoms; or a substituted or unsubstituted C 2 to C 30 divalent heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 L은 직접결합; 치환 또는 비치환된 탄소수 6 내지 30의 단환의 아릴렌기; 치환 또는 비치환된 탄소수 10 내지 30의 다환의 아릴렌기; 또는 치환 또는 비치환된 탄소수 2 내지 30의 2가의 N함유 헤테로고리기이다.In one embodiment of the present specification, L is a direct bond; a substituted or unsubstituted monocyclic arylene group having 6 to 30 carbon atoms; a substituted or unsubstituted polycyclic arylene group having 10 to 30 carbon atoms; or a substituted or unsubstituted divalent N-containing heterocyclic group having 2 to 30 carbon atoms.
본 명세서의 일 실시상태에 있어서, 상기 L은 직접결합; 치환 또는 비치환된 페닐렌기; 치환 또는 비치환된 비페닐렌기; 치환 또는 비치환된 나프틸렌기; 또는 치환 또는 비치환된 2가의 피리딘기이다.In one embodiment of the present specification, L is a direct bond; a substituted or unsubstituted phenylene group; a substituted or unsubstituted biphenylene group; a substituted or unsubstituted naphthylene group; or a substituted or unsubstituted divalent pyridine group.
본 명세서의 일 실시상태에 있어서, 상기 L은 직접결합; 중수소, 시아노기, 알킬기 및 아릴기로 이루어진 군에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 아릴렌기; 또는 직접결합; 중수소, 시아노기, 알킬기 및 아릴기로 이루어진 군에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 2가의 헤테로고리기이다.In one embodiment of the present specification, L is a direct bond; an arylene group unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a cyano group, an alkyl group, and an aryl group; or direct bonding; It is a divalent heterocyclic group unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a cyano group, an alkyl group and an aryl group.
본 명세서의 일 실시상태에 있어서, 상기 L은 직접결합; 중수소, 시아노기, 알킬기 및 아릴기로 이루어진 군에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 탄소수 6 내지 30의 아릴렌기; 또는 중수소, 시아노기, 알킬기 및 아릴기로 이루어진 군에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 탄소수 2 내지 30의 2가의 헤테로고리기이다.In one embodiment of the present specification, L is a direct bond; an arylene group having 6 to 30 carbon atoms that is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a cyano group, an alkyl group and an aryl group; or a divalent heterocyclic group having 2 to 30 carbon atoms which is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a cyano group, an alkyl group and an aryl group.
본 명세서의 일 실시상태에 있어서, 상기 L은 직접결합; 중수소, 시아노기, 알킬기 및 아릴기로 이루어진 군에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 페닐렌기; 중수소, 시아노기, 알킬기 및 아릴기로 이루어진 군에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 비페닐렌기; 중수소, 시아노기, 알킬기 및 아릴기로 이루어진 군에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 나프틸렌기; 또는 중수소, 시아노기, 알킬기 및 아릴기로 이루어진 군에서 선택되는 1 이상의 치환기로 치환 또는 비치환된 2가의 피리딘기이다.In one embodiment of the present specification, L is a direct bond; a phenylene group unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a cyano group, an alkyl group and an aryl group; a biphenylene group unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a cyano group, an alkyl group and an aryl group; a naphthylene group unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a cyano group, an alkyl group and an aryl group; or a divalent pyridine group unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a cyano group, an alkyl group, and an aryl group.
본 명세서의 일 실시상태에 있어서, 상기 L은 직접결합; 중수소, 시아노기, 알킬기 또는 아릴기로 치환 또는 비치환된 아릴렌기; 중수소, 시아노기, 알킬기 또는 아릴기로 치환 또는 비치환된 2가의 헤테로고리기이다.In one embodiment of the present specification, L is a direct bond; an arylene group unsubstituted or substituted with deuterium, a cyano group, an alkyl group, or an aryl group; It is a divalent heterocyclic group unsubstituted or substituted with deuterium, a cyano group, an alkyl group, or an aryl group.
본 명세서의 일 실시상태에 있어서, 상기 L은 직접결합; 중수소, 시아노기, 알킬기 또는 아릴기로 치환 또는 비치환된 페닐렌기; 중수소, 시아노기, 알킬기 또는 아릴기로 치환 또는 비치환된 비페닐렌기; 중수소, 시아노기, 알킬기 또는 아릴기로 치환 또는 비치환된 나프틸렌기; 또는 중수소, 시아노기, 알킬기 또는 아릴기로 치환 또는 비치환된 2가의 피리딘기이다.In one embodiment of the present specification, L is a direct bond; a phenylene group unsubstituted or substituted with deuterium, a cyano group, an alkyl group, or an aryl group; a biphenylene group unsubstituted or substituted with deuterium, a cyano group, an alkyl group, or an aryl group; a naphthylene group unsubstituted or substituted with deuterium, a cyano group, an alkyl group, or an aryl group; or a divalent pyridine group unsubstituted or substituted with deuterium, a cyano group, an alkyl group, or an aryl group.
본 명세서의 일 실시상태에 있어서, 상기 L은 직접결합; 시아노기 또는 알킬기로 치환 또는 비치환된 페닐렌기; 시아노기 또는 알킬기로 치환 또는 비치환된 비페닐렌기; 시아노기 또는 알킬기로 치환 또는 비치환된 나프틸렌기; 또는 시아노기 또는 알킬기로 치환 또는 비치환된 2가의 피리딘기이다.In one embodiment of the present specification, L is a direct bond; a phenylene group unsubstituted or substituted with a cyano group or an alkyl group; a biphenylene group unsubstituted or substituted with a cyano group or an alkyl group; a naphthylene group unsubstituted or substituted with a cyano group or an alkyl group; or a divalent pyridine group unsubstituted or substituted with a cyano group or an alkyl group.
본 명세서의 일 실시상태에 있어서, 상기 L은 직접결합; 페닐렌기; 시아노기로 치환 또는 비치환된 비페닐렌기; 나프틸렌기; 또는 2가의 피리딘기이다.In one embodiment of the present specification, L is a direct bond; phenylene group; a biphenylene group unsubstituted or substituted with a cyano group; naphthylene group; or a divalent pyridine group.
본 명세서의 일 실시상태에 있어서, 상기 R1 및 R2는 서로 같거나 상이하고, 각각 독립적으로 탄소수 6 내지 30의 치환 또는 비치환된 아릴기; 또는 탄소수 2 내지 30의 치환 또는 비치환된 헤테로고리기이다.In an exemplary embodiment of the present specification, R1 and R2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.
본 명세서의 일 실시상태에 있어서, 상기 R1 및 R2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 30의 단환의 아릴기; 치환 또는 비치환된 탄소수 10 내지 30의 다환의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 30의 헤테로고리기이다.In an exemplary embodiment of the present specification, R1 and R2 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic aryl group having 6 to 30 carbon atoms; a substituted or unsubstituted polycyclic aryl group having 10 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.
본 명세서의 일 실시상태에 있어서, 상기 R1 및 R2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 탄소수 6 내지 30의 단환의 아릴기; 치환 또는 비치환된 탄소수 10 내지 30의 다환의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 30의 N함유 헤테로고리기이다.In an exemplary embodiment of the present specification, R1 and R2 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic aryl group having 6 to 30 carbon atoms; a substituted or unsubstituted polycyclic aryl group having 10 to 30 carbon atoms; or a substituted or unsubstituted C 2 to C 30 N-containing heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 R1 및 R2는 서로 같거나 상이하고, 각각 독립적으로 탄소수 6 내지 30의 단환의 아릴기; 탄소수 10 내지 30의 다환의 아릴기; 또는 탄소수 2 내지 30의 N함유 헤테로고리기이다.In an exemplary embodiment of the present specification, R1 and R2 are the same as or different from each other, and each independently a monocyclic aryl group having 6 to 30 carbon atoms; a polycyclic aryl group having 10 to 30 carbon atoms; or an N-containing heterocyclic group having 2 to 30 carbon atoms.
본 명세서의 일 실시상태에 있어서, 상기 R1 및 R2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 페닐기; 치환 또는 비치환된 나프틸기; 또는 치환 또는 비치환된 피리딘기이다.In an exemplary embodiment of the present specification, R1 and R2 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group; a substituted or unsubstituted naphthyl group; Or a substituted or unsubstituted pyridine group.
본 명세서의 일 실시상태에 있어서, 상기 R1 및 R2는 서로 같거나 상이하고, 각각 독립적으로 페닐기; 나프틸기; 또는 피리딘기이다.In an exemplary embodiment of the present specification, R1 and R2 are the same as or different from each other, and each independently a phenyl group; naphthyl group; or a pyridine group.
본 명세서의 일 실시상태에 있어서, Ar1은 하기 구조 중 어느 하나이다.In an exemplary embodiment of the present specification, Ar1 is any one of the following structures.
Figure PCTKR2021007746-appb-img-000011
Figure PCTKR2021007746-appb-img-000011
상기 구조에 있어서,In the structure,
Figure PCTKR2021007746-appb-img-000012
는 L에 연결되는 부분이고,
Figure PCTKR2021007746-appb-img-000012
is a part connected to L,
c는 1 내지 5의 정수이고, c가 2 이상일 경우 2 이상의 G15는 서로 같거나 상이하며,c is an integer of 1 to 5, and when c is 2 or more, 2 or more G15 are the same as or different from each other,
d는 1 내지 4의 정수이고, d가 2 이상일 경우 2 이상의 G16은 서로 같거나 상이하며,d is an integer of 1 to 4, and when d is 2 or more, 2 or more G16 are the same as or different from each other,
X1 내지 X4는 서로 같거나 상이하고, 각각 독립적으로 N 또는 CR10이고, 단 X1 내지 X4 중 2 이상이 N이며,X1 to X4 are the same as or different from each other, and each independently represents N or CR10, provided that at least two of X1 to X4 are N;
R10 및 G1 내지 G16은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다.R10 and G1 to G16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, Ar1은 하기 구조 중 어느 하나이다.In an exemplary embodiment of the present specification, Ar1 is any one of the following structures.
Figure PCTKR2021007746-appb-img-000013
Figure PCTKR2021007746-appb-img-000013
상기 구조에 있어서, c, d, X1 내지 X4 및 G1 내지 G16은 전술한 바와 동일하다.In the above structure, c, d, X1 to X4 and G1 to G16 are the same as described above.
본 명세서의 일 실시상태에 있어서, 상기 X1 내지 X4 중 2개가 N이고, 다른 두개는 CR10이며, R10은 수소; 중수소; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다.In an exemplary embodiment of the present specification, two of X1 to X4 are N, the other two are CR10, and R10 is hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 X1 내지 X4 중 2개가 N이고, 다른 두개는 CR10이며, R10은 수소이다.In an exemplary embodiment of the present specification, two of X1 to X4 are N, the other two are CR10, and R10 is hydrogen.
본 명세서의 일 실시상태에 있어서, 상기 X2 및 X3는 N이고, X1 및 X4는 CR10이며, R10은 수소; 중수소; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다.In an exemplary embodiment of the present specification, X2 and X3 are N, X1 and X4 are CR10, R10 is hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 X2 및 X3는 N이고, X1 및 X4는 CR10이며, R10은 수소이다.In an exemplary embodiment of the present specification, X2 and X3 are N, X1 and X4 are CR10, and R10 is hydrogen.
본 명세서의 일 실시상태에 있어서, 상기 G1 내지 G16은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다.In an exemplary embodiment of the present specification, G1 to G16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 G1 내지 G16은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 탄소수 1 내지 20의 알킬기; 치환 또는 비치환된 탄소수 6 내지 30의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 30의 헤테로고리기이다.In an exemplary embodiment of the present specification, G1 to G16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted C 1 to C 20 alkyl group; a substituted or unsubstituted C6-C30 aryl group; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.
본 명세서의 일 실시상태에 있어서, 상기 G1 내지 G16은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 또는 치환 또는 비치환된 아릴기이다.In an exemplary embodiment of the present specification, G1 to G16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted aryl group.
본 명세서의 일 실시상태에 있어서, 상기 G1 내지 G16은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 또는 치환 또는 비치환된 탄소수 6 내지 30의 아릴기이다.In an exemplary embodiment of the present specification, G1 to G16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or a substituted or unsubstituted C6-C30 aryl group.
본 명세서의 일 실시상태에 있어서, 상기 G1 내지 G16은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 또는 중수소, 시아노기, 알킬기, 아릴기 또는 헤테로고리기로 치환 또는 비치환된 아릴기이다.In an exemplary embodiment of the present specification, G1 to G16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; or an aryl group unsubstituted or substituted with deuterium, a cyano group, an alkyl group, an aryl group, or a heterocyclic group.
본 명세서의 일 실시상태에 있어서, 상기 G1 내지 G16은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 페닐기; 치환 또는 비치환된 비페닐기; 치환 또는 비치환된 나프틸기; 치환 또는 비치환된 플루오란텐기; 치환 또는 비치환된 디벤조티오펜기; 또는 치환 또는 비치환된 디벤조퓨란기이다.In an exemplary embodiment of the present specification, G1 to G16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; a substituted or unsubstituted naphthyl group; a substituted or unsubstituted fluoranthene group; a substituted or unsubstituted dibenzothiophene group; Or a substituted or unsubstituted dibenzofuran group.
본 명세서의 일 실시상태에 있어서, 상기 G1 내지 G16은 서로 같거나 상이하고, 각각 독립적으로 수소; 또는 치환 또는 비치환된 페닐기이다.In an exemplary embodiment of the present specification, G1 to G16 are the same as or different from each other, and each independently hydrogen; or a substituted or unsubstituted phenyl group.
본 명세서의 일 실시상태에 있어서, 상기 G1 내지 G16은 서로 같거나 상이하고, 각각 독립적으로 수소; 또는 시아노기 또는 피리딘기로 치환 또는 비치환된 페닐기이다.In an exemplary embodiment of the present specification, G1 to G16 are the same as or different from each other, and each independently hydrogen; or a phenyl group unsubstituted or substituted with a cyano group or a pyridine group.
본 명세서의 일 실시상태에 있어서, b는 1 내지 3의 정수이다.In one embodiment of the present specification, b is an integer of 1 to 3.
본 명세서의 일 실시상태에 있어서, b는 1이다.In one embodiment of the present specification, b is 1.
본 명세서의 일 실시상태에 있어서, 상기 화학식 1은 하기 화학식 1-1 내지 1-4 중 어느 하나로 표시된다.In an exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-4.
[화학식 1-1][Formula 1-1]
Figure PCTKR2021007746-appb-img-000014
Figure PCTKR2021007746-appb-img-000014
[화학식 1-2][Formula 1-2]
Figure PCTKR2021007746-appb-img-000015
Figure PCTKR2021007746-appb-img-000015
[화학식 1-3][Formula 1-3]
Figure PCTKR2021007746-appb-img-000016
Figure PCTKR2021007746-appb-img-000016
[화학식 1-4][Formula 1-4]
Figure PCTKR2021007746-appb-img-000017
Figure PCTKR2021007746-appb-img-000017
상기 화학식 1-1 내지 1-4에 있어서,In Formulas 1-1 to 1-4,
Z, R1, R2, a, L 및 Ar1은 상기 화학식 1에서 정의한 바와 동일하다.Z, R1, R2, a, L and Ar1 are the same as defined in Formula 1 above.
본 명세서의 일 실시상태에 있어서, 상기 화학식 1은 상기 화학식 1-1로 표시된다.In the exemplary embodiment of the present specification, Chemical Formula 1 is represented by Chemical Formula 1-1.
본 명세서의 일 실시상태에 있어서, 상기 화학식 1은 상기 화학식 1-2로 표시된다.In the exemplary embodiment of the present specification, Chemical Formula 1 is represented by Chemical Formula 1-2.
본 명세서의 일 실시상태에 있어서, 상기 화학식 1은 상기 화학식 1-3으로 표시된다.In the exemplary embodiment of the present specification, Chemical Formula 1 is represented by Chemical Formula 1-3.
본 명세서의 일 실시상태에 있어서, 상기 화학식 1은 상기 화학식 1-4로 표시된다.In the exemplary embodiment of the present specification, Chemical Formula 1 is represented by Chemical Formula 1-4.
본 명세서의 일 실시상태에 있어서, 상기 화학식 1은 하기 화학식 1-5 내지 1-7 중 어느 하나로 표시된다.In the exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-5 to 1-7.
[화학식 1-5] [Formula 1-5]
Figure PCTKR2021007746-appb-img-000018
Figure PCTKR2021007746-appb-img-000018
[화학식 1-6] [Formula 1-6]
Figure PCTKR2021007746-appb-img-000019
Figure PCTKR2021007746-appb-img-000019
[화학식 1-7] [Formula 1-7]
Figure PCTKR2021007746-appb-img-000020
Figure PCTKR2021007746-appb-img-000020
상기 화학식 1-5 내지 1-7에 있어서,In Formulas 1-5 to 1-7,
Z, R1 내지 R6, L, a, b, 및 Ar1은 상기 화학식 1에서 정의한 바와 동일하다.Z, R1 to R6, L, a, b, and Ar1 are the same as defined in Formula 1 above.
본 명세서의 일 실시상태에 있어서, 상기 화학식 1은 상기 화학식 1-5로 표시된다.In the exemplary embodiment of the present specification, Chemical Formula 1 is represented by Chemical Formula 1-5.
본 명세서의 일 실시상태에 있어서, 상기 화학식 1은 상기 화학식 1-6으로 표시된다.In the exemplary embodiment of the present specification, Chemical Formula 1 is represented by Chemical Formula 1-6.
본 명세서의 일 실시상태에 있어서, 상기 화학식 1은 상기 화학식 1-7로 표시된다.In the exemplary embodiment of the present specification, Chemical Formula 1 is represented by Chemical Formula 1-7.
본 명세서의 일 실시상태에 있어서, 상기 화학식 1의 헤테로고리 화합물은 하기 구조 중 어느 하나이다.In an exemplary embodiment of the present specification, the heterocyclic compound of Formula 1 has any one of the following structures.
Figure PCTKR2021007746-appb-img-000021
Figure PCTKR2021007746-appb-img-000021
Figure PCTKR2021007746-appb-img-000022
Figure PCTKR2021007746-appb-img-000022
Figure PCTKR2021007746-appb-img-000023
Figure PCTKR2021007746-appb-img-000023
Figure PCTKR2021007746-appb-img-000024
Figure PCTKR2021007746-appb-img-000024
Figure PCTKR2021007746-appb-img-000025
Figure PCTKR2021007746-appb-img-000025
Figure PCTKR2021007746-appb-img-000026
Figure PCTKR2021007746-appb-img-000026
Figure PCTKR2021007746-appb-img-000027
Figure PCTKR2021007746-appb-img-000027
Figure PCTKR2021007746-appb-img-000028
Figure PCTKR2021007746-appb-img-000028
Figure PCTKR2021007746-appb-img-000029
Figure PCTKR2021007746-appb-img-000029
Figure PCTKR2021007746-appb-img-000030
Figure PCTKR2021007746-appb-img-000030
Figure PCTKR2021007746-appb-img-000031
Figure PCTKR2021007746-appb-img-000031
본 명세서의 일 실시상태에 따른 화학식 1의 코어구조는 하기 반응식과 같이 제조될 수 있고, 치환기는 당 기술분야에 알려져 있는 방법에 의하여 결합될 수 있으며, 치환기의 종류, 위치 또는 개수는 당 기술분야에 알려져 있는 기술에 따라 변경될 수 있다.The core structure of Chemical Formula 1 according to an exemplary embodiment of the present specification may be prepared as shown in the following reaction scheme, the substituents may be combined by methods known in the art, and the type, position or number of the substituents may be determined in the art. It can be changed according to the known technique.
<반응식><reaction formula>
Figure PCTKR2021007746-appb-img-000032
Figure PCTKR2021007746-appb-img-000032
상기 반응식에 있어서, In the above reaction formula,
Z, L, a, R1 내지 R6, Ar1 및 b는 화학식 1에서 정의한 바와 동일하고,Z, L, a, R1 to R6, Ar1 and b are the same as defined in Formula 1,
A는 Cl 또는 Br이다.A is Cl or Br.
본 명세서의 일 실시상태는 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비되는 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상이 전술한 헤테로고리 화합물을 포함하는 유기 발광 소자를 제공한다.An exemplary embodiment of the present specification includes a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one organic material layer of the organic material layer provides an organic light-emitting device including the above-described heterocyclic compound.
본 명세서의 유기 발광 소자는 유기물층 중 1층 이상이 본 명세서의 헤테로고리 화합물, 즉, 상기 화학식 1로 표시되는 헤테로고리 화합물을 포함하는 것을 제외하고는 당 기술분야에 알려져 있는 제조방법 및 재료에 의하여 제조될 수 있다.The organic light emitting device of the present specification is prepared by manufacturing methods and materials known in the art, except that at least one layer of the organic material layer contains the heterocyclic compound of the present specification, that is, the heterocyclic compound represented by Formula 1 above. can be manufactured.
예컨대, 본 명세서의 유기 발광 소자는 기판 상에 제1 전극, 유기물층 및 제2 전극을 순차적으로 적층시킴으로써 제조할 수 있다. 이 때 스퍼터링법(sputtering)이나 전자빔 증발법(e-beam evaporation)과 같은 물리 증착 방법(PVD: physical Vapor Deposition)을 이용하여, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 제1 전극을 형성하고, 그 위에 정공주입층, 정공수송층, 발광층 및 전자수송층을 포함하는 유기물층을 형성한 후, 그 위에 제2 전극으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다. 이와 같은 방법 외에도, 기판 상에 제2 전극 물질부터 유기물층, 제1 전극 물질을 차례로 증착시켜 유기 발광 소자를 만들 수 있다. 또한, 상기 화학식 1로 표시되는 헤테로고리 화합물은 유기 발광 소자의 제조시 진공 증착법 뿐만 아니라 용액 도포법에 의하여 유기물층으로 형성될 수 있다. 여기서, 용액 도포법이라 함은 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯프린팅, 스크린 프린팅, 스프레이법, 롤 코팅 등을 의미하지만, 이들만으로 한정되는 것은 아니다.For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to It can be manufactured by forming a first electrode, forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and then depositing a material that can be used as a second electrode thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing the second electrode material, the organic material layer, and the first electrode material on the substrate. In addition, the heterocyclic compound represented by Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution application method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.
상기 유기 발광 소자가 복수개의 유기물층을 포함하는 경우, 상기 유기물층은 동일한 물질 또는 다른 물질로 형성될 수 있다. When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.
상기 유기물층은 정공주입층, 정공수송층, 정공 주입과 정공 수송을 동시에 하는층, 전자억제층, 발광층 및 전자수송층, 전자주입층, 전자 주입과 전자 수송을 동시에 하는 층 등을 포함하는 다층 구조일 수도 있으나, 이에 한정되지 않고 단층 구조일 수 있다. 또한, 상기 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용매 공정(solvent process), 예컨대 스핀 코팅, 딥 코팅, 닥터 블레이딩, 스크린 프린팅, 잉크젯 프린팅 또는 열 전사법 등의 방법에 의하여 더 적은 수의 층으로 제조할 수 있다.The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a layer that simultaneously injects and transports holes, an electron suppression layer, a light emitting layer and an electron transport layer, an electron injection layer, a layer that simultaneously injects and transports electrons, etc. However, the present invention is not limited thereto and may have a single-layer structure. In addition, the organic layer is formed using a variety of polymer materials in a smaller number by a solvent process rather than a vapor deposition method, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer method. It can be made in layers.
본 명세서의 일 실시상태에 있어서, 상기 유기물층은 전자주입층, 전자수송층 또는 전자 주입과 전자 수송을 동시에 하는 층을 포함하고, 상기 전자주입층, 전자수송층 또는 전자 주입과 전자 수송을 동시에 하는 층은 상기 헤테로고리 화합물을 포함한다.In one embodiment of the present specification, the organic material layer includes an electron injection layer, an electron transport layer, or a layer that simultaneously injects and transports electrons, and the electron injection layer, the electron transport layer, or a layer that simultaneously injects and transports electrons and the heterocyclic compound.
본 명세서의 일 실시상태에 있어서, 상기 유기물층은 정공차단층을 포함하고, 상기 정공차단층은 상기 헤테로고리 화합물을 포함한다.In an exemplary embodiment of the present specification, the organic material layer includes a hole blocking layer, and the hole blocking layer includes the heterocyclic compound.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층으로 이루어진 군으로부터 선택되는 1층 이상을 더 포함할 수 있다.According to an exemplary embodiment of the present specification, the organic material layer may further include one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.
본 명세서의 일 실시상태에 있어서, 상기 제1 전극은 양극이고, 제2 전극은 음극이다.In the exemplary embodiment of the present specification, the first electrode is an anode, and the second electrode is a cathode.
또 하나의 일 실시상태에 따르면, 상기 제1 전극은 음극이고, 제2 전극은 양극이다.According to another exemplary embodiment, the first electrode is a cathode, and the second electrode is an anode.
예컨대, 본 명세서의 유기 발광 소자의 구조는 도 1 내지 도 4에 나타난 것과 같은 구조를 가질 수 있으나 이에만 한정되는 것은 아니다.For example, the structure of the organic light emitting diode of the present specification may have the structure shown in FIGS. 1 to 4 , but is not limited thereto.
도 1에는 기판(1) 위에 제1 전극(2), 발광층(3) 및 제2 전극(4)이 순차적으로 적층된 유기 발광 소자(10)의 구조가 예시 되어 있다. 상기 도 1은 본 명세서의 일 실시상태에 따른 유기 발광 소자의 예시적인 구조이며, 다른 유기물층을 더 포함할 수 있다.1 illustrates a structure of an organic light emitting diode 10 in which a first electrode 2 , a light emitting layer 3 , and a second electrode 4 are sequentially stacked on a substrate 1 . 1 is an exemplary structure of an organic light emitting device according to an exemplary embodiment of the present specification, and may further include another organic material layer.
도 2에는 기판(1) 위에 제1 전극(2), 정공주입층(5), 정공수송층(6), 발광층(3), 전자수송층(7), 전자주입층(8) 및 제2 전극(4)이 순차적으로 적층된 유기 발광 소자의 구조가 예시되어 있다. 상기 도 2는 본 명세서의 실시상태에 따른 예시적인 구조이며, 다른 유기물층을 더 포함할 수 있다.2 shows a first electrode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron transport layer 7, an electron injection layer 8 and a second electrode ( 4) The structure of the organic light emitting device stacked in this order is exemplified. 2 is an exemplary structure according to an embodiment of the present specification, and may further include another organic material layer.
도 3에는 기판(1) 위에 제1 전극(2), 정공주입층(5), 제1 정공수송층(6-1), 제2 정공수송층(6-2), 발광층(3), 전자 주입 및 수송층(9) 및 제2 전극(4)이 순차적으로 적층된 유기 발광 소자의 구조가 예시되어 있다. 상기 도 3은 본 명세서의 실시상태에 따른 예시적인 구조이며, 다른 유기물층을 더 포함할 수 있다.3 shows a first electrode 2, a hole injection layer 5, a first hole transport layer 6-1, a second hole transport layer 6-2, a light emitting layer 3, an electron injection and The structure of the organic light emitting device in which the transport layer 9 and the second electrode 4 are sequentially stacked is illustrated. 3 is an exemplary structure according to an embodiment of the present specification, and may further include another organic material layer.
도 4에는 기판(1) 위에 제1 전극(2), 정공주입층(5), 제1 정공수송층(6-1), 제2 정공수송층(6-2), 발광층(3), 정공차단층(10). 전자 주입 및 수송층(9) 및 제2 전극(4)이 순차적으로 적층된 유기 발광 소자의 구조가 예시되어 있다. 상기 도 4는 본 명세서의 실시상태에 따른 예시적인 구조이며, 다른 유기물층을 더 포함할 수 있다.4 shows a first electrode 2, a hole injection layer 5, a first hole transport layer 6-1, a second hole transport layer 6-2, a light emitting layer 3, and a hole blocking layer on the substrate 1 (10). The structure of the organic light emitting device in which the electron injection and transport layer 9 and the second electrode 4 are sequentially stacked is illustrated. 4 is an exemplary structure according to an embodiment of the present specification, and may further include another organic material layer.
구체적으로, 상기 유기 발광 소자는 상기 도면에 명시된 구조 외에 예컨대 하기와 같은 적층 구조를 가질 수 있으나, 이에만 한정되는 것은 아니다.Specifically, the organic light emitting device may have, for example, the following stacked structure in addition to the structure specified in the drawings, but is not limited thereto.
(1) 양극/정공수송층/발광층/음극(1) anode/hole transport layer/light emitting layer/cathode
(2) 양극/정공주입층/정공수송층/발광층/음극(2) anode / hole injection layer / hole transport layer / light emitting layer / cathode
(3) 양극/정공주입층/정공버퍼층/정공수송층/발광층/음극(3) anode / hole injection layer / hole buffer layer / hole transport layer / light emitting layer / cathode
(4) 양극/정공수송층/발광층/전자수송층/음극(4) anode / hole transport layer / light emitting layer / electron transport layer / cathode
(5) 양극/정공수송층/발광층/전자수송층/전자주입층/음극(5) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode
(6) 양극/정공주입층/정공수송층/발광층/전자수송층/음극(6) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode
(7) 양극/정공주입층/정공수송층/발광층/전자수송층/전자주입층/음극(7) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode
(8) 양극/정공주입층/정공버퍼층/정공수송층/발광층/전자수송층/음극(8) anode / hole injection layer / hole buffer layer / hole transport layer / light emitting layer / electron transport layer / cathode
(9) 양극/정공주입층/정공버퍼층/정공수송층/발광층/전자수송층/전자주입층 /음극(9) anode / hole injection layer / hole buffer layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode
(10) 양극/ 정공수송층/전자억제층/발광층/전자수송층/음극(10) anode / hole transport layer / electron suppression layer / light emitting layer / electron transport layer / cathode
(11) 양극/ 정공수송층/전자억제층/발광층/전자수송층/전자주입층/음극(11) anode / hole transport layer / electron suppression layer / light emitting layer / electron transport layer / electron injection layer / cathode
(12) 양극/정공주입층/정공수송층/전자억제층/발광층/전자수송층/음극(12) anode / hole injection layer / hole transport layer / electron suppression layer / light emitting layer / electron transport layer / cathode
(13) 양극/정공주입층/정공수송층/전자억제층/발광층/전자수송층/전자주입 층/음극(13) anode / hole injection layer / hole transport layer / electron suppression layer / light emitting layer / electron transport layer / electron injection layer / cathode
(14) 양극/정공수송층/발광층/정공억제층/전자수송층/음극(14) anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode
(15) 양극/정공수송층/발광층/ 정공억제층/전자수송층/전자주입층/음극(15) anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode
(16) 양극/정공주입층/정공수송층/발광층/정공억제층/전자수송층/음극(16) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode
(17) 양극/정공주입층/정공수송층/발광층/정공억제층/전자수송층/전자주입 층/음극(17) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode
(18) 양극/정공주입층/정공수송층/전자억제층/발광층/정공억제층/전자수송층/전자주입층/음극(18) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode
본 명세서의 일 실시상태에 있어서, 상기 정공수송층은 다층 구조로 이루어질 수 있다. 예컨대, 서로 상이한 물질을 포함하는 제1 정공수송층 및 제2 정공수송층으로 구성될 수 있다.In an exemplary embodiment of the present specification, the hole transport layer may have a multilayer structure. For example, it may be composed of a first hole transport layer and a second hole transport layer comprising different materials.
상기 양극은 정공을 주입하는 전극으로, 양극 물질로는 통상 유기물층으로 정공 주입이 원활할 수 있도록 일함수가 큰 물질이 바람직하다. 본 발명에서 사용될 수 있는 양극 물질의 구체적인 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연 산화물, 인듐 산화물, 인듐주석 산화물(ITO, Indium Tin Oxide), 인듐아연 산화물(IZO, Indium Zinc Oxide)과 같은 금속 산화물; ZnO:Al 또는 SnO2:Sb와 같은 금속과 산화물의 조합; 및 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDOT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다.The anode is an electrode for injecting holes, and as the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material that can be used in the present invention 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 Tin Oxide), and indium zinc oxide (IZO, Indium Zinc Oxide); combinations of metals and oxides such as ZnO:Al or SnO 2 :Sb; and conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto. .
상기 음극은 전자를 주입하는 전극으로, 음극 물질로는 통상 유기물층으로 전자 주입이 용이하도록 일함수가 작은 물질인 것이 바람직하다. 음극 물질의 구체적인 예로는 마그네슘, 칼슘, 나트륨, 칼륨, 티타늄, 인듐, 이트륨, 리튬, 가돌리늄, 알루미늄, 은, 주석 및 납과 같은 금속 또는 이들의 합금; LiF/Al 또는 LiO2/Al과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다.The cathode is an electrode for injecting electrons, and the cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and a multi-layered material such as LiF/Al or LiO2/Al, but is not limited thereto.
상기 정공주입층은 양극으로부터 발광층으로 정공의 주입을 원활하게 하는 역할을 하는 층이며, 정공 주입 물질로는 낮은 전압에서 양극으로부터 정공을 잘 주입 받을 수 있는 물질로서, 정공 주입 물질의 HOMO(highest occupied molecular orbital)가 양극 물질의 일함수와 주변 유기물층의 HOMO 사이인 것이 바람직하다. 정공 주입 물질의 예로는 금속 포피린(porphyrine), 올리고티오펜, 아릴아민 계열의 유기물, 헥사니트릴헥사아자트리페닐렌 계열의 유기물, 퀴나크리돈(quinacridone) 계열의 유기물, 페릴렌(perylene) 계열의 유기물, 카바졸 계열의 유기물, 플루오렌 계열의 유기물, 안트라퀴논 및 폴리아닐린과 폴리티오펜 계열의 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다. 구체적으로, 상기 정공 주입 물질로는 치환 또는 비치환된 카바졸과 치환 또는 비치환된 플루오렌을 포함하는 화합물이 사용될 수 있으나, 이에만 한정되지 않는다. The hole injection layer is a layer that facilitates injection of holes from the anode to the light emitting layer. As the hole injection material, holes can be well injected from the anode at a low voltage, and the highest occupied (HOMO) of the hole injection material is The molecular orbital) is preferably between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. Organic materials, carbazole-based organic materials, fluorene-based organic materials, anthraquinone, polyaniline and polythiophene-based conductive polymers, etc., but are not limited thereto. Specifically, as the hole injection material, a compound including a substituted or unsubstituted carbazole and a substituted or unsubstituted fluorene may be used, but is not limited thereto.
본 명세서의 일 실시상태에 있어서, 상기 정공주입층의 두께는 1nm 내지 150nm일 수 있다. 상기 정공주입층의 두께가 1nm 이상이면, 정공 주입 특성이 저하되는 것을 방지할 수 있는 이점이 있고, 150nm 이하이면, 정공주입층의 두께가 너무 두꺼워 정공의 이동을 향상시키기 위해 구동전압이 상승되는것을 방지할 수 있는 이점이 있다.In one embodiment of the present specification, the hole injection layer may have a thickness of 1 nm to 150 nm. When the thickness of the hole injection layer is 1 nm or more, there is an advantage in that the hole injection characteristics can be prevented from being deteriorated, and when it is 150 nm or less, the thickness of the hole injection layer is too thick, so that the driving voltage is increased to improve hole movement There are advantages to avoiding this.
상기 정공수송층은 정공의 수송을 원활하게 하는 역할을 할 수 있다. 정공 수송 물질로는 양극이나 정공주입층으로부터 정공을 수송 받아 발광층으로 옮겨줄 수 있는 물질로 정공에 대한 이동성이 큰 물질이 적합하다. 정공 수송 물질의 예로는 아릴아민 계열의 유기물, 카바졸 계열의 유기물, 퀴녹살린 계열의 유기물, 플루오렌 계열의 유기물, 전도성 고분자 및 공액 부분과 비공액 부분이 함께 있는 블록 공중합체 등이 있으나, 이들에만 한정되는 것은 아니다. 구체적으로, 상기 정공 수송 물질로는 퀴녹사졸린계 화합물 및 아릴아민계 화합물 등이 있으나, 이에만 한정되지 않는다.The hole transport layer may serve to facilitate hole transport. As the hole transport material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer is suitable, and a material having high hole mobility is suitable. Examples of the hole transport material include an arylamine-based organic material, a carbazole-based organic material, a quinoxaline-based organic material, a fluorene-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together. is not limited to Specifically, the hole transport material includes, but is not limited to, a quinoxazoline-based compound and an arylamine-based compound.
정공주입층과 정공수송층 사이에 추가로 정공버퍼층이 구비될 수 있으며, 당 기술분야에 알려져 있는 정공주입 또는 수송재료를 포함할 수 있다. A hole buffer layer may be additionally provided between the hole injection layer and the hole transport layer, and a hole injection or transport material known in the art may be included.
정공수송층과 발광층 사이에 전자억제층이 구비될 수 있다. 상기 전자억제층은 전술한 화합물 또는 당 기술분야에 알려져 있는 재료가 사용될 수 있다.An electron blocking layer may be provided between the hole transport layer and the light emitting layer. For the electron-blocking layer, the above-described compound or a material known in the art may be used.
상기 발광층은 적색, 녹색 또는 청색을 발광할 수 있으며, 인광 물질 또는 형광 물질로 이루어질 수 있다. 상기 발광 물질로는 정공수송층과 전자수송층으로부터 정공과 전자를 각각 수송받아 결합시킴으로써 가시광선 영역의 빛을 낼 수 있는 물질로서, 형광이나 인광에 대한 양자 효율이 좋은 물질이 바람직하다. 구체적인 예로는 8-히드록시-퀴놀린 알루미늄 착물(Alq3), 카르바졸 계열 화합물, 이량체화 스티릴(dimerized styryl) 화합물, BAlq, 10-히드록시벤조 퀴놀린-금속 화합물, 벤족사졸 계열의 화합물, 벤즈티아졸 계열의 화합물, 벤즈이미다졸 계열의 화합물, 폴리(p-페닐렌비닐렌)(PPV) 계열의 고분자, 스피로(spiro) 화합물, 폴리플루오렌 및 루브렌 등이 있으나, 이들에만 한정되는 것은 아니다.The light emitting layer may emit red, green, or blue light, and may be made of a phosphorescent material or a fluorescent material. The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq 3 ), carbazole-based compound, dimerized styryl compound, BAlq, 10-hydroxybenzoquinoline-metal compound, benzoxazole-based compound, benz There are thiazole-based compounds, benzimidazole-based compounds, poly(p-phenylenevinylene) (PPV)-based polymers, spiro compounds, polyfluorene and rubrene, etc., but are limited to these no.
본 명세서의 일 실시상태에 있어서, 상기 발광층은 호스트 및 도펀트를 포함한다. 상기 호스트로는 전술한 화합물, 축합 방향족환 유도체 및 헤테로고리 함유 화합물 등을 포함할 수 있다. 구체적으로 축합 방향족환 유도체로는 안트라센 유도체, 피렌 유도체, 나프탈렌 유도체, 펜타센 유도체, 페난트렌 화합물, 플루오란텐 화합물 등이 있고, 헤테로고리 함유 화합물로는 카바졸 유도체, 디벤조퓨란 유도체, 래더형 퓨란 화합물, 피리미딘 유도체 등이 있으나, 이에 한정되지 않는다.In an exemplary embodiment of the present specification, the light emitting layer includes a host and a dopant. The host may include the above-mentioned compounds, condensed aromatic ring derivatives, heterocyclic-containing compounds, and the like. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
상기 도펀트로는 PIQIr(acac)(bis(1-phenylisoquinoline)acetylacetonateiridium), PQIr(acac)(bis(1-phenylquinoline)acetylacetonate iridium), PQIr(tris(1-phenylquinoline)iridium), PtOEP(octaethylporphyrin platinum)와 같은 인광 물질이나, Alq3(tris(8-hydroxyquinolino)aluminum)와 같은 형광 물질이 사용될 수 있으나, 이에만 한정된 것은 아니다. 발광층이 녹색 발광을 하는 경우, 발광 도펀트로는 Ir(ppy)3(fac tris(2-phenylpyridine)iridium)와 같은 인광물질이나, Alq3(tris(8-hydroxyquinolino)aluminum)와 같은 형광 물질이 사용될 수 있으나, 이에만 한정된 것은 아니다. 발광층이 청색 발광을 하는 경우, 발광 도펀트로는 (4,6-F2ppy)2Irpic, spiro-DPVBi, spiro-6P, 디스틸벤젠(DSB), 디스트릴아릴렌(DSA), PFO계 고분자, PPV계, 피렌계, 아릴아민계 화합물 등이 사용될 수 있으나, 이에만 한정된 것은 아니다.As the dopant, PIQIr(acac)(bis(1-phenylisoquinoline)acetylacetonateiridium), PQIr(acac)(bis(1-phenylquinoline)acetylacetonate iridium), PQIr(tris(1-phenylquinoline)iridium), PtOEP(octaethylporphyrin platinum) and The same phosphorescent material or a fluorescent material such as Alq 3 (tris(8-hydroxyquinolino)aluminum) may be used, but is not limited thereto. When the emission layer emits green light, a phosphor such as Ir(ppy) 3 (fac tris(2-phenylpyridine)iridium) or a fluorescent material such as Alq3 (tris(8-hydroxyquinolino)aluminum) may be used as the emission dopant. However, the present invention is not limited thereto. When the light emitting layer emits blue light, as a light emitting dopant, (4,6-F 2 ppy) 2 Irpic, spiro-DPVBi, spiro-6P, distylbenzene (DSB), distrylarylene (DSA), PFO-based polymer , PPV-based, pyrene-based, arylamine-based compounds, etc. may be used, but is not limited thereto.
본 명세서의 일 실시상태에 있어서, 상기 전자수송층과 발광층 사이에 정공억제층이 구비될 수 있으며, 정공억제층에는 당 기술분야에 알려져 있는 재료가 사용될 수 있다.In one embodiment of the present specification, a hole blocking layer may be provided between the electron transport layer and the light emitting layer, and materials known in the art may be used for the hole blocking layer.
상기 전자수송층은 전자의 수송을 원활하게 하는 역할을 할 수 있다. 전자 수송 물질로는 음극으로부터 전자를 잘 주입 받아 발광층으로 옮겨줄 수 있는 물질로서, 전자에 대한 이동성이 큰 물질이 적합하다. 구체적인 예로는 8-히드록시퀴놀린의 Al 착물, Alq3를 포함한 착물, 유기 라디칼 화합물, 안트라센계 화합물, 이미다졸계 화합물, 히드록시플라본-금속 착체 등이 있으나, 이들에만 한정되는 것은 아니다. 전자수송층의 두께는 1nm 내지 50nm일 수 있다. 전자수송층의 두께가 1nm 이상이면, 전자 수송 특성이 저하되는 것을 방지할 수 있는 이점이 있고, 50nm 이하이면, 전자수송층의 두께가 너무 두꺼워 전자의 이동을 향상시키기 위해 구동전압이 상승되는 것을 방지할 수 있는 이점이 있다.The electron transport layer may serve to facilitate the transport of electrons. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high electron mobility is suitable. Specific examples include, but are not limited to, an Al complex of 8-hydroxyquinoline , a complex including Alq 3 , an organic radical compound, an anthracene-based compound, an imidazole-based compound, and a hydroxyflavone-metal complex. The electron transport layer may have a thickness of 1 nm to 50 nm. If the thickness of the electron transport layer is 1 nm or more, there is an advantage in that the electron transport characteristics can be prevented from being deteriorated, and if it is 50 nm or less, the thickness of the electron transport layer is too thick to prevent an increase in the driving voltage to improve the movement of electrons. There are advantages that can be
상기 전자주입층은 전자의 주입을 원활하게 하는 역할을 할 수 있다. 전자 주입 물질로는 전자를 수송하는 능력을 갖고, 음극으로부터의 전자주입 효과, 발광층 또는 발광 재료에 대하여 우수한 전자주입 효과를 가지며, 발광층에서 생성된 여기자의 정공주입층으로의 이동을 방지하고, 또한, 박막형성능력이 우수한 화합물이 바람직하다. 구체적으로는 플루오레논, 안트라퀴노다이메탄, 다이페노퀴논, 티오피란 다이옥사이드, 옥사졸, 옥사다이아졸, 트리아졸, 이미다졸, 페릴렌테트라카복실산, 프레오레닐리덴 메탄, 안트론, 안트라센, 이미다졸 등과 그들의 유도체; 금속 착체 화합물; 함질소 5원환 유도체; 및 리튬퀴놀레이트(LiQ) 등이 있으나, 이에 한정되지 않는다. The electron injection layer may serve to facilitate electron injection. The electron injection material has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, prevents the movement of excitons generated in the light emitting layer to the hole injection layer, and , a compound having excellent thin film forming ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, anthracene, imidazole and their derivatives; metal complex compounds; nitrogen-containing 5-membered ring derivatives; and lithium quinolate (LiQ), but is not limited thereto.
본 명세서의 일 실시상태에 있어서, 상기 화학식 1의 헤테로고리 화합물을 포함하는 유기물층은 전자주입층, 전자수송층 또는 전자 주입과 전자 수송을 동시에 하는 층이고, 상기 전자주입층, 전자수송층 또는 전자 주입과 전자 수송을 동시에 하는 층은 금속 착체를 더 포함한다.In an exemplary embodiment of the present specification, the organic material layer including the heterocyclic compound of Formula 1 is an electron injection layer, an electron transport layer, or a layer that simultaneously injects and transports electrons, and the electron injection layer, the electron transport layer or the electron injection and The layer that simultaneously transports electrons further includes a metal complex.
본 명세서의 일 실시상태에 있어서, 상기 금속 착체의 예로는 8-히드록시퀴놀린의 Al 착물(Alq3), LiQ, 금속 착체 화합물 등이 잇으나, 이에만 한정되지 않는다.In the exemplary embodiment of the present specification, examples of the metal complex include , but are not limited to, Al complex of 8-hydroxyquinoline (Alq 3 ), LiQ, and a metal complex compound.
상기 금속 착체 화합물로서는 8-하이드록시퀴놀리나토 리튬, 비스(8-하이드록시퀴놀리나토)아연, 비스(8-하이드록시퀴놀리나토)구리, 비스(8-하이드록시퀴놀리나토)망간, 트리스(8-하이드록시퀴놀리나토)알루미늄, 트리스(2-메틸-8-하이드록시퀴놀리나토)알루미늄, 트리스(8-하이드록시퀴놀리나토)갈륨, 비스(10-하이드록시벤조[h]퀴놀리나토)베릴륨, 비스(10-하이드록시벤조[h]퀴놀리나토)아연, 비스(2-메틸-8-퀴놀리나토)클로로갈륨, 비스(2-메틸-8-퀴놀리나토)(o-크레졸라토)갈륨, 비스(2-메틸-8-퀴놀리나토)(1-나프톨라토)알루미늄 및 비스(2-메틸-8-퀴놀리나토)(2-나프톨라토)갈륨 등이 있으나, 이에 한정되지 않는다.Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, However, the present invention is not limited thereto.
본 명세서의 일 실시상태에 있어서, 상기 전자주입층, 전자수송층 또는 전자 주입과 전자 수송을 동시에 하는 층 내에 화학식 1의 헤테로고리 화합물과 금속 착체는 0.5:1.5 내지 1.5:0.5의 질량비로 포함될 수 있다. In one embodiment of the present specification, the heterocyclic compound of Formula 1 and the metal complex in the electron injection layer, the electron transport layer, or the layer that simultaneously injects and transports electrons may be included in a mass ratio of 0.5:1.5 to 1.5:0.5. .
상기 정공차단층은 정공의 음극 도달을 저지하는 층으로, 일반적으로 정공주입층과 동일한 조건으로 형성될 수 있다. 구체적으로 옥사디아졸 유도체나 트리아졸 유도체, 페난트롤린 유도체, BCP 및 알루미늄 착물 (aluminum complex) 등이 있으나, 이에 한정되지 않는다.The hole blocking layer is a layer that blocks the holes from reaching the cathode, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP and aluminum complexes, but is not limited thereto.
본 명세서의 일 실시상태는 상기 화학식 1로 표시되는 화합물; 및 금속 착체를 포함하는 조성물을 제공한다. An exemplary embodiment of the present specification is a compound represented by Formula 1; And it provides a composition comprising a metal complex.
상기 조성물에 포함되는 금속 착체에 대한 설명은 전자주입층, 전자수송층 또는 전자 주입과 전자 수송을 동시에 하는 층에서 전술한 바와 동일하다.Description of the metal complex included in the composition is the same as described above in the electron injection layer, the electron transport layer, or the layer that simultaneously injects and transports electrons.
본 명세서의 일 실시상태에 있어서, 상기 조성물 내 화학식 1의 헤테로고리 화합물과 금속 착체는 0.5:1.5 내지 1.5:0.5의 질량비로 포함될 수 있다. In an exemplary embodiment of the present specification, the heterocyclic compound of Formula 1 and the metal complex in the composition may be included in a mass ratio of 0.5:1.5 to 1.5:0.5.
본 발명에 따른 유기 발광 소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic light emitting device according to the present invention may be a top emission type, a back emission type, or a double side emission type depending on the material used.
이하, 본 명세서를 구체적으로 설명하기 위해 실시예를 들어 상세하게 설명하기로 한다. 그러나, 본 명세서에 따른 실시예들은 여러 가지 다른 형태로 변형될 수 있으며, 본 명세서의 범위가 아래에서 상술하는 실시예들에 한정되는 것으로 해석되지 않는다. 본 명세서의 실시예들은 당업계에서 평균적인 지식을 가진 자에게 본 명세서를 보다 완전하게 설명하기 위해 제공되는 것이다.Hereinafter, examples will be given to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not to be construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely explain the present specification to those of ordinary skill in the art.
제조예production example 1-1: 화합물 E1의 제조 1-1: Preparation of compound E1
Figure PCTKR2021007746-appb-img-000033
Figure PCTKR2021007746-appb-img-000033
질소 분위기에서 E1-A(20 g, 43.4 mmol)와 E1-B(10.5 g, 43.4mmol)를 테트라하이드로 퓨란 400mL에 넣고 교반 및 환류하였다. 이후 포타슘카보네이트(18 g, 130.3mmol)를 물 18mL에 녹여 투입하고 충분히 교반한 후 테트라키스트리페닐-포스피노팔라듐(1.5 g, 1.3mmol)을 투입하였다. 2시간 반응 후 상온으로 식인 후 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시클로로포름 20배 468mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트 재결정을 통해 흰색의 고체 화합물 E1(18g, 77%, MS: [M+H]+ = 539)을 제조하였다.In a nitrogen atmosphere, E1-A (20 g, 43.4 mmol) and E1-B (10.5 g, 43.4 mmol) were placed in 400 mL of tetrahydrofuran, stirred and refluxed. Thereafter, potassium carbonate (18 g, 130.3 mmol) was dissolved in 18 mL of water, and after stirring sufficiently, tetrakistriphenyl-phosphinopalladium (1.5 g, 1.3 mmol) was added. After the reaction for 2 hours, after cooling to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in 20 times 468 mL of chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare a white solid compound E1 (18 g, 77%, MS: [M+H] + = 539).
제조예production example 1-2: 화합물 E2의 제조 1-2: Preparation of compound E2
Figure PCTKR2021007746-appb-img-000034
Figure PCTKR2021007746-appb-img-000034
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 1-1의 제조 방법과 동일한 방법으로 상기 화합물 E2을 제조하였다.Compound E2 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
MS: [M+H]+ = 589MS: [M+H] + = 589
제조예production example 1-3: 화합물 E3의 제조 1-3: Preparation of compound E3
Figure PCTKR2021007746-appb-img-000035
Figure PCTKR2021007746-appb-img-000035
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 1-1의 제조 방법과 동일한 방법으로 상기 화합물 E3을 제조하였다.Compound E3 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
MS: [M+H]+ = 691MS: [M+H] + = 691
제조예production example 1-4: 화합물 E4의 제조 1-4: Preparation of compound E4
Figure PCTKR2021007746-appb-img-000036
Figure PCTKR2021007746-appb-img-000036
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 1-1의 제조 방법과 동일한 방법으로 상기 화합물 E4을 제조하였다.Compound E4 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
MS: [M+H]+ = 639MS: [M+H] + = 639
제조예production example 1-5: 화합물 E5의 제조 1-5: Preparation of compound E5
Figure PCTKR2021007746-appb-img-000037
Figure PCTKR2021007746-appb-img-000037
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 1-1의 제조 방법과 동일한 방법으로 상기 화합물 E5을 제조하였다.Compound E5 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
MS: [M+H]+ = 641MS: [M+H] + = 641
제조예production example 1-6: 화합물 E6의 제조 1-6: Preparation of compound E6
Figure PCTKR2021007746-appb-img-000038
Figure PCTKR2021007746-appb-img-000038
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 1-1의 제조 방법과 동일한 방법으로 상기 화합물 E6을 제조하였다.Compound E6 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
MS: [M+H]+ = 528MS: [M+H] + = 528
제조예production example 1-7: 화합물 E7의 제조 1-7: Preparation of compound E7
Figure PCTKR2021007746-appb-img-000039
Figure PCTKR2021007746-appb-img-000039
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 1-1의 제조 방법과 동일한 방법으로 상기 화합물 E7을 제조하였다.Compound E7 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
MS: [M+H]+ = 566MS: [M+H] + = 566
제조예production example 1-8: 화합물 E8의 제조 1-8: Preparation of compound E8
Figure PCTKR2021007746-appb-img-000040
Figure PCTKR2021007746-appb-img-000040
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 1-1의 제조 방법과 동일한 방법으로 상기 화합물 E8을 제조하였다.Compound E8 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
MS: [M+H]+ = 616MS: [M+H] + = 616
제조예production example 1-9: 화합물 E9의 제조 1-9: Preparation of compound E9
Figure PCTKR2021007746-appb-img-000041
Figure PCTKR2021007746-appb-img-000041
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 1-1의 제조 방법과 동일한 방법으로 상기 화합물 E9을 제조하였다.Compound E9 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
MS: [M+H]+ = 614MS: [M+H] + = 614
제조예production example 1-10: 화합물 E10의 제조 1-10: Preparation of compound E10
Figure PCTKR2021007746-appb-img-000042
Figure PCTKR2021007746-appb-img-000042
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 1-1의 제조 방법과 동일한 방법으로 상기 화합물 E10을 제조하였다.Compound E10 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
MS: [M+H]+ = 616MS: [M+H] + = 616
제조예production example 1-11: 화합물 E11의 제조 1-11: Preparation of compound E11
Figure PCTKR2021007746-appb-img-000043
Figure PCTKR2021007746-appb-img-000043
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 1-1의 제조 방법과 동일한 방법으로 상기 화합물 E11을 제조하였다.Compound E11 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
MS: [M+H]+ = 589MS: [M+H] + = 589
제조예production example 1-12: 화합물 E12의 제조 1-12: Preparation of compound E12
Figure PCTKR2021007746-appb-img-000044
Figure PCTKR2021007746-appb-img-000044
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 1-1의 제조 방법과 동일한 방법으로 상기 화합물 E12을 제조하였다.Compound E12 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
MS: [M+H]+ = 563MS: [M+H] + = 563
제조예production example 1-13: 화합물 E13의 제조 1-13: Preparation of compound E13
Figure PCTKR2021007746-appb-img-000045
Figure PCTKR2021007746-appb-img-000045
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 1-1의 제조 방법과 동일한 방법으로 상기 화합물 E13을 제조하였다.Compound E13 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
MS: [M+H]+ = 630MS: [M+H] + = 630
제조예production example 1-14: 화합물 E14의 제조 1-14: Preparation of compound E14
Figure PCTKR2021007746-appb-img-000046
Figure PCTKR2021007746-appb-img-000046
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 1-1의 제조 방법과 동일한 방법으로 상기 화합물 E14을 제조하였다.Compound E14 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
MS: [M+H]+ = 707MS: [M+H] + = 707
제조예production example 1-15: 화합물 E15의 제조 1-15: Preparation of compound E15
Figure PCTKR2021007746-appb-img-000047
Figure PCTKR2021007746-appb-img-000047
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 1-1의 제조 방법과 동일한 방법으로 상기 화합물 E15을 제조하였다.Compound E15 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.
MS: [M+H]+ = 733MS: [M+H] + = 733
실시예Example 1-1. 1-1.
ITO(indium tin oxide)가 1000Å의 두께로 박막 코팅된 유리 기판을 세제를 녹인 증류수에 넣고 초음파로 세척하였다. 이때, 세제로는 피셔사(Fischer Co.) 제품을 사용하였으며, 증류수로는 밀리포어사(Millipore Co.) 제품의 필터(Filter)로 2차로 걸러진 증류수를 사용하였다. ITO를 30분간 세척한 후 증류수로 2회 반복하여 초음파 세척을 10분간 진행하였다. 증류수 세척이 끝난 후, 이소프로필알콜, 아세톤, 메탄올의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 수송시켰다. 또한, 산소 플라즈마를 이용하여 상기 기판을 5분간 세정한 후 진공 증착기로 기판을 수송시켰다. A glass substrate coated with indium tin oxide (ITO) to a thickness of 1000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing the ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, and after drying, it was transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.
이렇게 준비된 ITO 투명 전극 위에 하기 HI-A 화합물을 600Å의 두께로 열 진공 증착하여 정공주입층을 형성하였다. 상기 정공주입층 상에 하기 HAT 화합물 50Å 및 하기 HT-A 화합물 60Å를 순차적으로 진공 증착하여 제1 정공수송층 및 제2 정공수송층을 형성하였다. On the thus prepared ITO transparent electrode, the following HI-A compound was thermally vacuum deposited to a thickness of 600 Å to form a hole injection layer. A first hole transport layer and a second hole transport layer were formed by sequentially vacuum-depositing 50 Å of the HAT compound and 60 Å of the HT-A compound on the hole injection layer.
이어서, 상기 제2 정공수송층 상에 막 두께 20nm로 하기 BH 화합물 및 BD 화합물을 25:1의 중량비로 진공 증착하여 발광층을 형성하였다. Then, the following BH compound and BD compound were vacuum-deposited in a weight ratio of 25:1 to a thickness of 20 nm on the second hole transport layer to form a light emitting layer.
상기 발광층 상에 상기 제조예 1-1에서 제조된 화합물 E1과 하기 LiQ 화합물을 1:1의 중량비로 진공 증착하여 350Å의 두께로 전자 주입 및 수송층을 형성하였다. 상기 전자 주입 및 수송층 상에 순차적으로 10Å의 두께로 리튬 플루오라이드(LiF)와 1000Å 두께로 알루미늄을 증착하여 음극을 형성하였다. On the light emitting layer, the compound E1 prepared in Preparation Example 1-1 and the following LiQ compound were vacuum deposited in a weight ratio of 1:1 to form an electron injection and transport layer to a thickness of 350 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 10 Å and aluminum to a thickness of 1000 Å on the electron injection and transport layer.
상기의 과정에서 유기물의 증착 속도는 0.4 Å/sec 내지 0.9 Å/sec를 유지하였고, 음극의 리튬 플루오라이드는 0.3 Å/sec, 알루미늄은 2 Å/sec의 증착 속도를 유지하였으며, 증착시 진공도는 1×10-7 torr 내지 5×10-5 torr를 유지하여, 유기 발광 소자를 제조하였다.In the above process, the deposition rate of the organic material was maintained at 0.4 Å/sec to 0.9 Å/sec, the deposition rate of lithium fluoride of the negative electrode was maintained at 0.3 Å/sec, and the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was By maintaining 1×10 -7 torr to 5×10 -5 torr, an organic light emitting device was manufactured.
Figure PCTKR2021007746-appb-img-000048
Figure PCTKR2021007746-appb-img-000048
실시예Example 1-2 내지 1-15. 1-2 to 1-15.
상기 실시예 1-1의 화합물 E1 대신 하기 표 1에 기재된 화합물 E2 내지 E15을 각각 사용하는 것을 제외하고는, 상기 실시예 1-1과 동일한 방법으로 유기 발광 소자를 제조하였다. An organic light emitting diode was manufactured in the same manner as in Example 1-1, except that compounds E2 to E15 of Table 1 were used instead of compound E1 of Example 1-1.
비교예comparative example 1-1 내지 1-13. 1-1 to 1-13.
상기 실시예 1-1의 화합물 E1 대신 하기의 표 1에 기재된 화합물 ET-A 내지 ET-M을 각각 사용하는 것을 제외하고는, 상기 실시예 1-1과 동일한 방법으로 유기 발광 소자를 제조하였다.An organic light emitting diode was manufactured in the same manner as in Example 1-1, except that compounds ET-A to ET-M shown in Table 1 were used instead of Compound E1 of Example 1-1.
Figure PCTKR2021007746-appb-img-000049
Figure PCTKR2021007746-appb-img-000049
상기 실시예 1-1 내지 1-15 및 비교예 1-1 내지 1-13에서 제조한 유기 발광 소자에 대하여 10mA/cm2의 전류 밀도에서 구동 전압과 발광 효율을 측정하였고, 20mA/cm2의 전류 밀도에서 초기 휘도 대비 90%가 되는 시간(T90)을 측정하였다. 상기 결과를 하기 표 1에 나타내었다.For the organic light emitting diodes prepared in Examples 1-1 to 1-15 and Comparative Examples 1-1 to 1-13, the driving voltage and luminous efficiency were measured at a current density of 10 mA/cm 2 , and 20 mA/cm 2 The time (T90) at which the current density becomes 90% of the initial luminance was measured. The results are shown in Table 1 below.
구분division 화합물compound 전압
(V
@10 mA/cm2)Voltage
(V
@10 mA/cm 2 ) 		효율
(cd/A
@10 mA/cm2)efficiency
(cd/A
@10 mA/cm 2 ) 		색좌표
(x, y)color coordinates
(x, y) 		수명(h)
T90 at
20 mA/cm2)Life (h)
T90 at
20 mA/cm 2 )
실시예 1-1Example 1-1 E1E1 4.444.44 4.854.85 (0.140, 0.092)(0.140, 0.092) 155155
실시예 1-2Example 1-2 E2E2 4.534.53 4.754.75 (0.140, 0.093)(0.140, 0.093) 175175
실시예 1-3Examples 1-3 E3E3 4.484.48 5.005.00 (0.140, 0.093)(0.140, 0.093) 141141
실시예 1-4Examples 1-4 E4E4 4.484.48 4.854.85 (0.141, 0.092)(0.141, 0.092) 159159
실시예 1-5Examples 1-5 E5E5 4.574.57 4.974.97 (0.140, 0.092)(0.140, 0.092) 143143
실시예 1-6Examples 1-6 E6E6 4.574.57 4.664.66 (0.140, 0.093)(0.140, 0.093) 133133
실시예 1-7Examples 1-7 E7E7 4.484.48 4.824.82 (0.140, 0.093)(0.140, 0.093) 161161
실시예 1-8Examples 1-8 E8E8 4.494.49 4.804.80 (0.141, 0.092)(0.141, 0.092) 180180
실시예 1-9Examples 1-9 E9E9 4.664.66 4.614.61 (0.140, 0.092)(0.140, 0.092) 205205
실시예 1-10Examples 1-10 E10E10 4.484.48 4.954.95 (0.140, 0.093)(0.140, 0.093) 149149
실시예 1-11Examples 1-11 E11E11 4.444.44 4.924.92 (0.140, 0.093)(0.140, 0.093) 154154
실시예 1-12Examples 1-12 E12E12 4.574.57 4.604.60 (0.140, 0.092)(0.140, 0.092) 125125
실시예 1-13Examples 1-13 E13E13 4.714.71 4.664.66 (0.140, 0.093)(0.140, 0.093) 194194
실시예 1-14Examples 1-14 E14E14 4.534.53 5.055.05 (0.140, 0.093)(0.140, 0.093) 138138
실시예 1-15Examples 1-15 E15E15 4.534.53 4.924.92 (0.140, 0.092)(0.140, 0.092) 147147
비교예 1-1Comparative Example 1-1 ET-AET-A 4.974.97 3.403.40 (0.140, 0.093)(0.140, 0.093) 110110
비교예 1-2Comparative Example 1-2 ET-BET-B 5.215.21 3.143.14 (0.141, 0.092)(0.141, 0.092) 109109
비교예 1-3Comparative Example 1-3 ET-CET-C 5.025.02 3.503.50 (0.140, 0.092)(0.140, 0.092) 100100
비교예 1-4Comparative Example 1-4 ET-DET-D 5.025.02 3.493.49 (0.140, 0.093)(0.140, 0.093) 3737
비교예 1-5Comparative Example 1-5 ET-EET-E 5.125.12 3.423.42 (0.140, 0.093)(0.140, 0.093) 4444
비교예 1-6Comparative Example 1-6 ET-FET-F 5.075.07 3.603.60 (0.141, 0.092)(0.141, 0.092) 3737
비교예 1-7Comparative Example 1-7 ET-GET-G 5.075.07 3.493.49 (0.140, 0.092)(0.140, 0.092) 4141
비교예 1-8Comparative Examples 1-8 ET-HET-H 4.584.58 4.424.42 (0.140, 0.093)(0.140, 0.093) 3636
비교예 1-9Comparative Example 1-9 ET-IET-I 4.764.76 4.244.24 (0.140, 0.093)(0.140, 0.093) 4141
비교예 1-10Comparative Example 1-10 ET-JET-J 4.574.57 4.554.55 (0.141, 0.092)(0.141, 0.092) 3030
비교예 1-11Comparative Example 1-11 ET-KET-K 4.524.52 4.534.53 (0.141, 0.092)(0.141, 0.092) 3131
비교예 1-12Comparative Example 1-12 ET-LET-L 4.674.67 4.424.42 (0.141, 0.092)(0.141, 0.092) 3333
비교예 1-13Comparative Example 1-13 ET-MET-M 5.425.42 3.073.07 (0.141, 0.092)(0.141, 0.092) 8686
상기 표 1에 기재된 바와 같이, 본 명세서에 따른 화학식 1로 표시되는 화합물은 유기 발광 소자의 전자 주입과 수송을 동시에 하는 유기물층에 사용될 수 있다.As shown in Table 1, the compound represented by Formula 1 according to the present specification may be used in an organic material layer that simultaneously injects and transports electrons of an organic light emitting device.
상기 표 1의 실시예 1-1 내지 1-15와 비교예 1-1 및 1-3을 비교하면, 본 명세서에 따른 화학식 1의 헤테로고리 화합물을 적용한 유기 발광 소자는 퀴나졸린기가 상이한 위치로 치환된 화합물을 적용한 유기 발광 소자 보다 효율 면에서 현저히 우수한 특성을 보임을 확인할 수 있었다.Comparing Examples 1-1 to 1-15 of Table 1 and Comparative Examples 1-1 and 1-3, in the organic light emitting device to which the heterocyclic compound of Formula 1 according to the present specification is applied, a quinazoline group is substituted at a different position It was confirmed that the organic light-emitting device to which the used compound was applied showed significantly superior characteristics in terms of efficiency.
상기 표 1의 실시예 1-1 내지 1-15와 비교예 1-2 및 1-13을 비교하면, 본 명세서에 따른 화학식 1의 헤테로고리 화합물을 적용한 유기 발광 소자는 잔텐기의 양측이 모두 치환기를 포함하는 화합물을 적용한 유기 발광 소자 보다 효율 및 수명 면에서 현저히 우수한 특성을 보임을 확인할 수 있었다.Comparing Examples 1-1 to 1-15 of Table 1 and Comparative Examples 1-2 and 1-13, in the organic light emitting device to which the heterocyclic compound of Formula 1 according to the present specification is applied, both sides of the xanthene group are substituents It was confirmed that it showed significantly superior characteristics in terms of efficiency and lifespan than organic light emitting devices to which a compound containing
상기 표 1의 실시예 1-1 내지 1-15과 비교예 1-4 내지 1-7을 비교하면, 본 명세서에 따른 화학식 1의 헤테로고리 화합물을 적용한 유기 발광 소자는 Ar1으로 구조가 상이한 치환기가 치환된 화합물을 적용한 유기 발광 소자 보다 효율 및 수명 면에서 현저히 우수한 특성을 보임을 확인할 수 있었다.Comparing Examples 1-1 to 1-15 of Table 1 and Comparative Examples 1-4 to 1-7, in the organic light emitting device to which the heterocyclic compound of Formula 1 according to the present specification is applied, a substituent having a different structure is Ar1 It was confirmed that the organic light-emitting device to which the substituted compound was applied showed significantly superior characteristics in terms of efficiency and lifespan.
상기 표 1의 실시예 1-1 내지 1-15과 비교예 1-8 내지 1-12를 비교하면, 본 명세서에 따른 화학식 1의 헤테로고리 화합물을 적용한 유기 발광 소자는 R1 및 R2가 서로 결합하여 방향족 환을 형성하거나, 플루오렌기에 (L)a-Ar1이 치환된 화합물을 적용한 유기 발광 소자보다 수명 면에서 현저히 우수한 특성을 보임을 확인할 수 있었다.Comparing Examples 1-1 to 1-15 of Table 1 and Comparative Examples 1-8 to 1-12, in the organic light emitting device to which the heterocyclic compound of Formula 1 according to the present specification is applied, R1 and R2 are bonded to each other, It was confirmed that the organic light emitting diode formed an aromatic ring or applied a compound in which (L) a -Ar1 was substituted with a fluorene group showed significantly superior characteristics in terms of lifespan.
실시예Example 2-1. 2-1.
ITO(indium tin oxide)가 1000Å의 두께로 박막 코팅된 유리 기판을 세제를 녹인 증류수에 넣고 초음파로 세척하였다. 이때, 세제로는 피셔사(Fischer Co.) 제품을 사용하였으며, 증류수로는 밀리포어사(Millipore Co.) 제품의 필터(Filter)로 2차로 걸러진 증류수를 사용하였다. ITO를 30분간 세척한 후 증류수로 2회 반복하여 초음파 세척을 10분간 진행하였다. 증류수 세척이 끝난 후, 이소프로필알콜, 아세톤, 메탄올의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 수송시켰다. 또한, 산소 플라즈마를 이용하여 상기 기판을 5분간 세정한 후 진공 증착기로 기판을 수송시켰다. A glass substrate coated with indium tin oxide (ITO) to a thickness of 1000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing the ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, and after drying, it was transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.
이렇게 준비된 ITO 투명 전극 위에 하기 HI-A 화합물을 600Å의 두께로 열 진공 증착하여 정공주입층을 형성하였다. 상기 정공주입층 상에 하기 HAT 화합물 50Å 및 하기 HT-A 화합물 60Å를 순차적으로 진공 증착하여 제1 정공수송층 및 제2 정공수송층을 형성하였다. On the thus prepared ITO transparent electrode, the following HI-A compound was thermally vacuum deposited to a thickness of 600 Å to form a hole injection layer. A first hole transport layer and a second hole transport layer were formed by sequentially vacuum-depositing 50 Å of the HAT compound and 60 Å of the HT-A compound on the hole injection layer.
이어서, 상기 제2 정공수송층 상에 막 두께 20nm로 하기 BH 화합물 및 BD 화합물을 25:1의 중량비로 진공 증착하여 발광층을 형성하였다. Then, the following BH compound and BD compound were vacuum-deposited at a weight ratio of 25:1 to a thickness of 20 nm on the second hole transport layer to form a light emitting layer.
상기 발광층 상에 상기 제조예 1-1에서 제조된 화합물 E1을 50Å 두께로 진공 증착하여 정공차단층을 형성하였고, ET-N과 하기 LiQ 화합물을 1:1의 중량비로 진공 증착하여 300Å의 두께로 전자 주입 및 수송층을 형성하였다. 상기 전자 주입 및 수송층 상에 순차적으로 10Å의 두께로 리튬 플루오라이드(LiF)와 1000Å 두께로 알루미늄을 증착하여 음극을 형성하였다. On the light emitting layer, the compound E1 prepared in Preparation Example 1-1 was vacuum deposited to a thickness of 50 Å to form a hole blocking layer, and ET-N and the following LiQ compound were vacuum deposited in a weight ratio of 1:1 to a thickness of 300 Å. An electron injection and transport layer was formed. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 10 Å and aluminum to a thickness of 1000 Å on the electron injection and transport layer.
상기의 과정에서 유기물의 증착 속도는 0.4 Å/sec 내지 0.9 Å/sec를 유지하였고, 음극의 리튬 플루오라이드는 0.3 Å/sec, 알루미늄은 2 Å/sec의 증착 속도를 유지하였으며, 증착시 진공도는 1×10-7 torr 내지 5×10-5 torr를 유지하여, 유기 발광 소자를 제조하였다.In the above process, the deposition rate of the organic material was maintained at 0.4 Å/sec to 0.9 Å/sec, the deposition rate of lithium fluoride of the negative electrode was maintained at 0.3 Å/sec, and the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was By maintaining 1×10 -7 torr to 5×10 -5 torr, an organic light emitting device was manufactured.
Figure PCTKR2021007746-appb-img-000050
Figure PCTKR2021007746-appb-img-000050
실시예Example 2-2 내지 2-13. 2-2 to 2-13.
상기 실시예 2-1의 화합물 E1 대신 하기 표 2에 기재된 화합물 E2 내지 E8, E10 내지 E12, E14 및 E15를 각각 사용하는 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 유기 발광 소자를 제조하였다. An organic light emitting device was prepared in the same manner as in Example 2-1, except that compounds E2 to E8, E10 to E12, E14 and E15 described in Table 2 below were used instead of compound E1 of Example 2-1. prepared.
비교예comparative example 2-1 내지 2-11. 2-1 to 2-11.
상기 실시예 2-1의 화합물 E1 대신 하기의 표 2에 기재된 화합물 ET-A 내지 ET-H 및 ET-J 내지 ET-L 을 각각 사용하는 것을 제외하고는, 상기 실시예 2-1과 동일한 방법으로 유기 발광 소자를 제조하였다.The same method as in Example 2-1, except that compounds ET-A to ET-H and ET-J to ET-L described in Table 2 below were used instead of Compound E1 in Example 2-1 to manufacture an organic light emitting device.
상기 실시예 2-1 내지 2-13 및 비교예 2-1 내지 2-11에서 제조한 유기 발광 소자에 대하여 10mA/cm2의 전류 밀도에서 구동 전압과 발광 효율을 측정하였고, 20mA/cm2의 전류 밀도에서 초기 휘도 대비 90%가 되는 시간(T90)을 측정하였다. 상기 결과를 하기 표 2에 나타내었다.For the organic light emitting diodes prepared in Examples 2-1 to 2-13 and Comparative Examples 2-1 to 2-11, the driving voltage and luminous efficiency were measured at a current density of 10 mA/cm 2 , and 20 mA/cm 2 The time (T90) at which the current density becomes 90% of the initial luminance was measured. The results are shown in Table 2 below.
구분division 화합물compound 전압
(V
@10 mA/cm2)Voltage
(V
@10 mA/cm 2 ) 		효율
(cd/A
@10 mA/cm2)efficiency
(cd/A
@10 mA/cm 2 ) 		색좌표
(x, y)color coordinates
(x, y) 		수명(h)
T90 at
20 mA/cm2)Life (h)
T90 at
20 mA/cm 2 )
실시예 2-1Example 2-1 E1E1 4.354.35 5.095.09 (0.140, 0.092)(0.140, 0.092) 126126
실시예 2-2Example 2-2 E2E2 4.444.44 4.994.99 (0.140, 0.093)(0.140, 0.093) 138138
실시예 2-3Example 2-3 E3E3 4.264.26 5.255.25 (0.140, 0.093)(0.140, 0.093) 114114
실시예 2-4Example 2-4 E4E4 4.394.39 5.095.09 (0.141, 0.092)(0.141, 0.092) 128128
실시예 2-5Example 2-5 E5E5 4.264.26 5.225.22 (0.140, 0.092)(0.140, 0.092) 108108
실시예 2-6Example 2-6 E6E6 4.484.48 4.894.89 (0.140, 0.093)(0.140, 0.093) 108108
실시예 2-7Example 2-7 E7E7 4.314.31 5.125.12 (0.140, 0.093)(0.140, 0.093) 122122
실시예 2-8Examples 2-8 E8E8 4.404.40 5.045.04 (0.141, 0.092)(0.141, 0.092) 146146
실시예 2-9Examples 2-9 E10E10 4.314.31 5.195.19 (0.140, 0.093)(0.140, 0.093) 121121
실시예 2-10Example 2-10 E11E11 4.144.14 5.175.17 (0.140, 0.093)(0.140, 0.093) 117117
실시예 2-11Example 2-11 E12E12 4.484.48 5.005.00 (0.140, 0.092)(0.140, 0.092) 9595
실시예 2-12Example 2-12 E14E14 4.314.31 5.305.30 (0.140, 0.093)(0.140, 0.093) 112112
실시예 2-13Examples 2-13 E15E15 4.224.22 5.275.27 (0.140, 0.092)(0.140, 0.092) 103103
비교예 2-1Comparative Example 2-1 ET-AET-A 4.874.87 3.563.56 (0.140, 0.093)(0.140, 0.093) 8989
비교예 2-2Comparative Example 2-2 ET-BET-B 5.105.10 3.293.29 (0.141, 0.092)(0.141, 0.092) 6161
비교예 2-3Comparative Example 2-3 ET-CET-C 4.784.78 3.673.67 (0.140, 0.092)(0.140, 0.092) 8181
비교예 2-4Comparative Example 2-4 ET-DET-D 4.924.92 3.673.67 (0.140, 0.093)(0.140, 0.093) 3030
비교예 2-5Comparative Example 2-5 ET-EET-E 5.025.02 3.593.59 (0.140, 0.093)(0.140, 0.093) 3636
비교예 2-6Comparative Example 2-6 ET-FET-F 4.824.82 3.783.78 (0.141, 0.092)(0.141, 0.092) 3030
비교예 2-7Comparative Example 2-7 ET-GET-G 4.974.97 3.673.67 (0.140, 0.092)(0.140, 0.092) 3333
비교예 2-8Comparative Example 2-8 ET-HET-H 4.494.49 4.644.64 (0.140, 0.093)(0.140, 0.093) 2929
비교예 2-9Comparative Example 2-9 ET-JET-J 4.394.39 4.784.78 (0.141, 0.092)(0.141, 0.092) 2424
비교예 2-10Comparative Example 2-10 ET-KET-K 4.224.22 4.754.75 (0.141, 0.092)(0.141, 0.092) 2323
비교예 2-11Comparative Example 2-11 ET-LET-L 4.574.57 4.644.64 (0.141, 0.092)(0.141, 0.092) 2727
상기 표 2에 기재된 바와 같이, 본 명세서에 따른 화학식 1로 표시되는 화합물은 유기 발광 소자의 정공차단을 하는 유기물층에 사용될 수 있다.As shown in Table 2, the compound represented by Chemical Formula 1 according to the present specification may be used in the organic material layer for blocking holes of the organic light emitting device.
상기 표 2의 실시예 2-1 내지 2-13과 비교예 2-1 및 2-3을 비교하면, 본 명세서에 따른 화학식 1의 헤테로고리 화합물을 적용한 유기 발광 소자는 퀴나졸린기가 상이한 위치로 치환된 화합물을 적용한 유기 발광 소자 보다 효율 면에서 현저히 우수한 특성을 보임을 확인할 수 있었다.Comparing Examples 2-1 to 2-13 of Table 2 and Comparative Examples 2-1 and 2-3, in the organic light emitting device to which the heterocyclic compound of Formula 1 according to the present specification is applied, a quinazoline group is substituted at a different position It was confirmed that the organic light emitting device to which the used compound was applied showed significantly superior characteristics in terms of efficiency.
상기 표 2의 실시예 2-1 내지 2-13과 비교예 2-2를 비교하면, 본 명세서에 따른 화학식 1의 헤테로고리 화합물을 적용한 유기 발광 소자는 잔텐기의 양측이 모두 치환기를 포함하는 화합물을 적용한 유기 발광 소자 보다 효율, 수명 면에서 현저히 우수한 특성을 보임을 확인할 수 있었다.Comparing Examples 2-1 to 2-13 of Table 2 and Comparative Example 2-2, the organic light emitting device to which the heterocyclic compound of Formula 1 according to the present specification is applied is a compound in which both sides of the xanthene group include a substituent It was confirmed that it showed significantly superior characteristics in terms of efficiency and lifespan compared to organic light emitting devices to which .
상기 표 2의 실시예 2-1 내지 2-13과 비교예 2-4 내지 2-7을 비교하면, 본 명세서에 따른 화학식 1의 헤테로고리 화합물을 적용한 유기 발광 소자는 Ar1으로 구조가 상이한 치환기가 치환된 화합물을 적용한 유기 발광 소자 보다 효율, 수명 면에서 현저히 우수한 특성을 보임을 확인할 수 있었다.Comparing Examples 2-1 to 2-13 of Table 2 and Comparative Examples 2-4 to 2-7, in the organic light emitting device to which the heterocyclic compound of Formula 1 according to the present specification is applied, a substituent having a different structure is Ar1 It was confirmed that the organic light-emitting device to which the substituted compound was applied showed significantly superior characteristics in terms of efficiency and lifespan.
상기 표 2의 실시예 2-1 내지 2-13과 비교예 2-8 내지 2-11을 비교하면, 본 명세서에 따른 화학식 1의 헤테로고리 화합물을 적용한 유기 발광 소자는 R1 및 R2가 서로 결합하여 방향족 환을 형성하거나, 플루오렌기에 (L)a-Ar1이 치환된 화합물을 적용한 유기 발광 소자보다 수명 면에서 현저히 우수한 특성을 보임을 확인할 수 있었다.Comparing Examples 2-1 to 2-13 of Table 2 and Comparative Examples 2-8 to 2-11, in the organic light emitting device to which the heterocyclic compound of Formula 1 according to the present specification is applied, R1 and R2 are bonded to each other, It was confirmed that the organic light emitting diode formed an aromatic ring or applied a compound in which (L) a -Ar1 was substituted with a fluorene group showed significantly superior characteristics in terms of lifespan.

Claims (10)

  1. 하기 화학식 1의 헤테로고리 화합물:Heterocyclic compound of formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2021007746-appb-img-000051
    Figure PCTKR2021007746-appb-img-000051
    상기 화학식 1에 있어서,In Formula 1,
    Z는 O 또는 S이고,Z is O or S;
    R1 및 R2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이며,R1 and R2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
    R3 내지 R6는 각각 독립적으로 수소이거나, 서로 결합하여 탄화수소고리를 형성하고,R3 to R6 are each independently hydrogen, or combine with each other to form a hydrocarbon ring,
    L은 직접결합; 치환 또는 비치환된 아릴렌기; 또는 치환 또는 비치환된 2가의 헤테로고리기이며,L is a direct bond; a substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,
    a는 1 내지 3의 정수이고, a가 2 이상일 경우 2 이상의 L은 서로 같거나 상이하며,a is an integer of 1 to 3, and when a is 2 or more, L of 2 or more are the same as or different from each other,
    b 는 1 내지 4의 정수이고, b가 2 이상일 경우 괄호 안의 구조는 서로 같거나 상이하며,b is an integer of 1 to 4, and when b is 2 or more, the structures in parentheses are the same as or different from each other,
    Ar1은 하기로 구성되는 군으로부터 선택된 어느 하나이고,Ar1 is any one selected from the group consisting of
    Figure PCTKR2021007746-appb-img-000052
    Figure PCTKR2021007746-appb-img-000052
    상기 구조에 있어서,In the structure,
    Figure PCTKR2021007746-appb-img-000053
    는 L에 연결되는 부분이고,
    Figure PCTKR2021007746-appb-img-000053
    is a part connected to L,
    c는 1 내지 5의 정수이고, c가 2 이상일 경우 2 이상의 G15는 서로 같거나 상이하며,c is an integer of 1 to 5, and when c is 2 or more, 2 or more G15 are the same as or different from each other,
    d는 1 내지 4의 정수이고, d가 2 이상일 경우 2 이상의 G16은 서로 같거나 상이하며,d is an integer of 1 to 4, and when d is 2 or more, 2 or more G16 are the same as or different from each other,
    X1 내지 X4는 서로 같거나 상이하고, 각각 독립적으로 N 또는 CR10이고, 단 X1 내지 X4 중 2 이상이 N이며,X1 to X4 are the same as or different from each other, and each independently represents N or CR10, provided that at least two of X1 to X4 are N;
    R10 및 G1 내지 G16은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이다.R10 and G1 to G16 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.
  2. 청구항 1에 있어서,The method according to claim 1,
    상기 L은 직접결합; 치환 또는 비치환된 페닐렌기; 치환 또는 비치환된 비페닐렌기; 치환 또는 비치환된 나프틸렌기; 또는 치환 또는 비치환된 2가의 피리딘기인 것인 헤테로고리 화합물.L is a direct bond; a substituted or unsubstituted phenylene group; a substituted or unsubstituted biphenylene group; a substituted or unsubstituted naphthylene group; Or a substituted or unsubstituted divalent pyridine group heterocyclic compound.
  3. 청구항 1에 있어서,The method according to claim 1,
    상기 R1 및 R2는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 페닐기; 치환 또는 비치환된 나프틸기; 또는 치환 또는 비치환된 피리딘기인 것인 헤테로고리 화합물.wherein R1 and R2 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group; a substituted or unsubstituted naphthyl group; Or a substituted or unsubstituted pyridine group is a heterocyclic compound.
  4. 청구항 1에 있어서,The method according to claim 1,
    상기 화학식 1은 하기 화학식 1-1 내지 1-4 중 어느 하나인 것인 헤테로고리 화합물:Formula 1 is a heterocyclic compound of any one of Formulas 1-1 to 1-4:
    [화학식 1-1][Formula 1-1]
    Figure PCTKR2021007746-appb-img-000054
    Figure PCTKR2021007746-appb-img-000054
    [화학식 1-2][Formula 1-2]
    Figure PCTKR2021007746-appb-img-000055
    Figure PCTKR2021007746-appb-img-000055
    [화학식 1-3][Formula 1-3]
    Figure PCTKR2021007746-appb-img-000056
    Figure PCTKR2021007746-appb-img-000056
    [화학식 1-4][Formula 1-4]
    Figure PCTKR2021007746-appb-img-000057
    Figure PCTKR2021007746-appb-img-000057
    상기 화학식 1-1 내지 1-4에 있어서,In Formulas 1-1 to 1-4,
    Z, R1, R2, a, L 및 Ar1은 상기 화학식 1에서 정의한 바와 동일하다.Z, R1, R2, a, L and Ar1 are the same as defined in Formula 1 above.
  5. 청구항 1에 있어서, 상기 화학식 1은 하기 화학식 1-5 내지 1-7 중 어느 하나로 표시되는 것인 헤테로고리 화합물:The heterocyclic compound according to claim 1, wherein Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-5 to 1-7:
    [화학식 1-5] [Formula 1-5]
    Figure PCTKR2021007746-appb-img-000058
    Figure PCTKR2021007746-appb-img-000058
    [화학식 1-6] [Formula 1-6]
    Figure PCTKR2021007746-appb-img-000059
    Figure PCTKR2021007746-appb-img-000059
    [화학식 1-7] [Formula 1-7]
    Figure PCTKR2021007746-appb-img-000060
    Figure PCTKR2021007746-appb-img-000060
    상기 화학식 1-5 내지 1-7에 있어서,In Formulas 1-5 to 1-7,
    Z, R1 내지 R6, L, a, b, 및 Ar1은 상기 화학식 1에서 정의한 바와 동일하다.Z, R1 to R6, L, a, b, and Ar1 are the same as defined in Formula 1 above.
  6. 청구항 1에 있어서, 상기 화학식 1의 헤테로고리 화합물은 하기 구조 중 어느 하나인 것인 헤테로고리 화합물: The heterocyclic compound according to claim 1, wherein the heterocyclic compound of Formula 1 is any one of the following structures:
    Figure PCTKR2021007746-appb-img-000061
    Figure PCTKR2021007746-appb-img-000061
    Figure PCTKR2021007746-appb-img-000062
    Figure PCTKR2021007746-appb-img-000062
    Figure PCTKR2021007746-appb-img-000063
    Figure PCTKR2021007746-appb-img-000063
    Figure PCTKR2021007746-appb-img-000064
    Figure PCTKR2021007746-appb-img-000064
    Figure PCTKR2021007746-appb-img-000065
    Figure PCTKR2021007746-appb-img-000065
    Figure PCTKR2021007746-appb-img-000066
    Figure PCTKR2021007746-appb-img-000066
    Figure PCTKR2021007746-appb-img-000067
    Figure PCTKR2021007746-appb-img-000067
    Figure PCTKR2021007746-appb-img-000068
    Figure PCTKR2021007746-appb-img-000068
    Figure PCTKR2021007746-appb-img-000069
    Figure PCTKR2021007746-appb-img-000069
    Figure PCTKR2021007746-appb-img-000070
    Figure PCTKR2021007746-appb-img-000070
    Figure PCTKR2021007746-appb-img-000071
    .
    Figure PCTKR2021007746-appb-img-000071
    .
  7. 제1 전극; 상기 제1 전극에 대향하여 구비된 제2 전극; 및 상기 제1 전극과 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 청구항 1 내지 6 중 어느 한 항의 헤테로고리 화합물을 포함하는 것인 유기 발광 소자.a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises the heterocyclic compound of any one of claims 1 to 6. device.
  8. 청구항 7에 있어서, 상기 유기물층은 전자주입층, 전자수송층 또는 전자 주입과 전자 수송을 동시에 하는 층을 포함하고, 상기 전자주입층, 전자수송층 또는 전자 주입과 전자 수송을 동시에 하는 층은 상기 헤테로고리 화합물을 포함하는 것인 유기 발광 소자.The method according to claim 7, wherein the organic material layer comprises an electron injection layer, an electron transport layer, or a layer that simultaneously injects and transports electrons, the electron injection layer, the electron transport layer, or the layer that simultaneously injects and transports electrons is the heterocyclic compound An organic light emitting device comprising a.
  9. 청구항 8에 있어서, 상기 전자주입층, 전자수송층 또는 전자 주입과 전자 수송을 동시에 하는 층은 금속 착체을 더 포함하는 것인 유기 발광 소자.The organic light-emitting device according to claim 8, wherein the electron injection layer, the electron transport layer, or the layer that simultaneously injects and transports electrons further comprises a metal complex.
  10. 청구항 7에 있어서, 상기 유기물층은 정공차단층을 포함하고, 상기 정공차단층은 상기 헤테로고리 화합물을 포함하는 것인 유기 발광 소자.The organic light-emitting device of claim 7 , wherein the organic material layer includes a hole blocking layer, and the hole blocking layer includes the heterocyclic compound.
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