WO2020085765A1 - Polycyclic compound and organic light-emitting element comprising same - Google Patents

Polycyclic compound and organic light-emitting element comprising same Download PDF

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WO2020085765A1
WO2020085765A1 PCT/KR2019/013897 KR2019013897W WO2020085765A1 WO 2020085765 A1 WO2020085765 A1 WO 2020085765A1 KR 2019013897 W KR2019013897 W KR 2019013897W WO 2020085765 A1 WO2020085765 A1 WO 2020085765A1
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compound
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윤홍식
홍완표
김진주
이동훈
김명곤
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주식회사 엘지화학
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Priority to CN201980037279.1A priority Critical patent/CN112218861B/en
Publication of WO2020085765A1 publication Critical patent/WO2020085765A1/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
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D498/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains three hetero rings
    • C07D513/14—Ortho-condensed systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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
    • H10K50/15—Hole transporting layers

Definitions

  • the present specification relates to a polycyclic 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 are combined in an organic thin film and then paired to disappear, thereby emitting light.
  • the organic thin film may be composed of a single layer or multiple layers if necessary.
  • the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material.
  • An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween.
  • the organic material layer is often composed of a multi-layered structure composed of different materials, for example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like.
  • Patent Document 1 Korean Patent Publication No. 10-2012-032572
  • A1 and A2 are the same as or different from each other, and each independently a cyano group; Or a phenyl group substituted with a cyano group,
  • R1 to R4; And R5 and R6 which do not bind to * are the same as or different from each other, and each independently deuterium; Halogen group; Cyano group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or combine with adjacent groups to form a substituted or unsubstituted ring,
  • Y is an aryl group substituted or unsubstituted with one or more substituents selected from the group consisting of a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted heteroaryl group; Or a heteroaryl group containing O or S as a substituted or unsubstituted hetero element,
  • R not bonded to * is a substituted or unsubstituted aryl group
  • n1 to n6 are each an integer of 0 to 4, n1 + n2 + n3 + n4 + n5 + n6 is 1 or more,
  • n1 to n6 are each an integer of 2 or more, the substituents in 2 or more parentheses are the same or different from each other.
  • the present specification is 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, and at least one layer of the organic material layer includes a compound represented by Chemical Formula 1 above.
  • the compounds described herein can be used as a material for an organic material layer of an organic light emitting device.
  • the organic light emitting device including the compound according to an exemplary embodiment of the present specification, it is possible to obtain an organic light emitting device having excellent light emission efficiency, low driving voltage, high efficiency and long life.
  • FIG. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 6, and a cathode 10.
  • FIG. 2 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 6, an electron transport layer 8, and a cathode 10. It is done.
  • FIG. 3 is a substrate (1), anode (2), hole injection layer (3), hole transport layer (4), electron blocking layer (5), light emitting layer (6), hole blocking layer (7), electron injection and transport layer ( 9) and an example of an organic light emitting device comprising a cathode 10 is shown.
  • A1 and A2 are the same as or different from each other, and each independently a cyano group; Or a phenyl group substituted with a cyano group,
  • R1 to R4; And R5 and R6 which do not bind to * are the same as or different from each other, and each independently deuterium; Halogen group; Cyano group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or combine with adjacent groups to form a substituted or unsubstituted ring,
  • Y is an aryl group substituted or unsubstituted with one or more substituents selected from the group consisting of a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted heteroaryl group; Or a heteroaryl group containing O or S as a substituted or unsubstituted hetero element,
  • R not bonded to * is a substituted or unsubstituted aryl group
  • n1 to n6 are each an integer of 0 to 4, n1 + n2 + n3 + n4 + n5 + n6 is 1 or more,
  • n1 to n6 are each an integer of 2 or more, the substituents in 2 or more parentheses are the same or different from each other.
  • the compound represented by Chemical Formula 1 is a delayed fluorescent material.
  • the delayed fluorescent substance is a substance that converts the singlet exciton into a singlet exciton and converts it into light
  • the delayed fluorescent substance is a substance that converts the triplet exciton into singlet excitons and converts it into light, and exhibits a delayed fluorescent characteristic due to this process.
  • the phenomenon of delayed fluorescence also referred to as thermally activated delayed fluorescence (hereinafter abbreviated as 'TADF') refers to 75% of triplet excitons generated by electric field excitation at room temperature or at the temperature of the light emitting layer in the light emitting device, which is singlet This is a phenomenon where reverse intersystem crossing (hereinafter abbreviated as 'RISC') occurs with excitons.
  • 'RISC' reverse intersystem crossing
  • the singlet exciton generated by the crossing between inverses is fluoresced like the 25% singlet exciton generated by direct excitation, thereby enabling 100% internal quantum efficiency.
  • the delayed fluorescent material can convert both singlet excitons and triplet excitons to light, so 100% internal quantum efficiency is possible, so it is possible to overcome the limitations of lifetime and efficiency of phosphorescent materials.
  • the compound represented by Chemical Formula 1 may be included in the light emitting layer of the organic light emitting device. Since the energy difference between the triplet and the singlet is small in the compound represented by Chemical Formula 1, the rate and speed at which the exciton generated in the triplet moves to the singlet by reverse inter system (RISC) crossing Thus, since the time for the exciton to stay in the triplet is reduced, it has a characteristic of thermally activated delayed fluorescence (TADF), thereby increasing efficiency and lifetime when applied to the light emitting layer of the organic light emitting device.
  • RISC reverse inter system
  • substitution means that the hydrogen atom bonded to the carbon atom of the compound is replaced by another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where the substituent can be substituted, and when two or more are substituted , 2 or more substituents may be the same or different from each other.
  • substituted or unsubstituted in this specification is deuterium (-D); Halogen group; Cyano group; Hydroxy group; Silyl group; Boron group; Alkoxy groups; Alkyl groups; Cycloalkyl group; Aryl group; And one or two or more substituents selected from the group consisting of heterocyclic groups, or substituted with two or more substituents among the above-described substituents, or having no substituents.
  • a substituent having two or more substituents may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.
  • examples of the halogen group include fluorine (-F), chlorine (-Cl), bromine (-Br) or iodine (-I).
  • the silyl group may be represented by the formula of -SiY a Y b Y c , wherein Y a , Y b and Y c are each hydrogen; A substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group.
  • the silyl group specifically includes, but is not limited to, trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like. Does not.
  • the boron group may be represented by the formula of -BY d Y e , wherein Y d and Y e are each hydrogen; A substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group.
  • the boron group is specifically a trimethyl boron group, a triethyl boron group, a tert-butyl dimethyl boron group, a triphenyl boron group, a phenyl boron group, and the like, but is not limited thereto.
  • the alkyl group may be a straight chain or a branched chain, and carbon number is not particularly limited, but is preferably 1 to 60. According to an exemplary embodiment, the alkyl group has 1 to 30 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms.
  • alkyl group examples include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, n-pentyl group, hexyl group, n -Hexyl group, heptyl group, n-heptyl group, octyl group, n-octyl group, and the like, but is not limited to these.
  • the alkoxy group may be a straight chain, branched chain or cyclic chain.
  • the number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms.
  • Substituents comprising alkyl, alkoxy, and other alkyl group moieties described herein include both straight-chain or ground forms.
  • the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like, but is not limited thereto.
  • the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 40. According to one embodiment, the carbon number of the aryl group is 6 to 30.
  • the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a quarterphenyl group, etc., as a monocyclic aryl group, but is not limited thereto.
  • the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, triphenyl group, chrysenyl group, fluorenyl group, triphenylenyl group, etc., but is not limited thereto. no.
  • the fluorene group may be substituted, and two substituents may combine with each other to form a spiro structure.
  • Spirofluorene groups such as, (9,9-dimethylfluorene group), and It may be a substituted fluorene group such as (9,9-diphenylfluorene group). However, it is not limited thereto.
  • the heterocyclic group is a hetero atom and is a ring group containing at least one of N, O, P, S, Si, and Se, and carbon number is not particularly limited, but is preferably 2 to 60 carbon atoms. According to one embodiment, the number of carbon atoms in the heterocyclic group is 2 to 36.
  • heterocyclic group examples include pyridine group, pyrrole group, pyrimidine group, quinoline group, pyridazine group, furan group, thiophene group, imidazole group, pyrazole group, dibenzofuran group, dibenzothiophene group, Carbazole group, benzocarbazole group, benzonaphthofuran group, benzonaphthothiophene group, indenocarbazole group, indolocarbazole group, and the like, but are not limited thereto.
  • heterocyclic group may be applied, except that the heteroaryl group is aromatic.
  • ring is a hydrocarbon ring; Or a heterocycle.
  • the hydrocarbon ring may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and may be selected from examples of the cycloalkyl group or aryl group, except for the divalent group.
  • heterocyclic group can be applied to the heterocycle except that it is divalent.
  • A1 and A2 are the same as or different from each other, and each independently a cyano group; Or a phenyl group substituted with a cyano group.
  • A1 and A2 are respectively cyano groups.
  • A1 and A2 are each a phenyl group substituted with a cyano group.
  • one of A1 and A2 is a cyano group, and the other is a phenyl group substituted with a cyano group.
  • Y is substituted or unsubstituted with one or more substituents selected from the group consisting of a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted heteroaryl group.
  • Y is substituted or unsubstituted with one or more substituents selected from the group consisting of a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted heteroaryl group.
  • Y is a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, and a substituted or unsubstituted 2 to 30 carbon atoms. It is an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of heteroaryl groups.
  • Y is a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted aryl group with one or more substituents selected from the group consisting of a substituted or unsubstituted heteroaryl group, substituted with another substituent
  • Y is a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted aryl group with one or more substituents selected from the group consisting of a substituted or unsubstituted heteroaryl group, substituted with another substituent
  • Y is an aryl group substituted with a substituent containing a double bond
  • it forms radicals when exposed to electrons in the organic light emitting device, and thus has a lower luminescence lifetime than the compound of the present invention.
  • the compound of the present invention has a larger portion of overlap between the energy levels of HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) than the compound in which Y is a cyano group, resulting in a fluorescence quantum efficiency (PLQY). Yield) is high, so it has high efficiency when applied to organic light emitting devices.
  • Y is an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of a cyano group and an alkyl group having 1 to 20 carbon atoms; Or a heteroaryl group having 2 to 30 carbon atoms containing O or S as a substituted or unsubstituted hetero element.
  • Y is a phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of a cyano group and an alkyl group having 1 to 20 carbon atoms; A naphthyl group unsubstituted or substituted with one or more substituents selected from the group consisting of a cyano group and an alkyl group having 1 to 20 carbon atoms; A fluorene group unsubstituted or substituted with a cyano group and an alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted dibenzofuran group; Or a substituted or unsubstituted dibenzothiophene group.
  • Y is 6 to 30 aryl groups unsubstituted or substituted with one or more substituents selected from the group consisting of cyano, methyl and butyl groups; Or a heteroaryl group having 2 to 30 carbon atoms containing O or S as a substituted or unsubstituted hetero element.
  • Y is a phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of a cyano group, a methyl group, and a butyl group; A naphthyl group unsubstituted or substituted with one or more substituents selected from the group consisting of a cyano group, a methyl group, and a butyl group; A fluorene group unsubstituted or substituted with one or more substituents selected from the group consisting of a cyano group, a methyl group, and a butyl group; A substituted or unsubstituted dibenzofuran group; Or a substituted or unsubstituted dibenzothiophene group.
  • Y is a phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of a cyano group, a methyl group, and a butyl group; A naphthyl group unsubstituted or substituted with one or more substituents selected from the group consisting of a cyano group, a methyl group, and a butyl group; A fluorene group substituted with a methyl group; Dibenzofuran group; Or dibenzothiophene group.
  • Y is a phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of a cyano group, a methyl group, and a butyl group; Naphthyl group; A fluorene group substituted with a methyl group; Dibenzofuran group; Or dibenzothiophene group.
  • Y is a phenyl group substituted with a cyano group
  • a phenyl group substituted with a methyl group a phenyl group substituted with tert-butyl group
  • Naphthyl group 9,9-dimethylfluorene group
  • Dibenzofuran group Or dibenzothiophene group.
  • the n1 to n6 are each an integer of 0 to 4, n1 + n2 + n3 + n4 + n5 + n6 is 1 or more, and 2 or more parentheses when n1 to n6 are each an integer of 2 or more Substituents in the same or different from each other.
  • At least one of the three types of carbazole bound to benzene has a substituent, or two or more substituents combine with each other to form a ring, so that the compound and ring having no substituent attached to the carbazole Compared to compounds that do not contain condensed carbazole, it has the advantage of having excellent luminous efficiency and long life characteristics when applied to an organic light emitting device.
  • n1 + n2 + n3 + n4 + n5 + n6 is 1 to 24.
  • n1 + n2 + n3 + n4 + n5 + n6 is 1 to 16.
  • n1 + n2 + n3 + n4 + n5 + n6 is 1 to 8.
  • n1 + n2 + n3 + n4 + n5 + n6 is 1 to 6.
  • n1 + n2 + n3 + n4 + n5 + n6 is 1 to 4.
  • n1 + n2 + n3 + n4 + n5 + n6 is 1 to 3.
  • n1 + n2 + n3 + n4 + n5 + n6 is 1 or 2.
  • n1 + n2 + n3 + n4 + n5 + n6 is two or more.
  • n1 + n2 + n3 + n4 + n5 + n6 is 3 or more.
  • n1 + n2 + n3 + n4 + n5 + n6 is 4 or more.
  • any one of R5 and R6 or R is combined with *.
  • R is not bonded to the * is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.
  • R which is not bonded to * is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
  • R which is not bonded to the * is a substituted or unsubstituted phenyl group.
  • R which is not bonded to the * is a phenyl group.
  • the formula 1 is represented by the following formula 2 or 3.
  • R1 to R6, n1 to n6, Y, A1 and A2 are the same as defined in Formula 1,
  • R ' is a substituted or unsubstituted aryl group.
  • R ' is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.
  • R ' is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
  • R ' is a substituted or unsubstituted phenyl group.
  • R ' is a phenyl group.
  • the R1 To R4; And R5 and R6 which do not bind to * are the same as or different from each other, and each independently deuterium; Cyano group; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; 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, or combined with adjacent groups to form a substituted or unsubstituted 6 to 30 carbon ring.
  • R1 to R4; And R5 and R6 which do not bind to * are the same as or different from each other, and each independently deuterium; Cyano group; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or combined with adjacent groups to form a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms.
  • the R1 To R4; And R5 and R6 which do not bind to * are the same as or different from each other, and each independently deuterium; Cyano group; A substituted or unsubstituted methyl group; A substituted or unsubstituted propyl group; A substituted or unsubstituted butyl group; A substituted or unsubstituted phenyl group; A substituted or unsubstituted carbazole group; Or a substituted or unsubstituted benzocarbazole group, or combines with adjacent groups to form a ring to form any one of the following structures.
  • R11 is a substituted or unsubstituted aryl group
  • R12 and R13 are the same as or different from each other, and each independently an substituted or unsubstituted alkyl group,
  • the structures are deuterium; Cyano group; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or it may be substituted or unsubstituted with a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.
  • the R1 to R4; And R5 and R6 which do not bind to * are the same as or different from each other, and each independently deuterium; Cyano group; A methyl group unsubstituted or substituted with deuterium; Isopropyl group; tert-butyl group; Phenyl group; Carbazole; Or a benzocarbazole group, or combines with adjacent groups to form a ring to form any one of the following structures.
  • R11 is a substituted or unsubstituted aryl group
  • R12 and R13 are the same as or different from each other, and each independently an substituted or unsubstituted alkyl group,
  • the structures are deuterium; Cyano group; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or it may be substituted or unsubstituted with a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.
  • the structures are deuterium; Cyano group; A substituted or unsubstituted methyl group; A substituted or unsubstituted propyl group; A substituted or unsubstituted butyl group; A substituted or unsubstituted phenyl group; A substituted or unsubstituted carbazole group; Or it may be substituted or unsubstituted with a substituted or unsubstituted benzocarbazole group.
  • the structures are deuterium; Cyano group; A methyl group unsubstituted or substituted with deuterium; Isopropyl group; tert-butyl group; Phenyl group; Carbazole; Or it may be substituted or unsubstituted with a benzocarbazole group.
  • the structures are deuterium; Cyano group; CH 3 ; CD 3 ; Isopropyl group; tert-butyl group; Phenyl group; Carbazole; Or it may be substituted or unsubstituted with a benzocarbazole group.
  • R11 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
  • R11 is a substituted or unsubstituted phenyl group; Or a substituted or unsubstituted biphenyl group.
  • R11 is a phenyl group; Or a biphenyl group.
  • R12 and R13 are the same as or different from each other, and each independently an substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.
  • R12 and R13 are the same as or different from each other, and each independently a substituted or unsubstituted methyl group.
  • R12 and R13 are methyl groups.
  • the R1 To R4; And at least one of R5 and R6 which does not bind to * forms a ring by combining with an adjacent group to form a benzocarbazole ring.
  • the R1 To R4; And * and at least one of R5 and R6 which do not bind to form a ring by combining with an adjacent group to form a benzocarbazole ring one of the following structures.
  • the formula 1 is represented by any one of the following structures.
  • the triplet energy level of the compound represented by Chemical Formula 1 is 2.1 eV or more, preferably 2.1 eV or more and 3.0 eV or less, 2.2 eV or more, 3.0 eV or less, 2.4 eV or more 2.9 eV or less.
  • the triplet energy level of the compound represented by Chemical Formula 1 satisfies the above range, electron injection is facilitated and the exciton formation rate is increased, so that the luminous efficiency is increased.
  • the difference between the singlet energy level and the triplet energy level of the compound represented by Formula 1 is 0 eV or more and 0.3 eV or less, preferably 0 eV or more and 0.2 eV Is below.
  • the exciton generated in the triplet is converted into a singlet by inverse transition (RISC).
  • RISC inverse transition
  • the triplet energy can be measured using a spectral device such as JASCO FP-8600 capable of measuring fluorescence and phosphorescence, and in the case of measurement conditions, toluene or TIEF is used as a solvent in a cryogenic state using liquid nitrogen.
  • a spectral device such as JASCO FP-8600 capable of measuring fluorescence and phosphorescence
  • toluene or TIEF is used as a solvent in a cryogenic state using liquid nitrogen.
  • the electrons from the light source reverse, the time for the electrons to stay in the triplet is much longer than the time in the singlet, so it is possible to separate the two components in the cryogenic state.
  • the singlet energy is measured using a fluorescent device such as JASCO FP-8600, and the light source is irradiated at room temperature, unlike the triplet energy measurement method described above.
  • compounds having various energy band gaps can be synthesized by introducing various substituents to the core structure of the compound represented by Chemical Formula 1.
  • the HOMO and LUMO energy levels of the compound can be adjusted by introducing various substituents to the core structure having the above structure.
  • the organic light emitting device includes 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, and at least one layer of the organic material layer comprises the above-described compound.
  • the organic light-emitting device of the present specification may be manufactured by a conventional method and material for manufacturing an organic light-emitting device, except for forming one or more organic material layers using the compound represented by Chemical Formula 1 above.
  • an organic light emitting device having an organic material layer including the compound represented by Compound 1 it may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method.
  • the solution application method means spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited to these.
  • the organic material layer of the organic light emitting device of the present specification may have a single layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked.
  • the organic light emitting device of the present invention is a hole transport layer, a hole injection layer, an electron blocking layer, a layer simultaneously performing hole transport and hole injection, an electron transport layer, an electron injection layer, a hole blocking layer, and an electron transport and injection as an organic material layer It may have a structure including one or more of the layers.
  • the structure of the organic light emitting device of the present specification is not limited thereto, and may include fewer or more organic material layers.
  • the organic material layer includes a hole transport layer or a hole injection layer, and the hole transport layer or the hole injection layer may include a compound represented by Formula 1 described above.
  • the organic material layer may include an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer may include a compound represented by Formula 1 described above.
  • the organic material layer includes a light emitting layer, and the light emitting layer may include a compound represented by Chemical Formula 1 described above.
  • the organic material layer includes a light emitting layer, and the light emitting layer may include the compound as a host of the light emitting layer.
  • the organic material layer includes a light emitting layer
  • the light emitting layer may include the compound as a dopant in the light emitting layer.
  • the organic material layer includes a light emitting layer
  • the light emitting layer includes the compound as a dopant in the light emitting layer
  • the content of the dopant may be included in 1 part by weight to 60 parts by weight based on 100 parts by weight of the host, preferably 30 parts by weight to 50 parts by weight.
  • the organic material layer includes a light emitting layer, and the light emitting layer includes at least one selected from a condensed aromatic ring derivative and a heterocyclic compound as a host of the light emitting layer.
  • the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc.
  • heterocyclic compounds include carbazole derivatives , Dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
  • the emission layer may include the compound as a dopant, and further include a compound represented by Formula F as a host, but is not limited thereto.
  • L13 is a substituted or unsubstituted (b + 1) valent aryl group; Or a substituted or unsubstituted (b + 1) valent heteroaryl group,
  • G11 and G12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Cyano group; Or a heteroaryl group containing O or S,
  • b13 is an integer from 1 to 3, and when b13 is 2 or more, L13 is the same as or different from each other,
  • b is 1 or 2
  • if b is 2 Are the same or different from each other.
  • the organic material layer includes a light emitting layer
  • the light emitting layer includes a dopant containing the above-described compound and a host represented by Formula F in a weight ratio of 1:99 to 50:50.
  • L13 is a substituted or unsubstituted (b + 1) valent aryl group having 6 to 16 carbon atoms; Or a substituted or unsubstituted (b + 1) valent heteroaryl group having 2 to 16 carbon atoms.
  • L13 is a substituted or unsubstituted (b + 1) valent aryl group having 6 to 12 carbon atoms; Or a substituted or unsubstituted (b + 1) valent heteroaryl group having 2 to 12 carbon atoms.
  • L13 is a substituted or unsubstituted (b + 1) valent phenyl group; A substituted or unsubstituted (b + 1) valent biphenyl group; A substituted or unsubstituted (b + 1) valent dibenzofuranyl group; Or a substituted or unsubstituted (b + 1) valent pyridinyl group.
  • the substituent of the (b + 1) valent aryl group is an aryl group substituted with a heteroaryl group.
  • G11 and G12 are the same as or different from each other, and each independently hydrogen; Or cyano group.
  • b13 is 2.
  • the compound represented by Formula F is any one selected from the following compounds.
  • the organic material layer includes a light emitting layer
  • the light emitting layer includes the compound
  • the content of the fluorescent light-emitting material may be included from 0 parts by weight to 10 parts by weight based on 100 parts by weight of the compound. Since the fluorescent light-emitting material receives excitons from the compound and finally emits light, it is possible to increase the color purity of the device using a fluorescent light-emitting material having a narrow half-width, and prevent exciton-polaron quenching of the compound Therefore, there is an advantage of increasing the life of the device.
  • the half width refers to the thickness of the peak at a height that is half (1/2) of the maximum emission peak height on the emission spectrum.
  • Examples of the fluorescent material may be represented by anthracene-based compounds, pyrene-based compounds, florantene-based compounds, perylene-based compounds, boron-based compounds, or the following structures, but are not limited thereto.
  • 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 organic light emitting device may have a stacked structure as described below, but is not limited thereto.
  • the structure of the organic light emitting device of the present specification may have a structure as shown in FIGS. 1 to 3, but is not limited thereto.
  • FIG. 1 illustrates the structure of an organic light emitting device in which an anode 2, a light emitting layer 6, and a cathode 10 are sequentially stacked on a substrate 1.
  • the compound may be included in the light emitting layer (3).
  • an anode 2 a hole injection layer 3, a hole transport layer 4, a light emitting layer 6, an electron transport layer 8, and a cathode 10 are sequentially stacked on an organic light emitting device on a substrate 1
  • the structure is illustrated.
  • the organic light emitting device uses a metal vapor deposition (PVD) method, such as sputtering or e-beam evaporation, to have a metal or conductive metal oxide on the substrate or alloys thereof
  • PVD metal vapor deposition
  • an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, an electron transport layer and an electron injection layer, and then depositing a material that can be used as a cathode thereon Can be.
  • an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.
  • the organic material layer may be a multi-layered structure including a hole injection layer, a hole transport layer, an electron injection and electron transport layer, an electron blocking layer, a light emitting layer and an electron transport layer, an electron injection layer, an electron injection and electron transport layer, and the like. However, it is not limited thereto, and may be a single-layer structure.
  • the organic material layer may be made by using a variety of polymer materials, such as a solvent process (e.g., spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer), not a deposition method. Can be prepared in layers.
  • the positive electrode is an electrode for injecting holes
  • a positive electrode material is preferably a material having a large work function to facilitate hole injection into an organic material layer.
  • Specific examples of the positive electrode 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), and indium zinc oxide (IZO); A combination of metal and oxide such as ZnO: Al or SnO 2 : Sb; 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 that injects electrons
  • the cathode material is preferably a material having a small work function to facilitate electron injection into an 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;
  • There is a multilayer structure material such as LiF / Al or LiO 2 / Al, but is not limited thereto.
  • the hole injection layer is a layer that serves to smoothly inject holes from the anode to the light emitting layer.
  • a hole injection material can be well injected with holes from the anode, and HOMO (highest occupied) of the hole injection material It is preferable that the molecular orbital is 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 substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based substances.
  • the hole injection layer may have a thickness of 1 to 150 nm.
  • the thickness of the hole injection layer is 1 nm or more, there is an advantage of preventing the hole injection characteristics from being deteriorated. If 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 is an advantage that can be prevented.
  • the hole transport layer may serve to facilitate the transport of holes.
  • a material capable of receiving holes from the anode or the hole injection layer and transporting them to the light emitting layer is suitable for a material having high mobility for holes.
  • Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, but are not limited thereto.
  • An electron blocking layer may be provided between the hole transport layer and the light emitting layer.
  • the electron blocking layer may be a material known in the art.
  • the light emitting layer may emit red, green, or blue light, and may be made of a phosphorescent material or a fluorescent material.
  • a material capable of emitting light in the visible light region by receiving and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively is preferably a material having good quantum efficiency for fluorescence or phosphorescence.
  • Specific examples include 8-hydroxy-quinoline aluminum complex (Alq 3 ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole compounds; Poly (p-phenylenevinylene) (PPV) polymers; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited to these.
  • Alq 3 8-hydroxy-quinoline aluminum complex
  • Carbazole-based compounds Dimerized styryl compounds
  • BAlq 10-hydroxybenzo quinoline-metal compound
  • Benzoxazole, benzthiazole and benzimidazole compounds Benzoxazole, benzthiazole and benzimidazole compounds
  • Poly (p-phenylenevinylene) (PPV) polymers Spiro compounds
  • Polyfluorene, rubrene, and the like but are not limited to these.
  • the host material of the light emitting layer includes a condensed aromatic ring derivative or a heterocyclic compound.
  • condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc.
  • heterocyclic compounds include carbazole derivatives, dibenzofuran derivatives, and ladder types Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
  • PIQIr (acac) bis (1-phenylisoquinoline) acetylacetonateiridium
  • PQIr (acac) bis (1-phenylquinoline) acetylacetonate iridium
  • PQIr (tris (1-phenylquinoline) iridium are used as emission dopants.
  • Phosphorescent materials such as octaethylporphyrin platinum (PtOEP), or fluorescent materials such as Alq 3 (tris (8-hydroxyquinolino) aluminum) may be used, but is not limited thereto.
  • a phosphorescent material such as Ir (ppy) 3 (fac tris (2-phenylpyridine) iridium), or Alq3 (tris (8-hydroxyquinolino) aluminum), anthracene-based compound, or pyrene-based light emitting dopant Fluorescent materials such as compounds and boron-based compounds may be used, but are not limited thereto.
  • a phosphorescent material such as (4,6-F2ppy) 2 Irpic is used as a light emitting dopant, but spiro-DPVBi, spiro-6P, distylbenzene (DSB), distriarylene (DSA), Fluorescent materials such as PFO-based polymers, PPV-based polymers, anthracene-based compounds, pyrene-based compounds, and boron-based compounds may be used, but are not limited thereto.
  • 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 well and transferring them to the light emitting layer, a material having high mobility for electrons is suitable. Specific examples include the Al complex of 8-hydroxyquinoline; Complexes including Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited to these.
  • the thickness of the electron transport layer may be 1 to 50 nm. When the thickness of the electron transport layer is 1 nm or more, there is an advantage of preventing the electron transport properties from deteriorating, and when it is 50 nm or less, the thickness of the electron transport layer is too thick to prevent the driving voltage from rising to improve the movement of electrons. There are advantages.
  • the electron injection layer may serve to facilitate injection of electrons.
  • the electron injection material has the ability to transport electrons, has an electron injection effect from the cathode, has an excellent electron injection effect on the light emitting layer or the light emitting material, prevents movement of excitons generated in the light emitting layer to the hole injection layer, and also , A compound having excellent thin film forming ability is preferred.
  • fluorenone anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and their derivatives, metal Complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.
  • 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) ( There are o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, It is not limited to this.
  • the hole blocking layer is a layer that prevents the cathode from reaching the hole, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complex, and the like, but are not limited thereto.
  • the organic light emitting device may be a front emission type, a back emission type, or a double-sided emission type depending on the material used.
  • the compound represented by Chemical Formula 1 may be prepared from various types of isophthalonitrile substituted with halide as follows. Various compounds in the specific examples were synthesized through the following manufacturing method.
  • the glass substrate coated with ITO Indium Tin Oxide
  • ITO Indium Tin Oxide
  • Fischer Fischer Co.
  • distilled water filtered secondarily by a filter of Millipore Co. was used as distilled water.
  • ultrasonic cleaning was repeated twice for 10 minutes with distilled water.
  • ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner.
  • the substrate was transferred to a vacuum evaporator.
  • Each thin film was laminated on the prepared ITO transparent electrode with a vacuum degree of 5.0 ⁇ 10 -4 ⁇ by vacuum deposition.
  • a hole injection layer was formed by thermal vacuum deposition of hexaazatriphenylene-hexanitrile (HAT-CN) to a thickness of 500 Pa on ITO.
  • the following compound NPB was vacuum deposited on the hole injection layer to form a hole transport layer (300 kPa).
  • the following compound EB1 was vacuum deposited on the hole transport layer to a thickness of 100 mm 2 to form an electron blocking layer (100 mm 2).
  • the compound m-CBP and 4CzIPN having a thickness of 300 mm 3 were vacuum deposited on the electron blocking layer at a weight ratio of 70:30 to form a light emitting layer.
  • a hole blocking layer was formed by vacuum-depositing the following compound HB1 with a thickness of 100 mm 2 on the light emitting layer.
  • the following compound ET1 and the compound LiQ were vacuum deposited on the hole blocking layer at a weight ratio of 1: 1 to form an electron injection and transport layer with a thickness of 300 Pa.
  • lithium fluoride (LiF) with a thickness of 12 ⁇ and aluminum with a thickness of 2,000 ⁇ were sequentially deposited to form a negative electrode.
  • the deposition rate of the organic material was maintained at 0.4 ⁇ / sec to 0.7 ⁇ / sec
  • the lithium fluoride of the negative electrode was maintained at a deposition rate of 0.3 ⁇ / sec
  • aluminum at 2 ⁇ / sec.
  • An organic light emitting device was manufactured by maintaining 10 ⁇ 7 torr to 5 ⁇ 10 ⁇ 6 torr.
  • An organic light emitting diode was manufactured according to the same method as Comparative Example 1-1 except for using the compound of Table 1 below instead of the compound 4CzIPN in Comparative Example 1-1.
  • An organic light emitting diode was manufactured according to the same method as Comparative Example 1-1 except for using the compounds of T1 to T3 below instead of the compound 4CzIPN in Comparative Example 1-1.
  • the device of Experimental Examples 1-1 to 1-12 using the compound of Formula 1 has a lower voltage and improved efficiency than the device of the compound 4CzIPN in Comparative Example 1-1. .
  • the compound according to the present invention has excellent luminescence ability and high color purity, and thus can be applied to a delayed fluorescent organic light emitting device.
  • the glass substrate coated with ITO Indium Tin Oxide
  • ITO Indium Tin Oxide
  • Fischer Fischer Co.
  • distilled water filtered secondarily by a filter of Millipore Co. was used as distilled water.
  • ultrasonic cleaning was repeated twice for 10 minutes with distilled water.
  • ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner.
  • the substrate was transferred to a vacuum evaporator.
  • Each thin film was laminated on the prepared ITO transparent electrode with a vacuum degree of 5.0 ⁇ 10 -4 ⁇ by vacuum deposition.
  • a hole injection layer was formed by thermal vacuum deposition of hexaazatriphenylene-hexanitrile (HAT-CN) to a thickness of 500 Pa on ITO.
  • the following compound NPB was vacuum deposited on the hole injection layer to form a hole transport layer (300 kPa).
  • the following compound EB1 was vacuum deposited on the hole transport layer to a thickness of 100 mm 2 to form an electron blocking layer (100 mm 2).
  • the following compound m-CBP 4CzIPN and GD1 were deposited on the electron blocking layer at a thickness of 300 mm 3 in a weight ratio of 68: 30: 2 to form a light emitting layer.
  • a hole blocking layer was formed by vacuum-depositing the following compound HB1 with a thickness of 100 mm 2 on the light emitting layer.
  • the following compound ET1 and the compound LiQ were vacuum deposited on the hole blocking layer at a weight ratio of 1: 1 to form an electron injection and transport layer with a thickness of 300 Pa.
  • lithium fluoride (LiF) with a thickness of 12 ⁇ and aluminum with a thickness of 2,000 ⁇ were sequentially deposited to form a negative electrode.
  • the deposition rate of the organic material was maintained at 0.4 ⁇ / sec to 0.7 ⁇ / sec
  • the lithium fluoride of the negative electrode was maintained at a deposition rate of 0.3 ⁇ / sec
  • aluminum at 2 ⁇ / sec.
  • An organic light emitting device was manufactured by maintaining 10 ⁇ 7 torr to 5 ⁇ 10 ⁇ 6 torr.
  • An organic light emitting diode was manufactured according to the same method as Comparative Example 2-1 except for using the compound of Table 2 below instead of the compound 4CzIPN in Comparative Example 2-1.
  • An organic light emitting diode was manufactured according to the same method as Comparative Example 2-1 except for using the compound of Table 2 below instead of the compound 4CzIPN in Comparative Example 2-1.
  • the driving voltage (V) and the current efficiency (cd / A), 3000 cd, measured at a current density of 10 mA / cm 2 for the organic light emitting devices of Experimental Examples 2-1 to 2-12 and Comparative Examples 2-1 to 2-4 CIE color coordinates measured at a luminance of / m 2 were measured, and are shown in Table 2 below.
  • the compound according to the present invention has excellent luminescence ability and is capable of tuning the emission wavelength, thereby realizing an organic light emitting device having high color purity.

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Abstract

The present specification provides: a compound represented by chemical formula 1; and an organic light-emitting element comprising same.

Description

다환 화합물 및 이를 포함하는 유기발광소자Polycyclic compound and organic light emitting device including same
본 출원은 2018년 10월 22일 한국특허청에 제출된 한국 특허 출원 제 10-2018-0125957호의 출원일의 이익을 주장하며, 그 내용 전부는 본 명세서에 포함된다.This application claims the benefit of the filing date of Korean Patent Application No. 10-2018-0125957 filed with the Korean Intellectual Property Office on October 22, 2018, all of which is incorporated herein.
본 명세서는 다환 화합물 및 이를 포함하는 유기발광소자에 관한 것이다.The present specification relates to a polycyclic 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 정공이 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 are combined in an organic thin film and then paired to disappear, thereby emitting light. The organic thin film may be composed of a single layer or multiple layers if necessary.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기 발광 소자는 통상 양극과 음극 및 이 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물층은 유기 발광 소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층 등으로 이루어 질 수 있다. 이러한 유기 발광 소자의 구조에서 두 전극 사이에 전압을 걸어주게 되면 양극에서는 정공이, 음극에서는 전자가 유기물층에 주입되게 되고, 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 다시 바닥상태로 떨어질 때 빛이 나게 된다. In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often composed of a multi-layered structure composed of different materials, for example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected at the anode, and electrons are injected at the cathode, and an exciton is formed when the injected holes meet the electrons. When it falls to the ground again, it will shine.
상기와 같은 유기 발광 소자를 위한 새로운 재료의 개발이 계속 요구되고 있다.The development of new materials for such organic light-emitting devices continues to be required.
[선행기술문헌][Advanced technical literature]
(특허문헌 1) 한국특허공개 제10-2012-032572호(Patent Document 1) Korean Patent Publication No. 10-2012-032572
본 명세서에는 화합물 및 이를 포함하는 유기발광소자가 기재된다.In this specification, a compound and an organic light emitting device including the same are described.
본 명세서는 하기 화학식 1로 표시되는 화합물을 제공한다.The present specification provides a compound represented by Formula 1 below.
[화학식 1][Formula 1]
Figure PCTKR2019013897-appb-I000001
Figure PCTKR2019013897-appb-I000001
상기 화학식 1에 있어서,In Chemical Formula 1,
A1 및 A2는 서로 같거나 상이하고, 각각 독립적으로 시아노기; 또는 시아노기로 치환된 페닐기이며,A1 and A2 are the same as or different from each other, and each independently a cyano group; Or a phenyl group substituted with a cyano group,
R5 및 R6 중 어느 하나 또는 R은 *와 결합하고, Either R5 or R6 or R is combined with *,
R1 내지 R4; 및 *와 결합하지 않는 R5 및 R6는 서로 같거나 상이하고, 각각 독립적으로 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 사이클로알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이거나, 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하며,R1 to R4; And R5 and R6 which do not bind to * are the same as or different from each other, and each independently deuterium; Halogen group; Cyano group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or combine with adjacent groups to form a substituted or unsubstituted ring,
Y는 시아노기, 치환 또는 비치환된 알킬기, 치환 또는 비치환된 시클로알킬기 및 치환 또는 비치환된 헤테로아릴기로 이루어진 군으로부터 선택된 1 이상의 치환기로 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 이종원소로 O 또는 S를 포함하는 헤테로아릴기이고,Y is an aryl group substituted or unsubstituted with one or more substituents selected from the group consisting of a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted heteroaryl group; Or a heteroaryl group containing O or S as a substituted or unsubstituted hetero element,
*와 결합하지 않는 R은 치환 또는 비치환된 아릴기이며,R not bonded to * is a substituted or unsubstituted aryl group,
n1 내지 n6은 각각 0 내지 4의 정수이고, n1+n2+n3+n4+n5+n6는 1 이상이며,n1 to n6 are each an integer of 0 to 4, n1 + n2 + n3 + n4 + n5 + n6 is 1 or more,
n1 내지 n6가 각각 2 이상의 정수인 경우 2 이상의 괄호 내의 치환기는 서로 같거나 상이하다.When n1 to n6 are each an integer of 2 or more, the substituents in 2 or more parentheses are the same or different from each other.
또한, 본 명세서는 제1 전극; 상기 제1 전극과 대향하여 구비되는 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비되는 1층 이상의 유기물층을 포함하고, 상기 유기물층 중 1층 이상이 전술한 화학식 1로 표시되는 화합물을 포함하는 것인 유기 발광 소자를 제공한다.In addition, the present specification is 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, and at least one layer of the organic material layer includes a compound represented by Chemical Formula 1 above.
본 명세서에 기재된 화합물은 유기 발광 소자의 유기물층의 재료로서 사용될 수 있다. The compounds described herein can be used as a material for an organic material layer of an organic light emitting device.
본 명세서의 일 실시상태에 따른 화합물을 포함하는 유기 발광 소자를 제조하는 경우, 발광 효율이 우수하고, 낮은 구동전압, 고효율 및 장수명을 갖는 유기 발광 소자를 얻을 수 있다.When manufacturing the organic light emitting device including the compound according to an exemplary embodiment of the present specification, it is possible to obtain an organic light emitting device having excellent light emission efficiency, low driving voltage, high efficiency and long life.
도 1은 기판(1), 양극(2), 발광층(6) 및 음극(10)으로 이루어진 유기발광소자의 예를 도시한 것이다.1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 6, and a cathode 10.
도 2는 기판 (1), 양극(2), 정공주입층(3), 정공수송층(4), 발광층(6), 전자수송층(8) 및 음극(10)으로 이루어진 유기발광소자의 예를 도시한 것이다.FIG. 2 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 6, an electron transport layer 8, and a cathode 10. It is done.
도 3은 기판 (1), 양극(2), 정공주입층(3), 정공수송층(4), 전자차단층(5), 발광층(6), 정공차단층(7), 전자 주입 및 수송층(9) 및 음극(10)으로 이루어진 유기발광소자의 예를 도시한 것이다.3 is a substrate (1), anode (2), hole injection layer (3), hole transport layer (4), electron blocking layer (5), light emitting layer (6), hole blocking layer (7), electron injection and transport layer ( 9) and an example of an organic light emitting device comprising a cathode 10 is shown.
[부호의 설명][Description of codes]
1: 기판1: Substrate
2: 양극2: anode
3: 정공주입층3: hole injection layer
4: 정공수송층4: hole transport layer
5: 전자차단층5: electron blocking layer
6: 발광층6: light emitting layer
7: 정공차단층7: hole blocking layer
8: 전자수송층8: electron transport layer
9: 전자 주입 및 수송층9: electron injection and transport layer
10: 음극10: cathode
이하 본 명세서에 대하여 더욱 상세히 설명한다. Hereinafter, the present specification will be described in more detail.
본 명세서는 하기 화학식 1로 표시되는 화합물을 제공한다. The present specification provides a compound represented by Formula 1 below.
[화학식 1][Formula 1]
Figure PCTKR2019013897-appb-I000002
Figure PCTKR2019013897-appb-I000002
상기 화학식 1에 있어서,In Chemical Formula 1,
A1 및 A2는 서로 같거나 상이하고, 각각 독립적으로 시아노기; 또는 시아노기로 치환된 페닐기이며,A1 and A2 are the same as or different from each other, and each independently a cyano group; Or a phenyl group substituted with a cyano group,
R5 및 R6 중 어느 하나 또는 R은 *와 결합하고, Either R5 or R6 or R is combined with *,
R1 내지 R4; 및 *와 결합하지 않는 R5 및 R6는 서로 같거나 상이하고, 각각 독립적으로 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 사이클로알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이거나, 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하며,R1 to R4; And R5 and R6 which do not bind to * are the same as or different from each other, and each independently deuterium; Halogen group; Cyano group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or combine with adjacent groups to form a substituted or unsubstituted ring,
Y는 시아노기, 치환 또는 비치환된 알킬기, 치환 또는 비치환된 시클로알킬기 및 치환 또는 비치환된 헤테로아릴기로 이루어진 군으로부터 선택된 1 이상의 치환기로 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 이종원소로 O 또는 S를 포함하는 헤테로아릴기이고,Y is an aryl group substituted or unsubstituted with one or more substituents selected from the group consisting of a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted heteroaryl group; Or a heteroaryl group containing O or S as a substituted or unsubstituted hetero element,
*와 결합하지 않는 R은 치환 또는 비치환된 아릴기이며,R not bonded to * is a substituted or unsubstituted aryl group,
n1 내지 n6은 각각 0 내지 4의 정수이고, n1+n2+n3+n4+n5+n6는 1 이상이며,n1 to n6 are each an integer of 0 to 4, n1 + n2 + n3 + n4 + n5 + n6 is 1 or more,
n1 내지 n6가 각각 2 이상의 정수인 경우 2 이상의 괄호 내의 치환기는 서로 같거나 상이하다.When n1 to n6 are each an integer of 2 or more, the substituents in 2 or more parentheses are the same or different from each other.
상기 화학식 1로 표시되는 화합물은 지연 형광 물질이다. 지연 형광 물질은 일중항 엑시톤을 삼중항 엑시톤으로 바꾸어 빛으로 전환하는 인광 물질과 달리, 삼중항 엑시톤을 일중항 엑시톤로 바꾸어 빛으로 전환하는 물질이며, 이 과정 때문에 지연 형광 특색을 보인다. 지연 형광(열 여기형 지연 형광이라고도 함: Thermally Activated Delayed Fluorescence: 이하, 적절히 'TADF'라고 약기함) 현상이란 실온 또는 발광 소자 중의 발광층 온도에서 전계 여기에 의해 발생한 75%의 삼중항 엑시톤이 일중항 엑시톤으로 역항간 교차(Reverse Intersystem Crossing: 이하, 적절히 'RISC'라고 약기함)가 일어나는 현상이다. 역항간 교차에 의해 발생한 일중항 엑시톤이 직접 여기에 의해 발생한 25%의 일중항 엑시톤와 마찬가지로 형광 발광하여 100%의 내부 양자 효율이 가능하다.The compound represented by Chemical Formula 1 is a delayed fluorescent material. The delayed fluorescent substance is a substance that converts the singlet exciton into a singlet exciton and converts it into light, whereas the delayed fluorescent substance is a substance that converts the triplet exciton into singlet excitons and converts it into light, and exhibits a delayed fluorescent characteristic due to this process. The phenomenon of delayed fluorescence (also referred to as thermally activated delayed fluorescence (hereinafter abbreviated as 'TADF')) refers to 75% of triplet excitons generated by electric field excitation at room temperature or at the temperature of the light emitting layer in the light emitting device, which is singlet This is a phenomenon where reverse intersystem crossing (hereinafter abbreviated as 'RISC') occurs with excitons. The singlet exciton generated by the crossing between inverses is fluoresced like the 25% singlet exciton generated by direct excitation, thereby enabling 100% internal quantum efficiency.
이론적으로 지연형광물질은 일중항 엑시톤과 삼중항 엑시톤을 모두 빛으로 바꿀 수 있기 때문에 100% 내부 양자 효율이 가능하므로, 인광 물질이 가지고 있는 수명과 효율의 한계를 극복할 수 있다.Theoretically, the delayed fluorescent material can convert both singlet excitons and triplet excitons to light, so 100% internal quantum efficiency is possible, so it is possible to overcome the limitations of lifetime and efficiency of phosphorescent materials.
본 명세서의 일 예에 따르면, 상기 화학식 1로 표시되는 화합물은 유기발광소자의 발광층에 포함될 수 있다. 상기 화학식 1로 표시되는 화합물은 삼중항과 일중항 간의 에너지 차이가 작기 때문에 삼중항에서 생성된 엑시톤이 역계간전이(RISC: Reverse Inter System. Crossing)에 의해 일중항으로 이동하는 비율 및 속도가 증가하여 삼중항에 엑시톤이 머무는 시간이 줄어들게 되므로 지연형광(TADF: Thermally Activated Delayed Fluorescence) 특성을 갖게 되고, 이로 인하여 유기발광소자의 발광층에 적용시 효율 및 수명이 증가하는 이점을 갖는다.According to an example of the present specification, the compound represented by Chemical Formula 1 may be included in the light emitting layer of the organic light emitting device. Since the energy difference between the triplet and the singlet is small in the compound represented by Chemical Formula 1, the rate and speed at which the exciton generated in the triplet moves to the singlet by reverse inter system (RISC) crossing Thus, since the time for the exciton to stay in the triplet is reduced, it has a characteristic of thermally activated delayed fluorescence (TADF), thereby increasing efficiency and lifetime when applied to the light emitting layer 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, it means that the component may further include other components, not to exclude 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 it is said that a member is positioned "on" another member, this includes not only the case where one member is in contact with the other member but also another member between the two members.
본 명세서에서 치환기의 예시들은 아래에서 설명하나, 이에 한정되는 것은 아니다.Examples of the substituent in this 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 the hydrogen atom bonded to the carbon atom of the compound is replaced by another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where the substituent can be substituted, and when two or more are substituted , 2 or more substituents may be the same or different from each other.
본 명세서에서 "치환 또는 비치환된" 이라는 용어는 중수소(-D); 할로겐기; 시아노기; 히드록시기; 실릴기; 붕소기; 알콕시기; 알킬기; 사이클로알킬기; 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 수도 있다.The term "substituted or unsubstituted" in this specification is deuterium (-D); Halogen group; Cyano group; Hydroxy group; Silyl group; Boron group; Alkoxy groups; Alkyl groups; Cycloalkyl group; Aryl group; And one or two or more substituents selected from the group consisting of heterocyclic groups, or substituted with two or more substituents among the above-described substituents, or having no substituents. For example, "a substituent having two or more substituents" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.
상기 치환기들의 예시들은 아래에서 설명하나, 이에 한정되는 것은 아니다. Examples of the substituents are described below, but are not limited thereto.
본 명세서에 있어서, 할로겐기의 예로는 불소(-F), 염소(-Cl), 브롬(-Br) 또는 요오드(-I)가 있다.In the present specification, examples of the halogen group include fluorine (-F), chlorine (-Cl), bromine (-Br) or iodine (-I).
본 명세서에 있어서, 실릴기는 -SiYaYbYc의 화학식으로 표시될 수 있고, 상기 Ya, Yb 및 Yc는 각각 수소; 치환 또는 비치환된 알킬기; 또는 치환 또는 비치환된 아릴기일 수 있다. 상기 실릴기는 구체적으로 트리메틸실릴기, 트리에틸실릴기, tert-부틸디메틸실릴기, 비닐디메틸실릴기, 프로필디메틸실릴기, 트리페닐실릴기, 디페닐실릴기, 페닐실릴기 등이 있으나 이에 한정되지 않는다. In the present specification, the silyl group may be represented by the formula of -SiY a Y b Y c , wherein Y a , Y b and Y c are each hydrogen; A substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group. The silyl group specifically includes, but is not limited to, trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like. Does not.
본 명세서에 있어서, 붕소기는 -BYdYe의 화학식으로 표시될 수 있고, 상기 Yd 및 Ye는 각각 수소; 치환 또는 비치환된 알킬기; 또는 치환 또는 비치환된 아릴기일 수 있다. 상기 붕소기는 구체적으로 트리메틸붕소기, 트리에틸붕소기, tert-부틸디메틸붕소기, 트리페닐붕소기, 페닐붕소기 등이 있으나 이에 한정되지 않는다.In the present specification, the boron group may be represented by the formula of -BY d Y e , wherein Y d and Y e are each hydrogen; A substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group. The boron group is specifically a trimethyl boron group, a triethyl boron group, a tert-butyl dimethyl boron group, a triphenyl boron group, a phenyl boron group, and the like, but is not limited thereto.
본 명세서에 있어서, 상기 알킬기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나 1 내지 60인 것이 바람직하다. 일 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 30이다. 또 하나의 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 20이다. 또 하나의 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 10이다. 알킬기의 구체적인 예로는 메틸기, 에틸기, 프로필기, n-프로필기, 이소프로필기, 부틸기, n-부틸기, 이소부틸기, tert-부틸기, 펜틸기, n-펜틸기, 헥실기, n-헥실기, 헵틸기, n-헵틸기, 옥틸기, n-옥틸기 등이 있으나, 이들에 한정되지 않는다.In the present specification, the alkyl group may be a straight chain or a branched chain, and carbon number is not particularly limited, but is preferably 1 to 60. According to an exemplary embodiment, the alkyl group has 1 to 30 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. Specific examples of the alkyl group are methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, n-pentyl group, hexyl group, n -Hexyl group, heptyl group, n-heptyl group, octyl group, n-octyl group, and the like, but is not limited to these.
본 명세서에 있어서, 상기 알콕시기는 직쇄, 분지쇄 또는 고리쇄일 수 있다. 알콕시기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 20인 것이 바람직하다. 구체적으로, 메톡시, 에톡시, n-프로폭시, i-프로필옥시, 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. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, i-propyloxy, 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, but is not limited thereto.
본 명세서에 기재된 알킬기, 알콕시기 및 그 외 알킬기 부분을 포함하는 치환체는 직쇄 또는 분쇄 형태를 모두 포함한다.Substituents comprising alkyl, alkoxy, and other alkyl group moieties described herein include both straight-chain or ground forms.
본 명세서에 있어서, 사이클로알킬기는 특별히 한정되지 않으나, 탄소수 3 내지 60인 것이 바람직하며, 일 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 30이다. 또 하나의 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 20이다. 또 하나의 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 6이다. 구체적으로 사이클로프로필기, 사이클로부틸기, 사이클로펜틸기, 사이클로헥실기, 사이클로헵틸기, 사이클로옥틸기 등이 있으나, 이에 한정되지 않는다. In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like, but is not limited thereto.
본 명세서에 있어서, 아릴기는 특별히 한정되지 않으나 탄소수 6 내지 60인 것이 바람직하며, 단환식 아릴기 또는 다환식 아릴기일 수 있다. 일 실시상태에 따르면, 상기 아릴기의 탄소수는 6 내지 40이다. 일 실시상태에 따르면, 상기 아릴기의 탄소수는 6 내지 30이다. 상기 아릴기가 단환식 아릴기로는 페닐기, 바이페닐기, 터페닐기, 쿼터페닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다. 상기 다환식 아릴기로는 나프틸기, 안트라세닐기, 페난트레닐기, 파이레닐기, 페릴레닐기, 트리페닐기, 크라이세닐기, 플루오레닐기, 트리페닐레닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 40. According to one embodiment, the carbon number of the aryl group is 6 to 30. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a quarterphenyl group, etc., as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, triphenyl group, chrysenyl group, fluorenyl group, triphenylenyl group, etc., but is not limited thereto. no.
본 명세서에 있어서, 플루오렌기는 치환될 수 있고, 치환기 2개가 서로 결합하여 스피로 구조를 형성할 수 있다.In the present specification, the fluorene group may be substituted, and two substituents may combine with each other to form a spiro structure.
상기 플루오렌기가 치환되는 경우,
Figure PCTKR2019013897-appb-I000003
,
Figure PCTKR2019013897-appb-I000004
등의 스피로플루오렌기,
Figure PCTKR2019013897-appb-I000005
(9,9-디메틸플루오렌기), 및
Figure PCTKR2019013897-appb-I000006
(9,9-디페닐플루오렌기) 등의 치환된 플루오렌기가 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorene group is substituted,
Figure PCTKR2019013897-appb-I000003
,
Figure PCTKR2019013897-appb-I000004
Spirofluorene groups such as,
Figure PCTKR2019013897-appb-I000005
(9,9-dimethylfluorene group), and
Figure PCTKR2019013897-appb-I000006
It may be a substituted fluorene group such as (9,9-diphenylfluorene group). However, it is not limited thereto.
본 명세서에 있어서, 헤테로고리기는 이종원자로 N, O, P, S, Si 및 Se 중 1개 이상을 포함하는 고리기로서, 탄소수는 특별히 한정되지 않으나 탄소수 2 내지 60인 것이 바람직하다. 일 실시상태에 따르면, 상기 헤테로고리기의 탄소수는 2 내지 36이다. 헤테로 고리기의 예로는 예로는 피리딘기, 피롤기, 피리미딘기, 퀴놀린기, 피리다진기, 퓨란기, 티오펜기, 이미다졸기, 피라졸기, 디벤조퓨란기, 디벤조티오펜기, 카바졸기, 벤조카바졸기, 벤조나프토퓨란기, 벤조나프토티오펜기, 인데노카바졸기, 인돌로카바졸기 등이 있으나, 이들에만 한정되는 것은 아니다.In the present specification, the heterocyclic group is a hetero atom and is a ring group containing at least one of N, O, P, S, Si, and Se, and carbon number is not particularly limited, but is preferably 2 to 60 carbon atoms. According to one embodiment, the number of carbon atoms in the heterocyclic group is 2 to 36. Examples of the heterocyclic group include pyridine group, pyrrole group, pyrimidine group, quinoline group, pyridazine group, furan group, thiophene group, imidazole group, pyrazole group, dibenzofuran group, dibenzothiophene group, Carbazole group, benzocarbazole group, benzonaphthofuran group, benzonaphthothiophene group, indenocarbazole group, indolocarbazole group, and the like, but are not limited thereto.
본 명세서에 있어서, 헤테로아릴기는 방향족인 것을 제외하고는 전술한 헤테로고리기에 관한 설명이 적용될 수 있다.In the present specification, a description of the aforementioned heterocyclic group may be applied, except that the heteroaryl group is aromatic.
본 명세서에 있어서, 인접한 기와 서로 결합하여 형성되는 치환 또는 비치환된 고리에서, "고리"는 탄화수소 고리; 또는 헤테로고리를 의미한다.In the present specification, in the substituted or unsubstituted ring formed by bonding with adjacent groups to each other, "ring" is a hydrocarbon ring; Or a heterocycle.
상기 탄화수소 고리는 방향족, 지방족 또는 방향족과 지방족의 축합고리일 수 있으며, 상기 2가기인 것을 제외하고 상기 시클로알킬기 또는 아릴기의 예시 중에서 선택될 수 있다.The hydrocarbon ring may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and may be selected from examples of the cycloalkyl group or aryl group, except for the divalent group.
본 명세서에 있어서, 방향족 탄화수소고리는 2가인 것을 제외하고는 상기 아릴기에 관한 설명이 적용될 수 있다.In this specification, the description of the aryl group can be applied, except that the aromatic hydrocarbon ring is divalent.
상기 헤테로고리는 2가인 것을 제외하고는 상기 헤테로고리기에 대한 설명이 적용될 수 있다.The description of the heterocyclic group can be applied to the heterocycle except that it is divalent.
본 명세서의 일 실시상태에 따르면, 상기 A1 및 A2는 서로 같거나 상이하고, 각각 독립적으로 시아노기; 또는 시아노기로 치환된 페닐기이다.According to an exemplary embodiment of the present specification, A1 and A2 are the same as or different from each other, and each independently a cyano group; Or a phenyl group substituted with a cyano group.
또 하나의 일 실시상태에 따르면, 상기 A1 및 A2는 각각 시아노기이다.According to another exemplary embodiment, A1 and A2 are respectively cyano groups.
또 하나의 일 실시상태에 따르면, 상기 A1 및 A2는 각각 시아노기로 치환된 페닐기이다.According to another exemplary embodiment, A1 and A2 are each a phenyl group substituted with a cyano group.
또 하나의 일 실시상태에 따르면, 상기 A1 및 A2 중 어느 하나는 시아노기이고, 나머지 하나는 시아노기로 치환된 페닐기이다.According to another exemplary embodiment, one of A1 and A2 is a cyano group, and the other is a phenyl group substituted with a cyano group.
본 명세서의 일 실시상태에 따르면, 상기 Y는 시아노기, 치환 또는 비치환된 알킬기, 치환 또는 비치환된 시클로알킬기 및 치환 또는 비치환된 헤테로아릴기로 이루어진 군으로부터 선택된 1 이상의 치환기로 치환 또는 비치환된 탄소수 6 내지 60의 아릴기; 또는 치환 또는 비치환된 이종원소로 O 또는 S를 포함하는 탄소수 2 내지 60의 헤테로아릴기이다. According to the exemplary embodiment of the present specification, Y is substituted or unsubstituted with one or more substituents selected from the group consisting of a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted heteroaryl group. Aryl group having 6 to 60 carbon atoms; Or a heteroaryl group having 2 to 60 carbon atoms containing O or S as a substituted or unsubstituted hetero element.
또 하나의 일 실시상태에 따르면, 상기 Y는 시아노기, 치환 또는 비치환된 알킬기, 치환 또는 비치환된 시클로알킬기 및 치환 또는 비치환된 헤테로아릴기로 이루어진 군으로부터 선택된 1 이상의 치환기로 치환 또는 비치환된 탄소수 6 내지 30의 아릴기; 또는 치환 또는 비치환된 이종원소로 O 또는 S를 포함하는 탄소수 2 내지 30의 헤테로아릴기이다. According to another exemplary embodiment, Y is substituted or unsubstituted with one or more substituents selected from the group consisting of a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted heteroaryl group. Aryl group having 6 to 30 carbon atoms; Or a heteroaryl group having 2 to 30 carbon atoms containing O or S as a substituted or unsubstituted hetero element.
또 하나의 일 실시상태에 있어서, 상기 Y는 시아노기, 치환 또는 비치환된 탄소수 1 내지 20의 알킬기, 치환 또는 비치환된 탄소수 3 내지 40의 시클로알킬기 및 치환 또는 비치환된 탄소수 2 내지 30의 헤테로아릴기로 이루어진 군으로부터 선택된 1 이상의 치환기로 치환 또는 비치환된 탄소수 6 내지 30의 아릴기이다. 상기 Y가 시아노기, 치환 또는 비치환된 알킬기, 치환 또는 비치환된 시클로알킬기 및 치환 또는 비치환된 헤테로아릴기로 이루어진 군으로부터 선택된 1 이상의 치환기로 치환 또는 비치환된 아릴기인 경우, 다른 치환기로 치환된 아릴기인 경우보다 유기발광소자에 적용시 효율 및 수명이 높은 소자를 얻을 수 있다. In another exemplary embodiment, Y is a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, and a substituted or unsubstituted 2 to 30 carbon atoms. It is an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of heteroaryl groups. When Y is a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted aryl group with one or more substituents selected from the group consisting of a substituted or unsubstituted heteroaryl group, substituted with another substituent When applied to the organic light emitting device than the aryl group, it is possible to obtain a device having higher efficiency and life.
구체적으로, 상기 Y가 이중결합을 포함하는 치환기로 치환된 아릴기인 경우, 유기발광소자 내에서 전자에 노출될 때 라디칼을 형성하므로 본 발명의 화합물보다 발광 수명이 낮다. 또한, 본 발명의 화합물은 상기 Y가 시아노기인 화합물보다 HOMO(highest occupied molecular orbital)와 LUMO(lowest unoccupied molecular　orbital)의 에너지 준위간의 오버랩(overlap)되는 부분이 넓어 형광양자효율(PLQY, Photoluminescence Quantum Yield)이 높으므로 유기발광소자에 적용시 높을 효율을 갖는다.Specifically, when Y is an aryl group substituted with a substituent containing a double bond, it forms radicals when exposed to electrons in the organic light emitting device, and thus has a lower luminescence lifetime than the compound of the present invention. In addition, the compound of the present invention has a larger portion of overlap between the energy levels of HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) than the compound in which Y is a cyano group, resulting in a fluorescence quantum efficiency (PLQY). Yield) is high, so it has high efficiency when applied to organic light emitting devices.
또 하나의 일 실시상태에 따르면, 상기 Y는 시아노기 및 탄소수 1 내지 20의 알킬기로 이루어진 군으로부터 선택된 1 이상의 치환기로 치환 또는 비치환된 탄소수 6 내지 30의 아릴기; 또는 치환 또는 비치환된 이종원소로 O 또는 S를 포함하는 탄소수 2 내지 30의 헤테로아릴기이다.According to another exemplary embodiment, Y is an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with one or more substituents selected from the group consisting of a cyano group and an alkyl group having 1 to 20 carbon atoms; Or a heteroaryl group having 2 to 30 carbon atoms containing O or S as a substituted or unsubstituted hetero element.
또 하나의 일 실시상태에 있어서, 상기 Y는 시아노기 및 탄소수 1 내지 20의 알킬기로 이루어진 군으로부터 선택된 1 이상의 치환기로 치환 또는 비치환된 페닐기; 시아노기 및 탄소수 1 내지 20의 알킬기로 이루어진 군으로부터 선택된 1 이상의 치환기로 치환 또는 비치환된 나프틸기; 시아노기 및 탄소수 1 내지 20의 알킬기로 치환 또는 비치환된 플루오렌기; 치환 또는 비치환된 디벤조퓨란기; 또는 치환 또는 비치환된 디벤조티오펜기이다.In another exemplary embodiment, Y is a phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of a cyano group and an alkyl group having 1 to 20 carbon atoms; A naphthyl group unsubstituted or substituted with one or more substituents selected from the group consisting of a cyano group and an alkyl group having 1 to 20 carbon atoms; A fluorene group unsubstituted or substituted with a cyano group and an alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted dibenzofuran group; Or a substituted or unsubstituted dibenzothiophene group.
또 하나의 일 실시상태에 따르면, 상기 Y는 시아노기, 메틸기 및 부틸기로 이루어진 군으로부터 선택된 1 이상의 치환기로 치환 또는 비치환된 6 내지 30의 아릴기; 또는 치환 또는 비치환된 이종원소로 O 또는 S를 포함하는 탄소수 2 내지 30의 헤테로아릴기이다.According to another exemplary embodiment, Y is 6 to 30 aryl groups unsubstituted or substituted with one or more substituents selected from the group consisting of cyano, methyl and butyl groups; Or a heteroaryl group having 2 to 30 carbon atoms containing O or S as a substituted or unsubstituted hetero element.
또 하나의 일 실시상태에 따르면, 상기 Y는 시아노기, 메틸기 및 부틸기로 이루어진 군으로부터 선택된 1 이상의 치환기로 치환 또는 비치환된 페닐기; 시아노기, 메틸기 및 부틸기로 이루어진 군으로부터 선택된 1 이상의 치환기로 치환 또는 비치환된 나프틸기; 시아노기, 메틸기 및 부틸기로 이루어진 군으로부터 선택된 1 이상의 치환기로 치환 또는 비치환된 플루오렌기; 치환 또는 비치환된 디벤조퓨란기; 또는 치환 또는 비치환된 디벤조티오펜기이다.According to another exemplary embodiment, Y is a phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of a cyano group, a methyl group, and a butyl group; A naphthyl group unsubstituted or substituted with one or more substituents selected from the group consisting of a cyano group, a methyl group, and a butyl group; A fluorene group unsubstituted or substituted with one or more substituents selected from the group consisting of a cyano group, a methyl group, and a butyl group; A substituted or unsubstituted dibenzofuran group; Or a substituted or unsubstituted dibenzothiophene group.
또 하나의 일 실시상태에 있어서, 상기 Y는 시아노기, 메틸기 및 부틸기로 이루어진 군으로부터 선택된 1 이상의 치환기로 치환 또는 비치환된 페닐기; 시아노기, 메틸기 및 부틸기로 이루어진 군으로부터 선택된 1 이상의 치환기로 치환 또는 비치환된 나프틸기; 메틸기로 치환된 플루오렌기; 디벤조퓨란기; 또는 디벤조티오펜기이다.In another exemplary embodiment, Y is a phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of a cyano group, a methyl group, and a butyl group; A naphthyl group unsubstituted or substituted with one or more substituents selected from the group consisting of a cyano group, a methyl group, and a butyl group; A fluorene group substituted with a methyl group; Dibenzofuran group; Or dibenzothiophene group.
또 하나의 일 실시상태에 있어서, 상기 Y는 시아노기, 메틸기 및 부틸기로 이루어진 군으로부터 선택된 1 이상의 치환기로 치환 또는 비치환된 페닐기; 나프틸기; 메틸기로 치환된 플루오렌기; 디벤조퓨란기; 또는 디벤조티오펜기이다.In another exemplary embodiment, Y is a phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of a cyano group, a methyl group, and a butyl group; Naphthyl group; A fluorene group substituted with a methyl group; Dibenzofuran group; Or dibenzothiophene group.
또 하나의 일 실시상태에 있어서, 상기 Y는 시아노기로 치환된 페닐기; 메틸기로 치환된 페닐기; tert-부틸기로 치환된 페닐기; 나프틸기; 9,9-다이메틸플루오렌기; 디벤조퓨란기; 또는 디벤조티오펜기이다.In another exemplary embodiment, Y is a phenyl group substituted with a cyano group; A phenyl group substituted with a methyl group; a phenyl group substituted with tert-butyl group; Naphthyl group; 9,9-dimethylfluorene group; Dibenzofuran group; Or dibenzothiophene group.
본 명세서의 일 실시상태에 따르면, 상기 n1 내지 n6은 각각 0 내지 4의 정수이고, n1+n2+n3+n4+n5+n6는 1 이상이며, n1 내지 n6가 각각 2 이상의 정수인 경우 2 이상의 괄호 내의 치환기는 서로 같거나 상이하다. 상기 화학식 1로 표시되는 화합물은 벤젠에 결합된 3 종의 카바졸 중 1 이상이 치환기를 갖거나, 2 이상의 치환기가 서로 결합하여 고리를 형성함으로써, 카바졸에 치환기가 결합되지 않는 화합물과 고리가 축합된 카바졸을 포함하지 않는 화합물보다, 유기발광소자에 적용시 우수한 발광 효율 및 장수명 특성을 갖는 이점이 있다.According to an exemplary embodiment of the present specification, the n1 to n6 are each an integer of 0 to 4, n1 + n2 + n3 + n4 + n5 + n6 is 1 or more, and 2 or more parentheses when n1 to n6 are each an integer of 2 or more Substituents in the same or different from each other. In the compound represented by Formula 1, at least one of the three types of carbazole bound to benzene has a substituent, or two or more substituents combine with each other to form a ring, so that the compound and ring having no substituent attached to the carbazole Compared to compounds that do not contain condensed carbazole, it has the advantage of having excellent luminous efficiency and long life characteristics when applied to an organic light emitting device.
본 명세서의 일 실시상태에 따르면, n1+n2+n3+n4+n5+n6는 1 내지 24이다.According to the exemplary embodiment of the present specification, n1 + n2 + n3 + n4 + n5 + n6 is 1 to 24.
본 명세서의 일 실시상태에 따르면, n1+n2+n3+n4+n5+n6는 1 내지 16이다.According to an exemplary embodiment of the present specification, n1 + n2 + n3 + n4 + n5 + n6 is 1 to 16.
본 명세서의 일 실시상태에 따르면, n1+n2+n3+n4+n5+n6는 1 내지 8이다.According to one embodiment of the present specification, n1 + n2 + n3 + n4 + n5 + n6 is 1 to 8.
본 명세서의 일 실시상태에 따르면, n1+n2+n3+n4+n5+n6는 1 내지 6이다.According to an exemplary embodiment of the present specification, n1 + n2 + n3 + n4 + n5 + n6 is 1 to 6.
본 명세서의 일 실시상태에 따르면, n1+n2+n3+n4+n5+n6는 1 내지 4이다.According to an exemplary embodiment of the present specification, n1 + n2 + n3 + n4 + n5 + n6 is 1 to 4.
본 명세서의 일 실시상태에 따르면, n1+n2+n3+n4+n5+n6는 1 내지 3이다.According to an exemplary embodiment of the present specification, n1 + n2 + n3 + n4 + n5 + n6 is 1 to 3.
본 명세서의 일 실시상태에 따르면, n1+n2+n3+n4+n5+n6는 1 또는 2이다.According to an exemplary embodiment of the present specification, n1 + n2 + n3 + n4 + n5 + n6 is 1 or 2.
본 명세서의 일 실시상태에 따르면, n1+n2+n3+n4+n5+n6는 2 이상이다.According to an exemplary embodiment of the present specification, n1 + n2 + n3 + n4 + n5 + n6 is two or more.
본 명세서의 일 실시상태에 따르면, n1+n2+n3+n4+n5+n6는 3 이상이다.According to one embodiment of the present specification, n1 + n2 + n3 + n4 + n5 + n6 is 3 or more.
본 명세서의 일 실시상태에 따르면, n1+n2+n3+n4+n5+n6는 4 이상이다.According to the exemplary embodiment of the present specification, n1 + n2 + n3 + n4 + n5 + n6 is 4 or more.
본 명세서의 일 실시상태에 있어서, 상기 R5 및 R6 중 어느 하나 또는 R은 *와 결합한다.In one embodiment of the present specification, any one of R5 and R6 or R is combined with *.
본 명세서의 일 실시상태에 따르면, 상기 *와 결합하지 않는 R은 치환 또는 비치환된 탄소수 6 내지 60의 아릴기이다.According to an exemplary embodiment of the present specification, R is not bonded to the * is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.
또 하나의 하나의 일 실시상태에 있어서, 상기 *와 결합하지 않는 R은 치환 또는 비치환된 탄소수 6 내지 30의 아릴기이다.In another one exemplary embodiment, R which is not bonded to * is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
또 하나의 하나의 일 실시상태에 따르면, 상기 *와 결합하지 않는 R은 치환 또는 비치환된 페닐기이다.According to another exemplary embodiment, R which is not bonded to the * is a substituted or unsubstituted phenyl group.
또 하나의 하나의 일 실시상태에 있어서, 상기 *와 결합하지 않는 R은 페닐기이다.In another one exemplary embodiment, R which is not bonded to the * is a phenyl group.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1은 하기 화학식 2 또는 3으로 표시된다.According to an exemplary embodiment of the present specification, the formula 1 is represented by the following formula 2 or 3.
[화학식 2][Formula 2]
Figure PCTKR2019013897-appb-I000007
Figure PCTKR2019013897-appb-I000007
[화학식 3][Formula 3]
Figure PCTKR2019013897-appb-I000008
Figure PCTKR2019013897-appb-I000008
상기 화학식 2 및 3에 있어서,In Chemical Formulas 2 and 3,
R1 내지 R6, n1 내지 n6, Y, A1 및 A2의 정의는 상기 화학식 1에서 정의한 바와 같고, R1 to R6, n1 to n6, Y, A1 and A2 are the same as defined in Formula 1,
R'는 치환 또는 비치환된 아릴기이다.R 'is a substituted or unsubstituted aryl group.
본 명세서의 일 실시상태에 따르면, 상기 R'는 치환 또는 비치환된 탄소수 6 내지 60의 아릴기이다.According to an exemplary embodiment of the present specification, R 'is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.
또 하나의 하나의 일 실시상태에 있어서, 상기 R'는 치환 또는 비치환된 탄소수 6 내지 30의 아릴기이다.In another one exemplary embodiment, R 'is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
또 하나의 하나의 일 실시상태에 따르면, 상기 R'는 치환 또는 비치환된 페닐기이다.According to another exemplary embodiment, R 'is a substituted or unsubstituted phenyl group.
또 하나의 하나의 일 실시상태에 있어서, 상기 R'는 페닐기이다.In another one exemplary embodiment, R 'is a phenyl group.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R4; 및 *와 결합하지 않는 R5 및 R6는 서로 같거나 상이하고, 각각 독립적으로 중수소; 시아노기; 치환 또는 비치환된 탄소수 1 내지 20의 알킬기; 치환 또는 비치환된 탄소수 6 내지 30의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 30의 헤테로고리기이거나, 인접한 기와 서로 결합하여 치환 또는 비치환된 탄소수 6 내지 30의 고리를 형성한다.According to an exemplary embodiment of the present specification, the R1 To R4; And R5 and R6 which do not bind to * are the same as or different from each other, and each independently deuterium; Cyano group; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; 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, or combined with adjacent groups to form a substituted or unsubstituted 6 to 30 carbon ring.
본 명세서의 일 실시상태에 따르면, R1 내지 R4; 및 *와 결합하지 않는 R5 및 R6는 서로 같거나 상이하고, 각각 독립적으로 중수소; 시아노기; 치환 또는 비치환된 탄소수 1 내지 20의 알킬기; 또는 치환 또는 비치환된 탄소수 6 내지 30의 아릴기이거나, 인접한 기와 서로 결합하여 치환 또는 비치환된 탄소수 6 내지 30의 방향족 탄화수소 고리를 형성한다.According to an exemplary embodiment of the present specification, R1 to R4; And R5 and R6 which do not bind to * are the same as or different from each other, and each independently deuterium; Cyano group; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or combined with adjacent groups to form a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R4; 및 *와 결합하지 않는 R5 및 R6는 서로 같거나 상이하고, 각각 독립적으로 중수소; 시아노기; 치환 또는 비치환된 메틸기; 치환 또는 비치환된 프로필기; 치환 또는 비치환된 부틸기; 치환 또는 비치환된 페닐기; 치환 또는 비치환된 카바졸기; 또는 치환 또는 비치환된 벤조카바졸기이거나, 인접한 기와 서로 결합하여 고리를 형성하여 하기 구조들 중 어느 하나를 이룬다.According to an exemplary embodiment of the present specification, the R1 To R4; And R5 and R6 which do not bind to * are the same as or different from each other, and each independently deuterium; Cyano group; A substituted or unsubstituted methyl group; A substituted or unsubstituted propyl group; A substituted or unsubstituted butyl group; A substituted or unsubstituted phenyl group; A substituted or unsubstituted carbazole group; Or a substituted or unsubstituted benzocarbazole group, or combines with adjacent groups to form a ring to form any one of the following structures.
Figure PCTKR2019013897-appb-I000009
Figure PCTKR2019013897-appb-I000009
Figure PCTKR2019013897-appb-I000010
Figure PCTKR2019013897-appb-I000010
Figure PCTKR2019013897-appb-I000011
Figure PCTKR2019013897-appb-I000011
상기 구조들에 있어서,In the above structures,
R11은 치환 또는 비치환된 아릴기이고,R11 is a substituted or unsubstituted aryl group,
R12 및 R13은 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 알킬기이며,R12 and R13 are the same as or different from each other, and each independently an substituted or unsubstituted alkyl group,
상기 구조들은 중수소; 시아노기; 치환 또는 비치환된 탄소수 1 내지 20의 알킬기; 치환 또는 비치환된 탄소수 6 내지 30의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 30의 헤테로아릴기로 치환 또는 비치환될 수 있다.The structures are deuterium; Cyano group; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or it may be substituted or unsubstituted with a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.
또 하나의 일 실시상태에 따르면, 상기 R1 내지 R4; 및 *와 결합하지 않는 R5 및 R6는 서로 같거나 상이하고, 각각 독립적으로 중수소; 시아노기; 중수소로 치환 또는 비치환된 메틸기; 이소프로필기; tert-부틸기; 페닐기; 카바졸기; 또는 벤조카바졸기이거나, 인접한 기와 서로 결합하여 고리를 형성하여 하기 구조들 중 어느 하나를 이룬다.According to another exemplary embodiment, the R1 to R4; And R5 and R6 which do not bind to * are the same as or different from each other, and each independently deuterium; Cyano group; A methyl group unsubstituted or substituted with deuterium; Isopropyl group; tert-butyl group; Phenyl group; Carbazole; Or a benzocarbazole group, or combines with adjacent groups to form a ring to form any one of the following structures.
Figure PCTKR2019013897-appb-I000012
Figure PCTKR2019013897-appb-I000012
Figure PCTKR2019013897-appb-I000013
Figure PCTKR2019013897-appb-I000013
Figure PCTKR2019013897-appb-I000014
Figure PCTKR2019013897-appb-I000014
상기 구조들에 있어서,In the above structures,
R11은 치환 또는 비치환된 아릴기이고,R11 is a substituted or unsubstituted aryl group,
R12 및 R13은 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 알킬기이며,R12 and R13 are the same as or different from each other, and each independently an substituted or unsubstituted alkyl group,
상기 구조들은 중수소; 시아노기; 치환 또는 비치환된 탄소수 1 내지 20의 알킬기; 치환 또는 비치환된 탄소수 6 내지 30의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 30의 헤테로아릴기로 치환 또는 비치환될 수 있다.The structures are deuterium; Cyano group; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or it may be substituted or unsubstituted with a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.
본 명세서의 일 실시상태에 따르면, 상기 구조들은 중수소; 시아노기; 치환 또는 비치환된 메틸기; 치환 또는 비치환된 프로필기; 치환 또는 비치환된 부틸기; 치환 또는 비치환된 페닐기; 치환 또는 비치환된 카바졸기; 또는 치환 또는 비치환된 벤조카바졸기로 치환 또는 비치환될 수 있다.According to an exemplary embodiment of the present specification, the structures are deuterium; Cyano group; A substituted or unsubstituted methyl group; A substituted or unsubstituted propyl group; A substituted or unsubstituted butyl group; A substituted or unsubstituted phenyl group; A substituted or unsubstituted carbazole group; Or it may be substituted or unsubstituted with a substituted or unsubstituted benzocarbazole group.
본 명세서의 일 실시상태에 따르면, 상기 구조들은 중수소; 시아노기; 중수소로 치환 또는 비치환된 메틸기; 이소프로필기; tert-부틸기; 페닐기; 카바졸기; 또는 벤조카바졸기로 치환 또는 비치환될 수 있다.According to an exemplary embodiment of the present specification, the structures are deuterium; Cyano group; A methyl group unsubstituted or substituted with deuterium; Isopropyl group; tert-butyl group; Phenyl group; Carbazole; Or it may be substituted or unsubstituted with a benzocarbazole group.
본 명세서의 일 실시상태에 따르면, 상기 구조들은 중수소; 시아노기; CH3; CD3; 이소프로필기; tert-부틸기; 페닐기; 카바졸기; 또는 벤조카바졸기로 치환 또는 비치환될 수 있다.According to an exemplary embodiment of the present specification, the structures are deuterium; Cyano group; CH 3 ; CD 3 ; Isopropyl group; tert-butyl group; Phenyl group; Carbazole; Or it may be substituted or unsubstituted with a benzocarbazole group.
본 명세서의 일 실시상태에 따르면, 상기 R11은 치환 또는 비치환된 탄소수 6 내지 30의 아릴기이다.According to an exemplary embodiment of the present specification, R11 is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
또 하나의 일 실시상태에 따르면, 상기 R11은 치환 또는 비치환된 페닐기; 또는 치환 또는 비치환된 바이페닐기이다.According to another exemplary embodiment, R11 is a substituted or unsubstituted phenyl group; Or a substituted or unsubstituted biphenyl group.
또 하나의 일 실시상태에 있어서, 상기 R11은 페닐기; 또는 바이페닐기이다.In another exemplary embodiment, R11 is a phenyl group; Or a biphenyl group.
본 명세서의 일 실시상태에 따르면, 상기 R12 및 R13은 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 탄소수 1 내지 20의 알킬기이다.According to one embodiment of the present specification, R12 and R13 are the same as or different from each other, and each independently an substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.
또 하나의 일 실시상태에 있어서, 상기 R12 및 R13은 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 메틸기이다.In another exemplary embodiment, R12 and R13 are the same as or different from each other, and each independently a substituted or unsubstituted methyl group.
또 하나의 일 실시상태에 따르면, 상기 R12 및 R13은 메틸기이다.According to another exemplary embodiment, R12 and R13 are methyl groups.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R4; 및 *와 결합하지 않는 R5 및 R6 중 적어도 하나는 인접한 기와 서로 결합하여 고리를 형성하여 벤조카바졸 고리를 이룬다.According to an exemplary embodiment of the present specification, the R1 To R4; And at least one of R5 and R6 which does not bind to * forms a ring by combining with an adjacent group to form a benzocarbazole ring.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R4; 및 *와 결합하지 않는 R5 및 R6 중 적어도 하나는 인접한 기와 서로 결합하여 고리를 형성하여, 하기 구조 중 하나인 벤조카바졸 고리를 이룬다.According to an exemplary embodiment of the present specification, the R1 To R4; And * and at least one of R5 and R6 which do not bind to form a ring by combining with an adjacent group to form a benzocarbazole ring, one of the following structures.
Figure PCTKR2019013897-appb-I000015
Figure PCTKR2019013897-appb-I000015
본 명세서의 일 실시상태에 따르면, 상기 화학식 1은 하기 구조들 중 어느 하나로 표시된다.According to an exemplary embodiment of the present specification, the formula 1 is represented by any one of the following structures.
Figure PCTKR2019013897-appb-I000016
Figure PCTKR2019013897-appb-I000016
Figure PCTKR2019013897-appb-I000017
Figure PCTKR2019013897-appb-I000017
Figure PCTKR2019013897-appb-I000018
Figure PCTKR2019013897-appb-I000018
Figure PCTKR2019013897-appb-I000019
Figure PCTKR2019013897-appb-I000019
Figure PCTKR2019013897-appb-I000020
Figure PCTKR2019013897-appb-I000020
Figure PCTKR2019013897-appb-I000021
Figure PCTKR2019013897-appb-I000021
Figure PCTKR2019013897-appb-I000022
Figure PCTKR2019013897-appb-I000022
Figure PCTKR2019013897-appb-I000023
Figure PCTKR2019013897-appb-I000023
Figure PCTKR2019013897-appb-I000024
Figure PCTKR2019013897-appb-I000024
Figure PCTKR2019013897-appb-I000025
Figure PCTKR2019013897-appb-I000025
Figure PCTKR2019013897-appb-I000026
Figure PCTKR2019013897-appb-I000026
Figure PCTKR2019013897-appb-I000027
Figure PCTKR2019013897-appb-I000027
Figure PCTKR2019013897-appb-I000028
Figure PCTKR2019013897-appb-I000028
Figure PCTKR2019013897-appb-I000029
Figure PCTKR2019013897-appb-I000029
Figure PCTKR2019013897-appb-I000030
Figure PCTKR2019013897-appb-I000030
Figure PCTKR2019013897-appb-I000031
Figure PCTKR2019013897-appb-I000031
Figure PCTKR2019013897-appb-I000032
Figure PCTKR2019013897-appb-I000032
Figure PCTKR2019013897-appb-I000033
Figure PCTKR2019013897-appb-I000033
Figure PCTKR2019013897-appb-I000034
Figure PCTKR2019013897-appb-I000034
Figure PCTKR2019013897-appb-I000035
Figure PCTKR2019013897-appb-I000035
Figure PCTKR2019013897-appb-I000036
Figure PCTKR2019013897-appb-I000036
Figure PCTKR2019013897-appb-I000037
Figure PCTKR2019013897-appb-I000037
Figure PCTKR2019013897-appb-I000038
Figure PCTKR2019013897-appb-I000038
Figure PCTKR2019013897-appb-I000039
Figure PCTKR2019013897-appb-I000039
Figure PCTKR2019013897-appb-I000040
Figure PCTKR2019013897-appb-I000040
Figure PCTKR2019013897-appb-I000041
Figure PCTKR2019013897-appb-I000041
Figure PCTKR2019013897-appb-I000042
Figure PCTKR2019013897-appb-I000042
Figure PCTKR2019013897-appb-I000043
Figure PCTKR2019013897-appb-I000043
Figure PCTKR2019013897-appb-I000044
Figure PCTKR2019013897-appb-I000044
Figure PCTKR2019013897-appb-I000045
Figure PCTKR2019013897-appb-I000045
본 명세서의 일 실시상태에 따르면, 상기 화학식 1로 표시되는 화합물의 삼중항(triplet) 에너지 준위는 2.1 eV 이상이고, 바람직하게는 2.1 eV 이상 3.0 eV 이하, 2.2 eV 이상 3.0 eV 이하, 2.4 eV 이상 2.9 eV 이하일 수 있다. 상기 화학식 1로 표시되는 화합물의 삼중항(triplet) 에너지 준위가 상기 범위를 만족하는 경우, 전자 주입이 용이하게되어 엑시톤의 형성 비율이 높아지게 되므로, 발광 효율이 상승하는 이점이 있다.According to the exemplary embodiment of the present specification, the triplet energy level of the compound represented by Chemical Formula 1 is 2.1 eV or more, preferably 2.1 eV or more and 3.0 eV or less, 2.2 eV or more, 3.0 eV or less, 2.4 eV or more 2.9 eV or less. When the triplet energy level of the compound represented by Chemical Formula 1 satisfies the above range, electron injection is facilitated and the exciton formation rate is increased, so that the luminous efficiency is increased.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1로 표시되는 화합물의 일중항(singlet) 에너지 준위와 삼중항(triplet) 에너지 준위의 차는 0 eV 이상 0.3 eV 이하이고, 바람직하게는 0 eV 이상 0.2 eV 이하이다. 상기 화학식 1로 표시되는 화합물의 일중항(singlet) 에너지 준위와 삼중항(triplet) 에너지 준위의 차가 상기 범위를 만족하는 경우, 삼중항에서 생성된 엑시톤이 역계간전이(RISC)에 의해 일중항으로 이동하는 비율 및 속도가 증가하여 삼중항에 엑시톤이 머무는 시간이 줄어들게 되므로 유기발광소자의 효율 및 수명이 증가하는 이점이 있다.According to an exemplary embodiment of the present specification, the difference between the singlet energy level and the triplet energy level of the compound represented by Formula 1 is 0 eV or more and 0.3 eV or less, preferably 0 eV or more and 0.2 eV Is below. When the difference between the singlet energy level and the triplet energy level of the compound represented by Chemical Formula 1 satisfies the above range, the exciton generated in the triplet is converted into a singlet by inverse transition (RISC). As the moving rate and speed increase, the time for the exciton to stay in the triplet decreases, so there is an advantage of increasing the efficiency and life of the organic light emitting device.
본 명세서에 있어서, 삼중항 에너지는 형광과 인광 측정이 가능한 JASCO FP-8600 등의 분광 기기를 이용하여 측정 가능하고, 측정 조건의 경우 액화질소를 이용한 극저온 상태에서 톨루엔이나 티에치에프를 용매로 하여 10-6M 농도로 용액을 제조하고 용액에 물질의 흡수 파장대의 광원을 조사하여 발광하는 스펙트럼으로부터 일중항 발광을 제외하고, 삼중항에서 발광하는 스펙트럼을 분석하여 확인한다. 광원으로부터 전자가 역이되면 전자가 삼중항에 머물게되는 시간이 일중항에 머물게되는 시간보다 훨씬 길기 때문에 극저온 상태에서 두 성분의 분리가 가능하다.In the present specification, the triplet energy can be measured using a spectral device such as JASCO FP-8600 capable of measuring fluorescence and phosphorescence, and in the case of measurement conditions, toluene or TIEF is used as a solvent in a cryogenic state using liquid nitrogen. Prepare a solution at a concentration of 10 -6 M and irradiate the solution with a light source of an absorption wavelength band of the substance, except for singlet emission from the spectrum emitting light, and confirm by analyzing the spectrum emitted from triplet. When the electrons from the light source reverse, the time for the electrons to stay in the triplet is much longer than the time in the singlet, so it is possible to separate the two components in the cryogenic state.
본 명세서에 있어서, 일중항 에너지의 경우 JASCO FP-8600 등의 형광기기를 이용하여 측정하며, 전술한 삼중항 에너지 측정방법과 달리 상온에서 광원을 조사한다.In the present specification, the singlet energy is measured using a fluorescent device such as JASCO FP-8600, and the light source is irradiated at room temperature, unlike the triplet energy measurement method described above.
본 명세서에서는 상기 화학식 1로 표시되는 화합물의 코어 구조에 다양한 치환기를 도입함으로써 다양한 에너지 밴드갭을 갖는 화합물을 합성할 수 있다. 또한, 본 명세서에서는 상기와 같은 구조의 코어 구조에 다양한 치환기를 도입함으로써 화합물의 HOMO 및 LUMO 에너지 준위도 조절할 수 있다.In this specification, compounds having various energy band gaps can be synthesized by introducing various substituents to the core structure of the compound represented by Chemical Formula 1. In addition, in this specification, the HOMO and LUMO energy levels of the compound can be adjusted by introducing various substituents to the core structure having the above structure.
또한, 본 명세서에 따른 유기발광소자는 제1 전극; 상기 제1 전극과 대향하여 구비되는 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비되는 1층 이상의 유기물층을 포함하고, 상기 유기물층 중 1층 이상은 상기 전술한 화합물을 포함하는 것을 특징으로 한다.In addition, the organic light emitting device according to the present specification includes 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, and at least one layer of the organic material layer comprises the above-described compound.
본 명세서의 유기발광소자는 전술한 화학식 1로 표시되는 화합물을 이용하여 1층 이상의 유기물층을 형성하는 것을 제외하고는, 통상의 유기발광소자의 제조방법 및 재료에 의하여 제조될 수 있다.The organic light-emitting device of the present specification may be manufactured by a conventional method and material for manufacturing an organic light-emitting device, except for forming one or more organic material layers using the compound represented by Chemical Formula 1 above.
상기 화합물 1로 표시되는 화합물을 포함하는 유기물층이 형성된 유기발광소자의 제조시 진공 증착법 뿐만 아니라 용액 도포법에 의하여 유기물층으로 형성될 수 있다. 여기서, 용액 도포법이라 함은 스핀 코팅, 딥 코팅, 잉크젯 프린팅, 스크린 프린팅, 스프레이법, 롤 코팅 등을 의미하지만, 이들만으로 한정되는 것은 아니다.When manufacturing an organic light emitting device having an organic material layer including the compound represented by Compound 1, it may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method. Here, the solution application method means spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited to these.
본 명세서의 유기발광소자의 유기물층은 단층 구조로 이루어질 수도 있으나, 2층 이상의 유기물층이 적층된 다층 구조로 이루어질 수 있다. 예컨대, 본 발명의 유기발광소자는 유기물층으로서 정공수송층, 정공주입층, 전자차단층, 정공수송 및 정공주입을 동시에 하는 층, 전자수송층, 전자주입층, 정공차단층, 및 전자수송 및 주입을 동시에 하는 층 중 1층 이상을 포함하는 구조를 가질 수 있다. 그러나, 본 명세서의 유기발광소자의 구조는 이에 한정되지 않고 더 적은 수 또는 더 많은 수의 유기물층을 포함할 수 있다.The organic material layer of the organic light emitting device of the present specification may have a single layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention is a hole transport layer, a hole injection layer, an electron blocking layer, a layer simultaneously performing hole transport and hole injection, an electron transport layer, an electron injection layer, a hole blocking layer, and an electron transport and injection as an organic material layer It may have a structure including one or more of the layers. However, the structure of the organic light emitting device of the present specification is not limited thereto, and may include fewer or more organic material layers.
본 명세서의 유기발광소자에서, 상기 유기물층은 정공수송층 또는 정공주입층을 포함하고, 상기 정공수송층 또는 정공주입층은 전술한 화학식 1로 표시되는 화합물을 포함할 수 있다.In the organic light emitting device of the present specification, the organic material layer includes a hole transport layer or a hole injection layer, and the hole transport layer or the hole injection layer may include a compound represented by Formula 1 described above.
또 하나의 본 명세서의 유기발광소자에서, 상기 유기물층은 전자수송층 또는 전자주입층을 포함하고, 상기 전자수송층 또는 전자주입층은 전술한 화학식 1로 표시되는 화합물을 포함할 수 있다. In another organic light emitting device of the present specification, the organic material layer may include an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer may include a compound represented by Formula 1 described above.
또 하나의 본 명세서의 유기발광소자에서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 전술한 화학식 1로 표시되는 화합물을 포함할 수 있다.In another organic light emitting device of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer may include a compound represented by Chemical Formula 1 described above.
또 하나의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화합물을 발광층의 호스트로 포함할 수 있다.According to another exemplary embodiment, the organic material layer includes a light emitting layer, and the light emitting layer may include the compound as a host of the light emitting layer.
또 하나의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화합물을 발광층의 도펀트로 포함할 수 있다.According to another exemplary embodiment, the organic material layer includes a light emitting layer, and the light emitting layer may include the compound as a dopant in the light emitting layer.
본 명세서의 일 실시상태에 있어서, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화합물을 발광층의 도펀트로 포함하며, 호스트를 더 포함할 수 있다. 이때, 상기 도펀트의 함량은 호스트 100 중량부를 기준으로 1 중량부 내지 60 중량부로 포함될 수 있으며, 바람직하게는 30 중량부 내지 50 중량부로 포함된다.In one embodiment of the present specification, the organic material layer includes a light emitting layer, the light emitting layer includes the compound as a dopant in the light emitting layer, and may further include a host. At this time, the content of the dopant may be included in 1 part by weight to 60 parts by weight based on 100 parts by weight of the host, preferably 30 parts by weight to 50 parts by weight.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 축합 방향족환 유도체 및 헤테로고리 함유 화합물 중에서 선택되는 어느 하나 이상을 발광층의 호스트로서 포함한다.According to the exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes at least one selected from a condensed aromatic ring derivative and a heterocyclic compound as a host of the light emitting layer.
본 명세서의 일 실시상태에 따르면, 상기 축합 방향족환 유도체로는 안트라센 유도체, 피렌 유도체, 나프탈렌 유도체, 펜타센 유도체, 페난트렌 화합물, 플루오란텐 화합물 등이 있고, 헤테로 고리 함유 화합물로는 카바졸 유도체, 디벤조퓨란 유도체, 래더형 퓨란 화합물, 피리미딘 유도체 등이 있으나, 이에 한정되지 않는다.According to an exemplary embodiment of the present specification, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic compounds include carbazole derivatives , Dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
본 명세서의 일 실시상태에 따르면, 상기 발광층은 상기 화합물을 도펀트로서 포함하고, 하기 화학식 F로 표시되는 화합물을 호스트로서 더 포함할 수 있으나, 이에 한정되는 것은 아니다.According to the exemplary embodiment of the present specification, the emission layer may include the compound as a dopant, and further include a compound represented by Formula F as a host, but is not limited thereto.
[화학식 F][Formula F]
Figure PCTKR2019013897-appb-I000046
Figure PCTKR2019013897-appb-I000046
상기 화학식 F에 있어서,In the above formula F,
L13은 치환 또는 비치환된 (b+1)가의 아릴기; 또는 치환 또는 비치환된 (b+1)가의 헤테로아릴기이고,L13 is a substituted or unsubstituted (b + 1) valent aryl group; Or a substituted or unsubstituted (b + 1) valent heteroaryl group,
G11 및 G12는 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 시아노기; 또는 O 또는 S를 포함하는 헤테로아릴기이며,G11 and G12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Cyano group; Or a heteroaryl group containing O or S,
b13은 1 내지 3의 정수이며, b13이 2 이상이면 L13은 서로 같거나 상이하며,b13 is an integer from 1 to 3, and when b13 is 2 or more, L13 is the same as or different from each other,
b는 1 또는 2이며, b가 2이면
Figure PCTKR2019013897-appb-I000047
는 서로 같거나 상이하다.b is 1 or 2, if b is 2
Figure PCTKR2019013897-appb-I000047
Are the same or different from each other.
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 전술한 화합물을 포함하는 도펀트 및 상기 화학식 F 로 표시되는 호스트를 1:99 내지 50:50의 중량비로 포함한다.According to the exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes a dopant containing the above-described compound and a host represented by Formula F in a weight ratio of 1:99 to 50:50.
본 명세서의 일 실시상태에 있어서, 상기 화학식 F에 있어서, L13은 치환 또는 비치환된 탄소수 6 내지 16의 (b+1)가의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 16의 (b+1)가의 헤테로아릴기이다.In one embodiment of the present specification, in Chemical Formula F, L13 is a substituted or unsubstituted (b + 1) valent aryl group having 6 to 16 carbon atoms; Or a substituted or unsubstituted (b + 1) valent heteroaryl group having 2 to 16 carbon atoms.
본 명세서의 일 실시상태에 있어서, 상기 화학식 F에 있어서, L13은 치환 또는 비치환된 탄소수 6 내지 12의 (b+1)가의 아릴기; 또는 치환 또는 비치환된 탄소수 2 내지 12의 (b+1)가의 헤테로아릴기이다.In one embodiment of the present specification, in Chemical Formula F, L13 is a substituted or unsubstituted (b + 1) valent aryl group having 6 to 12 carbon atoms; Or a substituted or unsubstituted (b + 1) valent heteroaryl group having 2 to 12 carbon atoms.
본 명세서의 일 실시상태에 있어서, 상기 화학식 F에 있어서, L13은 치환 또는 비치환된 (b+1)가의 페닐기; 치환 또는 비치환된 (b+1)가의 바이페닐기; 치환 또는 비치환된 (b+1)가의 디벤조퓨라닐기; 또는 치환 또는 비치환된 (b+1)가의 피리디닐기이다.In one embodiment of the present specification, in Chemical Formula F, L13 is a substituted or unsubstituted (b + 1) valent phenyl group; A substituted or unsubstituted (b + 1) valent biphenyl group; A substituted or unsubstituted (b + 1) valent dibenzofuranyl group; Or a substituted or unsubstituted (b + 1) valent pyridinyl group.
본 명세서의 일 실시상태에 있어서, 상기 화학식 F에 있어서, L13이 치환된 (b+1)가의 아릴기일 때, 상기 (b+1)가의 아릴기의 치환기는 헤테로아릴기로 치환된 아릴기이다.In one embodiment of the present specification, in Formula F, when L13 is a substituted (b + 1) valent aryl group, the substituent of the (b + 1) valent aryl group is an aryl group substituted with a heteroaryl group.
본 명세서의 일 실시상태에 있어서, 상기 화학식 F에 있어서, G11 및 G12는 서로 같거나 상이하고, 각각 독립적으로 수소; 또는 시아노기이다.In one embodiment of the present specification, in Chemical Formula F, G11 and G12 are the same as or different from each other, and each independently hydrogen; Or cyano group.
본 명세서의 일 실시상태에 있어서, 상기 화학식 F에 있어서, b13은 1이다.In one embodiment of the present specification, in Chemical Formula F, b13 is 1.
본 명세서의 일 실시상태에 있어서, 상기 화학식 F에 있어서, b13은 2이다.In an exemplary embodiment of the present specification, in the formula F, b13 is 2.
본 명세서의 일 실시상태에 있어서, 상기 화학식 F로 표시되는 화합물은 하기의 화합물들 중에서 선택된 어느 하나이다.In one embodiment of the present specification, the compound represented by Formula F is any one selected from the following compounds.
Figure PCTKR2019013897-appb-I000048
Figure PCTKR2019013897-appb-I000048
본 명세서의 일 실시상태에 따르면, 상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화합물을 포함하고, 형광 발광형 물질을 더 포함한다. 이때, 상기 형광 발광형 물질의 함량은 상기 화합물 100 중량부를 기준으로 0 중량부 내지 10 중량부로 포함될 수 있다. 상기 형광 발광형 물질을 상기 화합물로부터 엑시톤을 전달받아 최종적으로 발광하는 역할을 하므로, 좁은 반치폭을 갖는 형광 발광형 물질을 이용하여 소자의 색순도를 높일 수 있고, 상기 화합물의 엑시톤-폴라론 퀜칭을 방지하여 소자의 수명을 증가시키는 이점이 있다. 상기 반치폭은 발광 스펙트럼 상에서 최대 발광 피크(peak) 높이의 절반(1/2)이 되는 높이에서 peak의 두께를 의미한다. According to the exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, the light emitting layer includes the compound, and further includes a fluorescent light emitting material. At this time, the content of the fluorescent light-emitting material may be included from 0 parts by weight to 10 parts by weight based on 100 parts by weight of the compound. Since the fluorescent light-emitting material receives excitons from the compound and finally emits light, it is possible to increase the color purity of the device using a fluorescent light-emitting material having a narrow half-width, and prevent exciton-polaron quenching of the compound Therefore, there is an advantage of increasing the life of the device. The half width refers to the thickness of the peak at a height that is half (1/2) of the maximum emission peak height on the emission spectrum.
상기 형광 발광형 물질의 예시로는 안트라센계 화합물, 파이렌계 화합물, 플로란텐계 화합물, 페릴렌계 화합물, 보론계 화합물, 또는 하기 구조들로 나타낼 수 있으나, 이에 한정되지 않는다.Examples of the fluorescent material may be represented by anthracene-based compounds, pyrene-based compounds, florantene-based compounds, perylene-based compounds, boron-based compounds, or the following structures, but are not limited thereto.
Figure PCTKR2019013897-appb-I000049
Figure PCTKR2019013897-appb-I000049
Figure PCTKR2019013897-appb-I000050
Figure PCTKR2019013897-appb-I000050
Figure PCTKR2019013897-appb-I000051
Figure PCTKR2019013897-appb-I000051
Figure PCTKR2019013897-appb-I000052
Figure PCTKR2019013897-appb-I000052
Figure PCTKR2019013897-appb-I000053
Figure PCTKR2019013897-appb-I000053
Figure PCTKR2019013897-appb-I000054
Figure PCTKR2019013897-appb-I000054
Figure PCTKR2019013897-appb-I000055
Figure PCTKR2019013897-appb-I000055
Figure PCTKR2019013897-appb-I000056
Figure PCTKR2019013897-appb-I000056
Figure PCTKR2019013897-appb-I000057
Figure PCTKR2019013897-appb-I000057
Figure PCTKR2019013897-appb-I000058
Figure PCTKR2019013897-appb-I000058
본 명세서의 일 실시상태에 있어서, 상기 제1 전극은 양극이고, 제2 전극은 음극이다.In one 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.
상기 유기발광소자는 예컨대 하기와 같은 적층 구조를 가질 수 있으나, 이에만 한정되는 것은 아니다.The organic light emitting device may have a stacked structure as described below, 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/정공수송층/발광층/전자수송층/음극(3) anode / hole transport layer / light emitting layer / electron transport layer / cathode
(4) 양극/정공수송층/발광층/전자수송층/전자주입층/음극(4) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode
(5) 양극/정공주입층/정공수송층/발광층/전자수송층/음극(5) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode
(6) 양극/정공주입층/정공수송층/발광층/전자수송층/전자주입층/음극(6) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode
(7) 양극/정공수송층/전자차단층/발광층/전자수송층/음극(7) anode / hole transport layer / electron blocking layer / light emitting layer / electron transport layer / cathode
(8) 양극/ 정공수송층/전자차단층/발광층/전자수송층/전자주입층/음극(8) anode / hole transport layer / electron blocking layer / light emitting layer / electron transport layer / electron injection layer / cathode
(9) 양극/정공주입층/정공수송층/전자차단층/발광층/전자수송층/음극(9) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / electron transport layer / cathode
(10) 양극/정공주입층/정공수송층/전자차단층/발광층/전자수송층/전자주입 층/음극(10) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / electron transport layer / electron injection layer / cathode
(11) 양극/정공수송층/발광층/정공차단층/전자수송층/음극(11) anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode
(12) 양극/정공수송층/발광층/정공차단층/전자수송층/전자주입층/음극(12) Anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode
(13) 양극/정공주입층/정공수송층/발광층/정공차단층/전자수송층/음극(13) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode
(14) 양극/정공주입층/정공수송층/발광층/정공차단층/전자수송층/전자주입 층/음극(14) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode
본 명세서의 유기발광소자의 구조는 도 1 내지 도 3에 나타낸 것과 같은 구조를 가질 수 있으나, 이에만 한정되는 것은 아니다.The structure of the organic light emitting device of the present specification may have a structure as shown in FIGS. 1 to 3, but is not limited thereto.
도 1에는 기판(1) 위에 양극(2), 발광층(6) 및 음극(10)이 순차적으로 적층된 유기발광소자의 구조가 예시되어 있다. 이와 같은 구조에 있어서, 상기 화합물은 상기 발광층(3)에 포함될 수 있다.1 illustrates the structure of an organic light emitting device in which an anode 2, a light emitting layer 6, and a cathode 10 are sequentially stacked on a substrate 1. In this structure, the compound may be included in the light emitting layer (3).
도 2에는 기판(1) 위에 양극(2), 정공주입층(3), 정공수송층(4), 발광층(6), 전자수송층(8) 및 음극(10)이 순차적으로 적층된 유기발광소자의 구조가 예시되어 있다. In FIG. 2, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 6, an electron transport layer 8, and a cathode 10 are sequentially stacked on an organic light emitting device on a substrate 1 The structure is illustrated.
도 3에는 기판(1) 위에 양극(2), 정공주입층(3), 정공수송층(4), 전자차단층(5), 발광층(6), 정공차단층(7), 전자 주입 및 수송층(9) 및 음극(10)이 순차적으로 적층된 유기발광소자의 구조가 예시되어 있다. 3, an anode 2, a hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light emitting layer 6, a hole blocking layer 7, an electron injection and transport layer on the substrate 1 ( 9) The structure of the organic light emitting device in which the cathode and the cathode 10 are sequentially stacked is illustrated.
예컨대, 본 명세서에 따른 유기발광소자는 스퍼터링(sputtering)이나 전자빔 증발(e-beam evaporation)과 같은 PVD(physical vapor deposition) 방법을 이용하여, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 정공주입층, 정공수송층, 발광층, 전자차단층, 전자수송층 및 전자주입층을 포함하는 유기물층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다. 이와 같은 방법 외에도, 기판 상에 음극 물질부터 유기물층, 양극 물질을 차례로 증착시켜 유기 발광 소자를 만들 수도 있다.For example, the organic light emitting device according to the present specification uses a metal vapor deposition (PVD) method, such as sputtering or e-beam evaporation, to have a metal or conductive metal oxide on the substrate or alloys thereof To form an anode, to form an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, an electron transport layer and an electron injection layer, and then depositing a material that can be used as a cathode thereon Can be. In addition to this method, an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.
상기 유기물층은 정공주입층, 정공수송층, 전자주입 및 전자수송을 동시에 하는 층, 전자차단층, 발광층 및 전자수송층, 전자주입층, 전자주입 및 전자수송을 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 be a multi-layered structure including a hole injection layer, a hole transport layer, an electron injection and electron transport layer, an electron blocking layer, a light emitting layer and an electron transport layer, an electron injection layer, an electron injection and electron transport layer, and the like. However, it is not limited thereto, and may be a single-layer structure. In addition, the organic material layer may be made by using a variety of polymer materials, such as a solvent process (e.g., spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer), not a deposition method. Can be prepared in layers.
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; 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 positive electrode is an electrode for injecting holes, and a positive electrode material is preferably a material having a large work function to facilitate hole injection into an organic material layer. Specific examples of the positive electrode 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), and indium zinc oxide (IZO); A combination of metal and oxide such as ZnO: Al or SnO 2 : Sb; 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 that injects electrons, and the cathode material is preferably a material having a small work function to facilitate electron injection into an 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; There is a multilayer structure material such as LiF / Al or LiO 2 / 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 구체적인 예로는 금속 포피린(porphyrine), 올리고티오펜, 아릴아민 계열의 유기물, 헥사니트릴헥사아자트리페닐렌 계열의 유기물, 퀴나크리돈(quinacridone) 계열의 유기물, 페릴렌(perylene) 계열의 유기물, 안트라퀴논 및 폴리아닐린과 폴리티오펜 계열의 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다. 정공주입층의 두께는 1 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 상승되는 것을 방지할 수 있는 이점이 있다.The hole injection layer is a layer that serves to smoothly inject holes from the anode to the light emitting layer. As the hole injection material, a hole injection material can be well injected with holes from the anode, and HOMO (highest occupied) of the hole injection material It is preferable that the molecular orbital is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based substances. Organic materials, anthraquinones, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto. The hole injection layer may have a thickness of 1 to 150 nm. When the thickness of the hole injection layer is 1 nm or more, there is an advantage of preventing the hole injection characteristics from being deteriorated. If 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 is an advantage that can be prevented.
상기 정공수송층은 정공의 수송을 원활하게 하는 역할을 할 수 있다. 정공 수송 물질로는 양극이나 정공 주입층으로부터 정공을 수송받아 발광층으로 옮겨줄 수 있는 물질로 정공에 대한 이동성이 큰 물질이 적합하다. 구체적인 예로는 아릴아민 계열의 유기물, 전도성 고분자, 및 공액 부분과 비공액 부분이 함께 있는 블록 공중합체 등이 있으나, 이들에만 한정되는 것은 아니다. The hole transport layer may serve to facilitate the transport of holes. As the hole transporting material, a material capable of receiving holes from the anode or the hole injection layer and transporting them to the light emitting layer is suitable for a material having high mobility for holes. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, but are not limited thereto.
상기 정공수송층과 발광층 사이에 전자차단층이 구비될 수 있다. 상기 전자차단층은 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. The electron blocking layer may be a material known in the art.
상기 발광층은 적색, 녹색 또는 청색을 발광할 수 있으며, 인광 물질 또는 형광 물질로 이루어질 수 있다. 상기 발광 물질로는 정공 수송층과 전자 수송층으로부터 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, 벤즈티아졸 및 벤즈이미다졸 계열의 화합물; 폴리(p-페닐렌비닐렌)(PPV) 계열의 고분자; 스피로(spiro) 화합물; 폴리플루오렌, 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. As the light-emitting material, a material capable of emitting light in the visible light region by receiving and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, is preferably a material having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq 3 ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole compounds; Poly (p-phenylenevinylene) (PPV) polymers; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited to these.
발광층의 호스트 재료로는 축합 방향족환 유도체 또는 헤테로환 함유 화합물 등이 있다. 구체적으로 축합 방향족환 유도체로는 안트라센 유도체, 피렌 유도체, 나프탈렌 유도체, 펜타센 유도체, 페난트렌 화합물, 플루오란텐 화합물 등이 있고, 헤테로환 함유 화합물로는 카바졸 유도체, 디벤조퓨란 유도체, 래더형 퓨란 화합물, 피리미딘 유도체 등이 있으나, 이에 한정되지 않는다.The host material of the light emitting layer includes a condensed aromatic ring derivative or a heterocyclic compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic compounds include carbazole derivatives, dibenzofuran derivatives, and ladder types Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
발광층이 적색 발광을 하는 경우, 발광 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), 안트라센계 화합물, 파이렌계 화합물, 보론계 화합물 등과 같은 형광 물질이 사용될 수 있으나, 이에만 한정된 것은 아니다. 발광층이 청색 발광을 하는 경우, 발광 도펀트로는 (4,6-F2ppy)2Irpic와 같은 인광 물질이나, spiro-DPVBi, spiro-6P, 디스틸벤젠(DSB), 디스트릴아릴렌(DSA), PFO계 고분자, PPV계 고분자, 안트라센계 화합물, 파이렌계 화합물, 보론계 화합물 등과 같은 형광 물질이 사용될 수 있으나, 이에만 한정된 것은 아니다.When the light-emitting layer emits red light, PIQIr (acac) (bis (1-phenylisoquinoline) acetylacetonateiridium), PQIr (acac) (bis (1-phenylquinoline) acetylacetonate iridium), PQIr (tris (1-phenylquinoline) iridium are used as emission dopants. ), Phosphorescent materials such as octaethylporphyrin platinum (PtOEP), or fluorescent materials such as Alq 3 (tris (8-hydroxyquinolino) aluminum) may be used, but is not limited thereto. When the light-emitting layer emits green light, a phosphorescent material such as Ir (ppy) 3 (fac tris (2-phenylpyridine) iridium), or Alq3 (tris (8-hydroxyquinolino) aluminum), anthracene-based compound, or pyrene-based light emitting dopant Fluorescent materials such as compounds and boron-based compounds may be used, but are not limited thereto. When the light emitting layer emits blue light, a phosphorescent material such as (4,6-F2ppy) 2 Irpic is used as a light emitting dopant, but spiro-DPVBi, spiro-6P, distylbenzene (DSB), distriarylene (DSA), Fluorescent materials such as PFO-based polymers, PPV-based polymers, anthracene-based compounds, pyrene-based compounds, and boron-based compounds may be used, but are not limited thereto.
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; 히드록시플라본-금속 착물 등이 있으나, 이들에만 한정되는 것은 아니다. 전자수송층의 두께는 1 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 well and transferring them to the light emitting layer, a material having high mobility for electrons is suitable. Specific examples include the Al complex of 8-hydroxyquinoline; Complexes including Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited to these. The thickness of the electron transport layer may be 1 to 50 nm. When the thickness of the electron transport layer is 1 nm or more, there is an advantage of preventing the electron transport properties from deteriorating, and when it is 50 nm or less, the thickness of the electron transport layer is too thick to prevent the driving voltage from rising to improve the movement of electrons. There are advantages.
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 정공 주입층에의 이동을 방지하고, 또한, 박막형성능력이 우수한 화합물이 바람직하다. 구체적으로는 플루오레논, 안트라퀴노다이메탄, 다이페노퀴논, 티오피란 다이옥사이드, 옥사졸, 옥사다이아졸, 트리아졸, 이미다졸, 페릴렌테트라카복실산, 프레오레닐리덴 메탄, 안트론 등과 그들의 유도체, 금속 착체 화합물 및 함질소 5원환 유도체 등이 있으나, 이에 한정되지 않는다. The electron injection layer may serve to facilitate injection of electrons. The electron injection material has the ability to transport electrons, has an electron injection effect from the cathode, has an excellent electron injection effect on the light emitting layer or the light emitting material, prevents movement of excitons generated in the light emitting layer to the hole injection layer, and also , A compound having excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and their derivatives, metal Complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.
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, 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) ( There are o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, It is not limited to this.
상기 정공차단층은 정공의 음극 도달을 저지하는 층으로, 일반적으로 정공주입층과 동일한 조건으로 형성될 수 있다. 구체적으로 옥사디아졸 유도체나 트리아졸 유도체, 페난트롤린 유도체, BCP, 알루미늄 착물 (aluminum complex) 등이 있으나, 이에 한정되지 않는다.The hole blocking layer is a layer that prevents the cathode from reaching the hole, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complex, and the like, but are not limited thereto.
본 발명에 따른 유기발광소자는 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 front emission type, a back emission type, or a double-sided emission type depending on the material used.
이하, 본 명세서를 구체적으로 설명하기 위해 실시예를 들어 상세하기 설명하기로 한다. 그러나, 본 명세서에 따른 실시예들은 여러가지 다른 형태로 변형될 수 있으며, 본 출원의 범위가 아래에서 상술하는 실시예들에 한정되는 것으로 해석되지 않는다. 본 출원의 실시예들은 당업계에서 평균적인 지식을 가진 자에게 본 명세서를 보다 완전하게 설명하기 위해 제공되는 것이다.Hereinafter, examples will be described in detail to specifically describe the present specification. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present application is not interpreted to be limited to the embodiments described below. The embodiments of the present application are provided to more fully describe the present specification to those skilled in the art.
<제조예><Production Example>
상기 화학식 1로 표시되는 화합물은 하기와 같이 할라이드가 치환된 다양한 종류의 아이소프탈로나이트릴로부터 제조할 수 있다. 하기 제조 방법을 통해 구체예 상의 다양한 화합물들을 합성하였다.The compound represented by Chemical Formula 1 may be prepared from various types of isophthalonitrile substituted with halide as follows. Various compounds in the specific examples were synthesized through the following manufacturing method.
제조예 1-1: 화합물 1-A의 합성Preparation Example 1-1: Synthesis of Compound 1-A
Figure PCTKR2019013897-appb-I000059
Figure PCTKR2019013897-appb-I000059
2-브로모-4,6-다이클로로-5-플루오로아이소프탈로나이트릴 20g(68.1mmol), (4-시아노페닐)보로닉액시드 70mmol, 티에치에프 200mL, 물 100mL 및 포타슘카보네이트 204mmol를 혼합하고 70℃로 가열하였다. 테트라키스트라이페닐포스핀팔라듐(1.3mmol)을 첨가하여 리플럭스 상태로 3시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액에서 물층을 제거한 후, 유기층을 클로로포름/헥산(2:3) 컬럼크로마토그래피를 이용하여 정제하여, 화합물 1-A 19.8 g을 얻었다(수율 92%).2-bromo-4,6-dichloro-5-fluoroisophthalonitrile 20 g (68.1 mmol), (4-cyanophenyl) boronic acid 70 mmol, thiechf 200 mL, water 100 mL and potassium carbonate 204 mmol Were mixed and heated to 70 ° C. Tetrakistriphenylphosphine palladium (1.3mmol) was added and stirred for 3 hours in a reflux state. After the reaction, the water layer was removed from the reaction solution returned to room temperature, and the organic layer was purified using chloroform / hexane (2: 3) column chromatography to obtain 19.8 g of Compound 1-A (yield 92%).
MS[M+H]+ = 316MS [M + H] + = 316
제조예 1-2: 화합물 1-B의 합성Preparation Example 1-2: Synthesis of Compound 1-B
Figure PCTKR2019013897-appb-I000060
Figure PCTKR2019013897-appb-I000060
2-브로모-4,6-다이클로로-5-플루오로아이소프탈로나이트릴 20g(68.1mmol), 나프탈렌-2-일보로닉액시드 70mmol, 티에치에프 200mL, 물 100mL 및 포타슘카보네이트 204mmol를 혼합하고 70℃로 가열하였다. 테트라키스트라이페닐포스핀팔라듐(1.3mmol)을 첨가하여 리플럭스 상태로 3시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액에서 물층을 제거한 후, 유기층을 클로로포름/헥산(2:3) 컬럼크로마토그래피를 이용하여 정제하여, 화합물 1-B 20.2 g을 얻었다(수율 87%).2-bromo-4,6-dichloro-5-fluoroisophthalonitrile 20g (68.1mmol), naphthalene-2-ylboronic acid 70mmol, thiechf 200mL, water 100mL and potassium carbonate 204mmol mixed And heated to 70 ° C. Tetrakistriphenylphosphine palladium (1.3mmol) was added and stirred for 3 hours in a reflux state. After the reaction, the water layer was removed from the reaction solution returned to room temperature, and the organic layer was purified using chloroform / hexane (2: 3) column chromatography to obtain 20.2 g of Compound 1-B (yield 87%).
MS[M+H]+ = 341MS [M + H] + = 341
제조예 1-3: 화합물 1-C의 합성Preparation Example 1-3: Synthesis of Compound 1-C
Figure PCTKR2019013897-appb-I000061
Figure PCTKR2019013897-appb-I000061
2-브로모-4,6-다이클로로-5-플루오로아이소프탈로나이트릴 20g(68.1mmol), 다이벤조[b,d]퓨란-2-일보로닉액시드 70mmol, 티에치에프 200mL, 물 100mL 및 포타슘카보네이트 204mmol를 혼합하고 70℃로 가열하였다. 테트라키스트라이페닐포스핀팔라듐(1.3mmol)을 첨가하여 리플럭스 상태로 3시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액에서 물층을 제거한 후, 유기층을 클로로포름/헥산(2:3) 컬럼크로마토그래피를 이용하여 정제하여, 화합물 1-C 21.8 g을 얻었다(수율 84%).2-bromo-4,6-dichloro-5-fluoroisophthalonitrile 20g (68.1mmol), dibenzo [b, d] furan-2-ylboronic acid 70mmol, Thieff 200mL, water 100 mL and 204 mmol of potassium carbonate were mixed and heated to 70 ° C. Tetrakistriphenylphosphine palladium (1.3mmol) was added and stirred for 3 hours in a reflux state. After the reaction, the water layer was removed from the reaction solution returned to room temperature, and the organic layer was purified using chloroform / hexane (2: 3) column chromatography to obtain 21.8 g of Compound 1-C (yield 84%).
MS[M+H]+ = 381MS [M + H] + = 381
제조예 1-4: 화합물 1-D의 합성Preparation Example 1-4: Synthesis of Compound 1-D
Figure PCTKR2019013897-appb-I000062
Figure PCTKR2019013897-appb-I000062
5-브로모-4,6-다이클로로-2-플루오로아이소프탈로나이트릴 20g(68.1mmol), p-톨릴보로닉액시드 70mmol, 티에치에프 200mL, 물 100mL 및 포타슘카보네이트 204mmol를 혼합하고 70℃로 가열하였다. 테트라키스트라이페닐포스핀팔라듐(1.3mmol)을 첨가하여 리플럭스 상태로 3시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액에서 물층을 제거한 후, 유기층을 클로로포름/헥산(2:3) 컬럼크로마토그래피를 이용하여 정제하여, 화합물 1-D 17.9 g을 얻었다(수율 86%).20 g (68.1 mmol) of 5-bromo-4,6-dichloro-2-fluoroisophthalonitrile, 70 mmol of p-tolyl boronic acid, 200 mL of THF, 100 mL of water, and 204 mmol of potassium carbonate were mixed, Heated to 70 ° C. Tetrakistriphenylphosphine palladium (1.3mmol) was added and stirred for 3 hours in a reflux state. After the reaction, the water layer was removed from the reaction solution returned to room temperature, and then the organic layer was purified using chloroform / hexane (2: 3) column chromatography to obtain 17.9 g of Compound 1-D (yield 86%).
MS[M+H]+ = 305MS [M + H] + = 305
제조예 1-5: 화합물 1-E의 합성Preparation Example 1-5: Synthesis of Compound 1-E
Figure PCTKR2019013897-appb-I000063
Figure PCTKR2019013897-appb-I000063
5-브로모-4,6-다이클로로-2-플루오로아이소프탈로나이트릴 20g(68.1mmol), (4-시아노페닐)보로닉액시드 70mmol, 티에치에프 200mL, 물 100mL 및 포타슘카보네이트 204mmol를 혼합하고 70℃로 가열하였다. 테트라키스트라이페닐포스핀팔라듐(1.3mmol)을 첨가하여 리플럭스 상태로 3시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액에서 물층을 제거한 후, 유기층을 클로로포름/헥산(2:3) 컬럼크로마토그래피를 이용하여 정제하여, 화합물 1-E 18.3 g을 얻었다(수율 85%).5-bromo-4,6-dichloro-2-fluoroisophthalonitrile 20 g (68.1 mmol), (4-cyanophenyl) boronic acid 70 mmol, thiechf 200 mL, water 100 mL and potassium carbonate 204 mmol Were mixed and heated to 70 ° C. Tetrakistriphenylphosphine palladium (1.3mmol) was added and stirred for 3 hours in a reflux state. After the reaction, after removing the water layer from the reaction solution returned to room temperature, the organic layer was purified using chloroform / hexane (2: 3) column chromatography to obtain 18.3 g of compound 1-E (yield 85%).
MS[M+H]+ = 316MS [M + H] + = 316
제조예 1-6: 화합물 1-F의 합성Preparation Example 1-6: Synthesis of Compound 1-F
Figure PCTKR2019013897-appb-I000064
Figure PCTKR2019013897-appb-I000064
5-브로모-4,6-다이클로로-2-플루오로아이소프탈로나이트릴 20g(68.1mmol), 다이벤조[b,d]사이오펜-2-일보로닉액시드 70mmol, 티에치에프 200mL, 물 100mL 및 포타슘카보네이트 204mmol를 혼합하고 70℃로 가열하였다. 테트라키스트라이페닐포스핀팔라듐(1.3mmol)을 첨가하여 리플럭스 상태로 3시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액에서 물층을 제거한 후, 유기층을 클로로포름/헥산(2:3) 컬럼크로마토그래피를 이용하여 정제하여, 화합물 1-F 21.9 g을 얻었다(수율 81%).5-bromo-4,6-dichloro-2-fluoroisophthalonitrile 20g (68.1mmol), dibenzo [b, d] thiophen-2-ylboronic acid 70mmol, thieff 200mL, 100 mL of water and 204 mmol of potassium carbonate were mixed and heated to 70 ° C. Tetrakistriphenylphosphine palladium (1.3mmol) was added and stirred for 3 hours in a reflux state. After the reaction, after removing the water layer from the reaction solution returned to room temperature, the organic layer was purified using chloroform / hexane (2: 3) column chromatography to obtain 21.9 g of compound 1-F (yield 81%).
MS[M+H]+ = 397MS [M + H] + = 397
제조예 1-7: 화합물 1-G의 합성Preparation Example 1-7: Synthesis of Compound 1-G
Figure PCTKR2019013897-appb-I000065
Figure PCTKR2019013897-appb-I000065
5-브로모-4,6-다이클로로-2-플루오로아이소프탈로나이트릴 20g(68.1mmol), (4-(터트-뷰틸)페닐)보로닉액시드 70mmol, 티에치에프 200mL, 물 100mL 및 포타슘카보네이트 204mmol를 혼합하고 70℃로 가열하였다. 테트라키스트라이페닐포스핀팔라듐(1.3mmol)을 첨가하여 리플럭스 상태로 3시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액에서 물층을 제거한 후, 유기층을 클로로포름/헥산(2:3) 컬럼크로마토그래피를 이용하여 정제하여, 화합물 1-G 20.3 g을 얻었다(수율 86%).5-bromo-4,6-dichloro-2-fluoroisophthalonitrile 20 g (68.1 mmol), (4- (tert-butyl) phenyl) boronic acid 70 mmol, Thieff 200 mL, water 100 mL and 204 mmol of potassium carbonate was mixed and heated to 70 ° C. Tetrakistriphenylphosphine palladium (1.3mmol) was added and stirred for 3 hours in a reflux state. After the reaction, the water layer was removed from the reaction solution returned to room temperature, and the organic layer was purified using chloroform / hexane (2: 3) column chromatography to obtain 20.3 g of compound 1-G (yield 86%).
MS[M+H]+ = 347MS [M + H] + = 347
제조예 2-1: 화합물 2-A의 합성Preparation Example 2-1: Synthesis of Compound 2-A
Figure PCTKR2019013897-appb-I000066
Figure PCTKR2019013897-appb-I000066
1-A 17.1g(54mmol), 5H-벤조[b]카바졸 54mmol, 디엠에프 150mL 및 포타슘카보네이트 108mmol를 혼합하고 100℃로 가열하여 3시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 2-A 24.4 g을 얻었다(수율 88%).1-A 17.1g (54mmol), 5H-benzo [b] carbazole 54mmol, DMF 150mL and potassium carbonate 108mmol were mixed and heated to 100 ° C and stirred for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 24.4 g of compound 2-A (yield 88%).
MS[M+H]+ = 513MS [M + H] + = 513
제조예 2-2: 화합물 2-B의 합성Preparation Example 2-2: Synthesis of Compound 2-B
Figure PCTKR2019013897-appb-I000067
Figure PCTKR2019013897-appb-I000067
1-A 17.1g(54mmol), 9H-카바졸 54mmol, 디엠에프 150mL 및 포타슘카보네이트 108mmol를 혼합하고 100℃로 가열하여 3시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 2-B 22.8 g을 얻었다(수율 91%).1-A 17.1g (54mmol), 9H-carbazole 54mmol, DMF 150mL and potassium carbonate 108mmol was mixed and heated to 100 ℃ and stirred for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 22.8 g of compound 2-B (yield 91%).
MS[M+H]+ = 463MS [M + H] + = 463
제조예 2-3: 화합물 2-C의 합성Preparation 2-3: Synthesis of Compound 2-C
Figure PCTKR2019013897-appb-I000068
Figure PCTKR2019013897-appb-I000068
1-B 18.4g(54mmol), 5H-벤조[b]카바졸 54mmol, 디엠에프 160mL 및 포타슘카보네이트 108mmol를 혼합하고 100℃로 가열하여 3시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 2-C 25 g을 얻었다(수율 86%).1-B 18.4g (54mmol), 5H-benzo [b] carbazole 54mmol, DMF 160mL and potassium carbonate 108mmol were mixed and heated to 100 ℃ and stirred for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 25 g of compound 2-C (yield 86%).
MS[M+H]+ = 538MS [M + H] + = 538
제조예 2-4: 화합물 2-D의 합성Preparation Example 2-4: Synthesis of Compound 2-D
Figure PCTKR2019013897-appb-I000069
Figure PCTKR2019013897-appb-I000069
1-C 20.6g(54mmol), 9H-카바졸 54mmol, 디엠에프 180mL 및 포타슘카보네이트 108mmol를 혼합하고 100℃로 가열하여 3시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 2-D 25.4 g을 얻었다(수율 89%).1-C 20.6g (54mmol), 9H-carbazole 54mmol, DMF 180mL and potassium carbonate 108mmol were mixed and heated to 100 ℃ and stirred for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 25.4 g of compound 2-D (yield 89%).
MS[M+H]+ = 528MS [M + H] + = 528
제조예 2-5: 화합물 2-E의 합성Preparation Example 2-5: Synthesis of Compound 2-E
Figure PCTKR2019013897-appb-I000070
Figure PCTKR2019013897-appb-I000070
1-D 16.5g(54mmol), 9H-카바졸 54mmol, 디엠에프 150mL 및 포타슘카보네이트 108mmol를 혼합하고 100℃로 가열하여 3시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 2-E 22.2 g을 얻었다(수율 91%).1-D 16.5g (54mmol), 9H-carbazole 54mmol, DMF 150mL and potassium carbonate 108mmol were mixed and heated to 100 ° C and stirred for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 22.2 g of compound 2-E (yield 91%).
MS[M+H]+ = 452MS [M + H] + = 452
제조예 2-6: 화합물 2-F의 합성Preparation Example 2-6: Synthesis of Compound 2-F
Figure PCTKR2019013897-appb-I000071
Figure PCTKR2019013897-appb-I000071
1-D 16.5g(54mmol), 5H-벤조[b]카바졸 54mmol, 디엠에프 150mL 및 포타슘카보네이트 108mmol를 혼합하고 100℃로 가열하여 3시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 2-F 22.8 g을 얻었다(수율 84%).1-D 16.5g (54mmol), 5H-benzo [b] carbazole 54mmol, DMF 150mL and potassium carbonate 108mmol were mixed and heated to 100 ° C and stirred for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 22.8 g of compound 2-F (yield 84%).
MS[M+H]+ = 502MS [M + H] + = 502
제조예 2-7: 화합물 2-G의 합성Preparation Example 2-7: Synthesis of Compound 2-G
Figure PCTKR2019013897-appb-I000072
Figure PCTKR2019013897-appb-I000072
1-E 17.1g(54mmol), 9H-카바졸 54mmol, 디엠에프 150mL 및 포타슘카보네이트 108mmol를 혼합하고 100℃로 가열하여 3시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 2-G 21.3 g을 얻었다(수율 85%).1-E 17.1g (54mmol), 9H-carbazole 54mmol, DMF 150mL and potassium carbonate 108mmol were mixed and heated to 100 ℃ and stirred for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 21.3 g of compound 2-G (yield 85%).
MS[M+H]+ = 463MS [M + H] + = 463
제조예 2-8: 화합물 2-H의 합성Preparation Example 2-8: Synthesis of Compound 2-H
Figure PCTKR2019013897-appb-I000073
Figure PCTKR2019013897-appb-I000073
1-E 17.1g(54mmol), 3,6-다이페닐-9H-카바졸 54mmol, 디엠에프 150mL 및 포타슘카보네이트 108mmol를 혼합하고 100℃로 가열하여 3시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 2-H 26.6 g을 얻었다(수율 80%).1-E 17.1g (54mmol), 3,6-diphenyl-9H-carbazole 54mmol, DMF 150mL and potassium carbonate 108mmol was mixed and heated to 100 ℃ and stirred for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 26.6 g of compound 2-H (yield 80%).
MS[M+H]+ = 615MS [M + H] + = 615
제조예 2-9: 화합물 2-I의 합성Preparation Example 2-9: Synthesis of Compound 2-I
Figure PCTKR2019013897-appb-I000074
Figure PCTKR2019013897-appb-I000074
1-E 17.1g(54mmol), 5-페닐-5,8-다이하이드로인돌로[2,3-c]카바졸 54mmol, 디엠에프 150mL 및 포타슘카보네이트 108mmol를 혼합하고 100℃로 가열하여 3시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 2-I 28.2 g을 얻었다(수율 83%).1-E 17.1g (54mmol), 5-phenyl-5,8-dihydroindolo [2,3-c] carbazole 54mmol, Diem 150mL and potassium carbonate 108mmol were mixed and heated to 100 ℃ and stirred for 3 hours Did. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 28.2 g of compound 2-I (yield 83%).
MS[M+H]+ = 628MS [M + H] + = 628
제조예 2-10: 화합물 2-J의 합성Preparation Example 2-10: Synthesis of Compound 2-J
Figure PCTKR2019013897-appb-I000075
Figure PCTKR2019013897-appb-I000075
1-F 21.5g(54mmol), 9H- 카바졸 54mmol, 디엠에프 150mL 및 포타슘카보네이트 108mmol를 혼합하고 100℃로 가열하여 3시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 2-J 25.6 g을 얻었다(수율 87%).1-F 21.5g (54mmol), 9H- carbazole 54mmol, DMF 150mL and potassium carbonate 108mmol were mixed and heated to 100 ℃ and stirred for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 25.6 g of compound 2-J (yield 87%).
MS[M+H]+ = 544MS [M + H] + = 544
제조예 2-11: 화합물 2-K의 합성Preparation Example 2-11: Synthesis of Compound 2-K
Figure PCTKR2019013897-appb-I000076
Figure PCTKR2019013897-appb-I000076
1-G 18.7g(54mmol), 9H- 카바졸 54mmol, 디엠에프 150mL 및 포타슘카보네이트 108mmol를 혼합하고 100℃로 가열하여 3시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 2-K 24.3 g을 얻었다(수율 91%).1-G 18.7g (54mmol), 9H- carbazole 54mmol, DMF 150mL and potassium carbonate 108mmol were mixed and heated to 100 ° C and stirred for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 24.3 g of compound 2-K (yield 91%).
MS[M+H]+ = 494MS [M + H] + = 494
제조예 2-12: 화합물 2-L의 합성Preparation Example 2-12: Synthesis of Compound 2-L
Figure PCTKR2019013897-appb-I000077
Figure PCTKR2019013897-appb-I000077
1-G 18.7g(54mmol), 3,6-다이페닐-9H-카바졸 54mmol, 디엠에프 150mL 및 포타슘카보네이트 108mmol를 혼합하고 100℃로 가열하여 3시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 2-L 30 g을 얻었다(수율 86%).1-G 18.7g (54mmol), 3,6-diphenyl-9H-carbazole 54mmol, DMF 150mL and potassium carbonate 108mmol were mixed and heated to 100 ℃ and stirred for 3 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 30 g of compound 2-L (yield 86%).
MS[M+H]+ = 646MS [M + H] + = 646
제조예 3-1: 화합물 1의 합성Preparation Example 3-1: Synthesis of Compound 1
Figure PCTKR2019013897-appb-I000078
Figure PCTKR2019013897-appb-I000078
2-A 19g(37mmol), 9H-카바졸 74mmol, 자일렌 180mL, 소듐-터트-뷰톡사이드 89mmol 및 테트라키스트라이페닐포스핀팔라듐 1.8mmol를 혼합하고 리플럭스하여 2시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 1 23.2 g을 얻었다(수율 81%).2-A 19g (37mmol), 9H-carbazole 74mmol, xylene 180mL, sodium-tert-butoxide 89mmol and tetrakistriphenylphosphine palladium 1.8mmol were mixed and refluxed and stirred for 2 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 23.2 g of compound 1 (yield 81%).
MS[M+H]+ = 775MS [M + H] + = 775
제조예 3-2: 화합물 2의 합성Preparation Example 3-2: Synthesis of Compound 2
Figure PCTKR2019013897-appb-I000079
Figure PCTKR2019013897-appb-I000079
2-B 17.1g(37mmol), 3,6-다이메틸-9H-카바졸 74mmol, 자일렌 180mL, 소듐-터트-뷰톡사이드 89mmol 및 테트라키스트라이페닐포스핀팔라듐 1.8mmol를 혼합하고 리플럭스하여 2시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 2 21.7 g을 얻었다(수율 75%).2-B 17.1g (37mmol), 3,6-dimethyl-9H-carbazole 74mmol, xylene 180mL, sodium-tert-butoxide 89mmol and tetrakistriphenylphosphine palladium 1.8mmol mixed and refluxed 2 Stir for hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 21.7 g of compound 2 (yield 75%).
MS[M+H]+ = 781MS [M + H] + = 781
제조예 3-3: 화합물 3의 합성Preparation Example 3-3: Synthesis of Compound 3
Figure PCTKR2019013897-appb-I000080
Figure PCTKR2019013897-appb-I000080
2-C 19.9g(37mmol), 9H-카바졸 74mmol, 자일렌 180mL, 소듐-터트-뷰톡사이드 89mmol 및 테트라키스트라이페닐포스핀팔라듐 1.8mmol를 혼합하고 리플럭스하여 2시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 3 23.1 g을 얻었다(수율 78%).2-C 19.9g (37mmol), 9H-carbazole 74mmol, xylene 180mL, sodium-tert-butoxide 89mmol and tetrakistriphenylphosphine palladium 1.8mmol were mixed and refluxed and stirred for 2 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 23.1 g of compound 3 (yield 78%).
MS[M+H]+ = 800MS [M + H] + = 800
제조예 3-4: 화합물 4의 합성Preparation Example 3-4: Synthesis of Compound 4
Figure PCTKR2019013897-appb-I000081
Figure PCTKR2019013897-appb-I000081
2-D 19.6g(37mmol), 3,6-다이메틸-9H-카바졸 74mmol, 자일렌 180mL, 소듐-터트-뷰톡사이드 89mmol 및 테트라키스트라이페닐포스핀팔라듐 1.8mmol를 혼합하고 리플럭스하여 2시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 4 22.8 g을 얻었다(수율 73%).2-D 19.6g (37mmol), 3,6-dimethyl-9H-carbazole 74mmol, xylene 180mL, sodium-tert-butoxide 89mmol and tetrakistriphenylphosphine palladium 1.8mmol were mixed and refluxed 2 Stir for hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 22.8 g of compound 4 (yield 73%).
MS[M+H]+ = 847MS [M + H] + = 847
제조예 3-5: 화합물 5의 합성Preparation Example 3-5: Synthesis of Compound 5
Figure PCTKR2019013897-appb-I000082
Figure PCTKR2019013897-appb-I000082
2-E 16.7g(37mmol), 3,6-다이메틸-9H-카바졸 74mmol, 자일렌 180mL, 소듐-터트-뷰톡사이드 89mmol 및 테트라키스트라이페닐포스핀팔라듐 1.8mmol를 혼합하고 리플럭스하여 2시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 5 20.2 g을 얻었다(수율 71%).2-E 16.7g (37mmol), 3,6-dimethyl-9H-carbazole 74mmol, xylene 180mL, sodium-tert-butoxide 89mmol and tetrakistriphenylphosphine palladium 1.8mmol mixed and refluxed 2 Stir for hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 20.2 g of compound 5 (yield 71%).
MS[M+H]+ = 770MS [M + H] + = 770
제조예 3-6: 화합물 6의 합성Preparation Example 3-6: Synthesis of Compound 6
Figure PCTKR2019013897-appb-I000083
Figure PCTKR2019013897-appb-I000083
2-F 18.6g(37mmol), 9H-카바졸 74mmol, 자일렌 180mL, 소듐-터트-뷰톡사이드 89mmol 및 테트라키스트라이페닐포스핀팔라듐 1.8mmol를 혼합하고 리플럭스하여 2시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 6 22.3 g을 얻었다(수율 79%).2-F 18.6g (37mmol), 9H-carbazole 74mmol, xylene 180mL, sodium-tert-butoxide 89mmol and tetrakistriphenylphosphine palladium 1.8mmol were mixed and refluxed and stirred for 2 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 22.3 g of compound 6 (yield 79%).
MS[M+H]+ = 764MS [M + H] + = 764
제조예 3-7: 화합물 7의 합성Preparation Example 3-7: Synthesis of Compound 7
Figure PCTKR2019013897-appb-I000084
Figure PCTKR2019013897-appb-I000084
2-G 17.1g(37mmol), 3,6-다이메틸-9H-카바졸 74mmol, 자일렌 180mL, 소듐-터트-뷰톡사이드 89mmol 및 테트라키스트라이페닐포스핀팔라듐 1.8mmol를 혼합하고 리플럭스하여 2시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 7 21.1 g을 얻었다(수율 73%).2-G 17.1g (37mmol), 3,6-dimethyl-9H-carbazole 74mmol, xylene 180mL, sodium-tert-butoxide 89mmol and tetrakistriphenylphosphine palladium 1.8mmol were mixed and refluxed 2 Stir for hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 21.1 g of compound 7 (yield 73%).
MS[M+H]+ = 781MS [M + H] + = 781
제조예 3-8: 화합물 8의 합성Preparation Example 3-8: Synthesis of Compound 8
Figure PCTKR2019013897-appb-I000085
Figure PCTKR2019013897-appb-I000085
2-H 22.8g(37mmol), 9H-카바졸 74mmol, 자일렌 180mL, 소듐-터트-뷰톡사이드 89mmol 및 테트라키스트라이페닐포스핀팔라듐 1.8mmol를 혼합하고 리플럭스하여 2시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 8 25 g을 얻었다(수율 77%).2-H 22.8g (37mmol), 9H-carbazole 74mmol, xylene 180mL, sodium-tert-butoxide 89mmol and tetrakistriphenylphosphine palladium 1.8mmol were mixed and refluxed and stirred for 2 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and the solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 25 g of compound 8 (yield 77%).
MS[M+H]+ = 877MS [M + H] + = 877
제조예 3-9: 화합물 9의 합성Preparation Example 3-9: Synthesis of Compound 9
Figure PCTKR2019013897-appb-I000086
Figure PCTKR2019013897-appb-I000086
2-I 23.2g(37mmol), 9H-카바졸 74mmol, 자일렌 180mL, 소듐-터트-뷰톡사이드 89mmol 및 테트라키스트라이페닐포스핀팔라듐 1.8mmol를 혼합하고 리플럭스하여 2시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 9 25.7 g을 얻었다(수율 78%).2-I 23.2g (37mmol), 9H-carbazole 74mmol, xylene 180mL, sodium-tert-butoxide 89mmol and tetrakistriphenylphosphine palladium 1.8mmol were mixed and refluxed and stirred for 2 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 25.7 g of compound 9 (yield 78%).
MS[M+H]+ = 890MS [M + H] + = 890
제조예 3-10: 화합물 10의 합성Preparation Example 3-10: Synthesis of Compound 10
Figure PCTKR2019013897-appb-I000087
Figure PCTKR2019013897-appb-I000087
2-J 20.1g(37mmol), 3,6-다이메틸-9H-카바졸 74mmol, 자일렌 180mL, 소듐-터트-뷰톡사이드 89mmol 및 테트라키스트라이페닐포스핀팔라듐 1.8mmol를 혼합하고 리플럭스하여 2시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 10 23 g을 얻었다(수율 72%).2-J 20.1g (37mmol), 3,6-dimethyl-9H-carbazole 74mmol, xylene 180mL, sodium-tert-butoxide 89mmol and tetrakistriphenylphosphine palladium 1.8mmol was mixed and refluxed 2 Stir for hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 23 g of compound 10 (yield 72%).
MS[M+H]+ = 862MS [M + H] + = 862
제조예 3-11: 화합물 11의 합성Preparation Example 3-11: Synthesis of Compound 11
Figure PCTKR2019013897-appb-I000088
Figure PCTKR2019013897-appb-I000088
2-K 18.3g(37mmol), 3,6-다이메틸-9H-카바졸 74mmol, 자일렌 180mL, 소듐-터트-뷰톡사이드 89mmol 및 테트라키스트라이페닐포스핀팔라듐 1.8mmol를 혼합하고 리플럭스하여 2시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 11 21 g을 얻었다(수율 70%).2-K 18.3g (37mmol), 3,6-dimethyl-9H-carbazole 74mmol, xylene 180mL, sodium-tert-butoxide 89mmol and tetrakistriphenylphosphine palladium 1.8mmol were mixed and refluxed 2 Stir for hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 21 g of compound 11 (yield 70%).
MS[M+H]+ = 812MS [M + H] + = 812
제조예 3-12: 화합물 12의 합성Preparation Example 3-12: Synthesis of Compound 12
Figure PCTKR2019013897-appb-I000089
Figure PCTKR2019013897-appb-I000089
2-L 23.9g(37mmol), 9H-카바졸 74mmol, 자일렌 180mL, 소듐-터트-뷰톡사이드 89mmol 및 테트라키스트라이페닐포스핀팔라듐 1.8mmol를 혼합하고 리플럭스하여 2시간 교반하였다. 반응 후 실온으로 되돌린 반응 용액을 필터하여 고체를 얻은 후, 이 고체를 테트라하이드로퓨란과 에탄올으로 2회 재결정을 실시하여, 화합물 12 24.9 g을 얻었다(수율 74%).2-L 23.9g (37mmol), 9H-carbazole 74mmol, xylene 180mL, sodium-tert-butoxide 89mmol and tetrakistriphenylphosphine palladium 1.8mmol were mixed and refluxed and stirred for 2 hours. After the reaction, the reaction solution returned to room temperature was filtered to obtain a solid, and this solid was recrystallized twice with tetrahydrofuran and ethanol to obtain 24.9 g of compound 12 (yield: 74%).
MS[M+H]+ = 908MS [M + H] + = 908
<비교예 1-1><Comparative Example 1-1>
ITO(Indium Tin Oxide)가 1,000Å의 두께로 박막 코팅된 유리 기판을 세제를 녹인 증류수에 넣고 초음파로 세척하였다. 이 때, 세제로는 피셔사(Fischer Co.) 제품을 사용하였으며, 증류수로는 밀러포어사(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 및 메탄올의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 수송시켰다. 또한, 산소 플라즈마를 이용하여 상기 기판을 5분간 세정한 후 진공 증착기로 기판을 수송시켰다. 이렇게 준비된 ITO 투명 전극 위에 각 박막을 진공 증착법으로 진공도 5.0Х10-4 ㎩로 적층하였다. 먼저, ITO 상에 헥사아자트리페닐렌-헥사니트릴(HAT-CN)을 500Å의 두께로 열 진공 증착하여 정공 주입층을 형성하였다.The glass substrate coated with ITO (Indium Tin Oxide) with a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, Fischer (Fischer Co.) was used as a detergent, and distilled water filtered secondarily by a filter of Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice for 10 minutes with distilled water. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after the substrate was cleaned for 5 minutes using oxygen plasma, the substrate was transferred to a vacuum evaporator. Each thin film was laminated on the prepared ITO transparent electrode with a vacuum degree of 5.0Х10 -4 으로 by vacuum deposition. First, a hole injection layer was formed by thermal vacuum deposition of hexaazatriphenylene-hexanitrile (HAT-CN) to a thickness of 500 Pa on ITO.
상기 정공 주입층 위에 하기 화합물 NPB를 진공 증착하여 정공 수송층(300Å)을 형성하였다.The following compound NPB was vacuum deposited on the hole injection layer to form a hole transport layer (300 kPa).
상기 정공 수송층 위에 막 두께 100Å으로 하기 화합물 EB1를 진공 증착하여 전자 차단층(100Å)을 형성하였다.The following compound EB1 was vacuum deposited on the hole transport layer to a thickness of 100 mm 2 to form an electron blocking layer (100 mm 2).
이어서, 상기 전자 차단층 위에 막 두께 300Å으로 하기 화합물 m-CBP와 4CzIPN을 70:30의 중량비로 진공 증착하여 발광층을 형성하였다.Subsequently, the compound m-CBP and 4CzIPN having a thickness of 300 mm 3 were vacuum deposited on the electron blocking layer at a weight ratio of 70:30 to form a light emitting layer.
상기 발광층 위에 막 두께 100Å으로 하기 화합물 HB1을 진공 증착하여 정공 차단층을 형성하였다.A hole blocking layer was formed by vacuum-depositing the following compound HB1 with a thickness of 100 mm 2 on the light emitting layer.
상기 정공 차단층 위에 하기 화합물 ET1과 화합물 LiQ(Lithium Quinolate)를 1:1의 중량비로 진공 증착하여 300Å의 두께로 전자 주입 및 수송층을 형성하였다. 상기 전자 주입 및 수송층 위에 순차적으로 12Å 두께로 리튬플로라이드(LiF)와 2,000Å 두께로 알루미늄을 증착하여 음극을 형성하였다.The following compound ET1 and the compound LiQ (Lithium Quinolate) were vacuum deposited on the hole blocking layer at a weight ratio of 1: 1 to form an electron injection and transport layer with a thickness of 300 Pa. On the electron injection and transport layer, lithium fluoride (LiF) with a thickness of 12 Å and aluminum with a thickness of 2,000 순차적 were sequentially deposited to form a negative electrode.
상기의 과정에서 유기물의 증착속도는 0.4Å/sec내지 0.7Å/sec를 유지하였고, 음극의 리튬플로라이드는 0.3Å/sec, 알루미늄은 2Å/sec의 증착 속도를 유지하였으며, 증착시 진공도는 2×10-7torr 내지 5×10-6torr를 유지하여, 유기 발광소자를 제작하였다.In the above process, the deposition rate of the organic material was maintained at 0.4Å / sec to 0.7Å / sec, the lithium fluoride of the negative electrode was maintained at a deposition rate of 0.3Å / sec, and aluminum at 2Å / sec. An organic light emitting device was manufactured by maintaining 10 × 7 torr to 5 × 10 −6 torr.
Figure PCTKR2019013897-appb-I000090
Figure PCTKR2019013897-appb-I000090
<실험예 1-1 내지 1-12><Experimental Examples 1-1 to 1-12>
상기 비교예 1-1에서 화합물 4CzIPN 대신 하기 표 1의 화합물을 사용한 것을 제외하고는 비교예 1-1과 동일한 방법으로 유기 발광 소자를 제작하였다.An organic light emitting diode was manufactured according to the same method as Comparative Example 1-1 except for using the compound of Table 1 below instead of the compound 4CzIPN in Comparative Example 1-1.
Figure PCTKR2019013897-appb-I000091
Figure PCTKR2019013897-appb-I000091
<비교예 1-2 내지 1-4><Comparative Examples 1-2 to 1-4>
상기 비교예 1-1에서 화합물 4CzIPN 대신 하기 T1 내지 T3의 화합물을 사용한 것을 제외하고는 비교예 1-1과 동일한 방법으로 유기 발광 소자를 제작하였다.An organic light emitting diode was manufactured according to the same method as Comparative Example 1-1 except for using the compounds of T1 to T3 below instead of the compound 4CzIPN in Comparative Example 1-1.
Figure PCTKR2019013897-appb-I000092
Figure PCTKR2019013897-appb-I000092
실험예 1-1 내지 1-12 및 비교예 1-1 내지 1-4의 유기 발광 소자에 대하여 10㎃/㎠의 전류밀도에서 측정한 구동 전압(V)과 전류효율(cd/A), 3000cd/m2의 휘도에서 측정한 CIE 색좌표 및 3000cd/m2에서 밝기가 95%로 감소될 때까지의 시간(T95)을 측정하여, 하기 표 1에 나타내었다.The driving voltage (V) and the current efficiency (cd / A), 3000 cd, measured at a current density of 10 mA / cm 2 for the organic light emitting devices of Experimental Examples 1-1 to 1-12 and Comparative Examples 1-1 to 1-4 / m and at a luminance of the second brightness in the CIE color coordinate and 3000cd / m 2 measured at the time (T 95) until a reduction by 95%, shown in Table 1 below.
구분division 화합물(발광층)Compound (light emitting layer) 전압(V)Voltage (V) 효율(cd/A)Efficiency (cd / A) CIE 색좌표(x,y)CIE color coordinate (x, y) T95(hr)T 95 (hr)
실험예 1-1Experimental Example 1-1 1One 4.14.1 2121 (0.22, 0.64)(0.22, 0.64) 9595
실험예 1-2Experimental Example 1-2 22 4.14.1 2020 (0.23, 0.64)(0.23, 0.64) 9191
실험예 1-3Experimental Example 1-3 33 4.24.2 2020 (0.22, 0.63)(0.22, 0.63) 9090
실험예 1-4Experimental Example 1-4 44 4.14.1 2121 (0.23, 0.63)(0.23, 0.63) 9494
실험예 1-5Experimental Example 1-5 55 4.14.1 2121 (0.22, 0.64)(0.22, 0.64) 9191
실험예 1-6Experimental Example 1-6 66 4.24.2 2020 (0.22, 0.63)(0.22, 0.63) 9090
실험예 1-7Experimental Example 1-7 77 4.14.1 2222 (0.22, 0.64)(0.22, 0.64) 9292
실험예 1-8Experimental Example 1-8 88 4.24.2 2121 (0.23, 0.64)(0.23, 0.64) 9393
실험예 1-9Experimental Example 1-9 99 4.24.2 2222 (0.22, 0.63)(0.22, 0.63) 9090
실험예 1-10Experimental Example 1-10 1010 4.14.1 2121 (0.22, 0.64)(0.22, 0.64) 9696
실험예 1-11Experimental Example 1-11 1111 4.24.2 2020 (0.22, 0.63)(0.22, 0.63) 9393
실험예 1-12Experimental Example 1-12 1212 4.14.1 2020 (0.22, 0.64)(0.22, 0.64) 9292
비교예 1-1Comparative Example 1-1 4CzIPN4CzIPN 4.74.7 1515 (0.21, 0.61)(0.21, 0.61) 5151
비교예 1-2Comparative Example 1-2 T1T1 4.84.8 88 (0.16, 0.52)(0.16, 0.52) 1010
비교예 1-3Comparative Example 1-3 T2T2 4.84.8 1010 (0.16, 0.51)(0.16, 0.51) 1212
비교예 1-4Comparative Example 1-4 T3T3 4.74.7 77 (0.18, 0.51)(0.18, 0.51) 1010
상기 표 1에서 보는 바와 같이, 상기 화학식 1의 화합물을 사용한 실험예 1-1 내지 1-12의 소자는 비교예 1-1에서 화합물 4CzIPN의 물질을 사용한 소자보다 전압이 낮아지고, 효율이 향상되었다.As shown in Table 1, the device of Experimental Examples 1-1 to 1-12 using the compound of Formula 1 has a lower voltage and improved efficiency than the device of the compound 4CzIPN in Comparative Example 1-1. .
또한, 페닐렌에 결합된 카바졸이 전부 비치환되거나, 페닐렌에 2개의 카바졸만이 결합된 화합물을 사용한 비교예 1-2 내지 1-4와 비교하여, 상기 화학식 1의 화합물을 사용한 소자가 전압, 효율, 색순도 및 수명 면에서 특성이 모두 향상됨을 알 수 있었다.In addition, compared to Comparative Examples 1-2 to 1-4 using a compound in which all carbazoles bonded to phenylene are unsubstituted or only two carbazoles are bonded to phenylene, a device using the compound of Formula 1 It was found that the characteristics were improved in terms of voltage, efficiency, color purity, and life.
따라서, 본 발명에 따른 화합물은 발광 능력이 우수하고 색순도가 높아 지연 형광 유기 발광 소자에 적용 가능함을 확인할 수 있었다. Therefore, it was confirmed that the compound according to the present invention has excellent luminescence ability and high color purity, and thus can be applied to a delayed fluorescent organic light emitting device.
<비교예 2-1><Comparative Example 2-1>
ITO(Indium Tin Oxide)가 1,000Å의 두께로 박막 코팅된 유리 기판을 세제를 녹인 증류수에 넣고 초음파로 세척하였다. 이 때, 세제로는 피셔사(Fischer Co.) 제품을 사용하였으며, 증류수로는 밀러포어사(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 및 메탄올의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 수송시켰다. 또한, 산소 플라즈마를 이용하여 상기 기판을 5분간 세정한 후 진공 증착기로 기판을 수송시켰다. 이렇게 준비된 ITO 투명 전극 위에 각 박막을 진공 증착법으로 진공도 5.0Х10-4㎩로 적층하였다. 먼저, ITO 상에 헥사아자트리페닐렌-헥사니트릴(HAT-CN)을 500Å의 두께로 열 진공 증착하여 정공 주입층을 형성하였다.The glass substrate coated with ITO (Indium Tin Oxide) with a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, Fischer (Fischer Co.) was used as a detergent, and distilled water filtered secondarily by a filter of Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice for 10 minutes with distilled water. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after the substrate was cleaned for 5 minutes using oxygen plasma, the substrate was transferred to a vacuum evaporator. Each thin film was laminated on the prepared ITO transparent electrode with a vacuum degree of 5.0Х10 -4 으로 by vacuum deposition. First, a hole injection layer was formed by thermal vacuum deposition of hexaazatriphenylene-hexanitrile (HAT-CN) to a thickness of 500 Pa on ITO.
상기 정공 주입층 위에 하기 화합물 NPB를 진공 증착하여 정공 수송층(300Å)을 형성하였다.The following compound NPB was vacuum deposited on the hole injection layer to form a hole transport layer (300 kPa).
상기 정공 수송층 위에 막 두께 100Å으로 하기 화합물 EB1를 진공 증착하여 전자 차단층(100Å)을 형성하였다.The following compound EB1 was vacuum deposited on the hole transport layer to a thickness of 100 mm 2 to form an electron blocking layer (100 mm 2).
이어서, 상기 전자 차단층 위에 막 두께 300Å으로 하기 화합물 m-CBP 4CzIPN 및 GD1을 68:30:2의 중량비로 진공 증착하여 발광층을 형성하였다.Subsequently, the following compound m-CBP 4CzIPN and GD1 were deposited on the electron blocking layer at a thickness of 300 mm 3 in a weight ratio of 68: 30: 2 to form a light emitting layer.
상기 발광층 위에 막 두께 100Å으로 하기 화합물 HB1을 진공 증착하여 정공 차단층을 형성하였다.A hole blocking layer was formed by vacuum-depositing the following compound HB1 with a thickness of 100 mm 2 on the light emitting layer.
상기 정공 차단층 위에 하기 화합물 ET1과 화합물 LiQ(Lithium Quinolate)를 1:1의 중량비로 진공 증착하여 300Å의 두께로 전자 주입 및 수송층을 형성하였다. 상기 전자 주입 및 수송층 위에 순차적으로 12Å 두께로 리튬플로라이드(LiF)와 2,000Å 두께로 알루미늄을 증착하여 음극을 형성하였다.The following compound ET1 and the compound LiQ (Lithium Quinolate) were vacuum deposited on the hole blocking layer at a weight ratio of 1: 1 to form an electron injection and transport layer with a thickness of 300 Pa. On the electron injection and transport layer, lithium fluoride (LiF) with a thickness of 12 Å and aluminum with a thickness of 2,000 순차적 were sequentially deposited to form a negative electrode.
상기의 과정에서 유기물의 증착속도는 0.4Å/sec 내지 0.7Å/sec를 유지하였고, 음극의 리튬플로라이드는 0.3Å/sec, 알루미늄은 2Å/sec의 증착 속도를 유지하였으며, 증착시 진공도는 2×10-7torr 내지 5×10-6torr를 유지하여, 유기 발광소자를 제작하였다.In the above process, the deposition rate of the organic material was maintained at 0.4Å / sec to 0.7Å / sec, the lithium fluoride of the negative electrode was maintained at a deposition rate of 0.3Å / sec, and aluminum at 2Å / sec. An organic light emitting device was manufactured by maintaining 10 × 7 torr to 5 × 10 −6 torr.
Figure PCTKR2019013897-appb-I000093
Figure PCTKR2019013897-appb-I000093
<실험예 2-1 내지 2-12><Experimental Examples 2-1 to 2-12>
상기 비교예 2-1에서 화합물 4CzIPN 대신 하기 표 2의 화합물을 사용한 것을 제외하고는 비교예 2-1과 동일한 방법으로 유기 발광 소자를 제작하였다.An organic light emitting diode was manufactured according to the same method as Comparative Example 2-1 except for using the compound of Table 2 below instead of the compound 4CzIPN in Comparative Example 2-1.
Figure PCTKR2019013897-appb-I000094
Figure PCTKR2019013897-appb-I000094
<비교예 2-2 내지 2-4><Comparative Examples 2-2 to 2-4>
상기 비교예 2-1에서 화합물 4CzIPN 대신 하기 표 2의 화합물을 사용한 것을 제외하고는 비교예 2-1과 동일한 방법으로 유기 발광 소자를 제작하였다.An organic light emitting diode was manufactured according to the same method as Comparative Example 2-1 except for using the compound of Table 2 below instead of the compound 4CzIPN in Comparative Example 2-1.
Figure PCTKR2019013897-appb-I000095
Figure PCTKR2019013897-appb-I000095
실험예 2-1 내지 2-12 및 비교예 2-1 내지 2-4의 유기 발광 소자에 대하여 10㎃/㎠의 전류밀도에서 측정한 구동 전압(V)과 전류효율(cd/A), 3000cd/m2의 휘도에서 측정한 CIE 색좌표를 측정하여, 하기 표 2에 나타내었다.The driving voltage (V) and the current efficiency (cd / A), 3000 cd, measured at a current density of 10 mA / cm 2 for the organic light emitting devices of Experimental Examples 2-1 to 2-12 and Comparative Examples 2-1 to 2-4 CIE color coordinates measured at a luminance of / m 2 were measured, and are shown in Table 2 below.
구분division 화합물(발광층)Compound (light emitting layer) 전압(V)Voltage (V) 효율(cd/A)Efficiency (cd / A) CIE 색좌표(x,y)CIE color coordinate (x, y)
실험예 2-1Experimental Example 2-1 1One 4.14.1 2222 (0.19, 0.69)(0.19, 0.69)
실험예 2-2Experimental Example 2-2 22 4.04.0 2121 (0.19, 0.69)(0.19, 0.69)
실험예 2-3Experimental Example 2-3 33 4.14.1 2222 (0.20, 0.68)(0.20, 0.68)
실험예 2-4Experimental Example 2-4 44 4.14.1 2222 (0.19, 0.70)(0.19, 0.70)
실험예 2-5Experimental Example 2-5 55 4.24.2 2020 (0.20, 0.69)(0.20, 0.69)
실험예 2-6Experimental Example 2-6 66 4.04.0 2121 (0.19, 0.69)(0.19, 0.69)
실험예 2-7Experimental Example 2-7 77 4.14.1 2121 (0.19, 0.68)(0.19, 0.68)
실험예 2-8Experimental Example 2-8 88 4.14.1 2222 (0.19, 0.69)(0.19, 0.69)
실험예 2-9Experimental Example 2-9 99 4.24.2 2121 (0.20, 0.69)(0.20, 0.69)
실험예 2-10Experimental Example 2-10 1010 4.04.0 2222 (0.19, 0.70)(0.19, 0.70)
실험예 2-11Experimental Example 2-11 1111 4.14.1 2020 (0.19, 0.68)(0.19, 0.68)
실험예 2-12Experimental Example 2-12 1212 4.14.1 2121 (0.20, 0.68)(0.20, 0.68)
비교예 2-1Comparative Example 2-1 4CzIPN4CzIPN 4.64.6 1616 (0.16, 0.67)(0.16, 0.67)
비교예 2-2Comparative Example 2-2 T1T1 4.74.7 1010 (0.15, 0.60)(0.15, 0.60)
비교예 2-3Comparative Example 2-3 T2T2 4.84.8 1010 (0.14, 0.59)(0.14, 0.59)
비교예 2-4Comparative Example 2-4 T3T3 4.74.7 1111 (0.16, 0.60)(0.16, 0.60)
상기 표 2에서 보는 바와 같이, 상기 화학식 1의 화합물을 사용한 실험예 2-1 내지 2-12의 소자는 비교예 2-1의 화합물 4CzIPN의 물질을 사용한 소자보다 전압이 낮아지고, 효율이 향상되었다.As shown in Table 2, the device of Experimental Examples 2-1 to 2-12 using the compound of Formula 1 had a lower voltage and improved efficiency than the device of the compound 4CzIPN of Comparative Example 2-1. .
또한, 페닐렌에 결합된 카바졸이 전부 비치환되거나, 페닐렌에 2개의 카바졸만이 결합된 화합물을 사용한 비교예 2-1 내지 2-4와 비교하여, 상기 화학식 1의 화합물을 사용한 소자가 전압, 효율 면에서 특성이 모두 향상됨을 알 수 있었다.In addition, compared to Comparative Examples 2-1 to 2-4 using a compound in which all carbazoles bonded to phenylene are unsubstituted or only two carbazoles are bonded to phenylene, a device using the compound of Formula 1 It was found that the characteristics were improved in terms of voltage and efficiency.
따라서, 본 발명에 따른 화합물은 발광 능력이 우수하고 발광 파장 튜닝이 가능하여 높은 색순도의 유기 발광 소자 구현이 가능함을 확인할 수 있었다.Therefore, it was confirmed that the compound according to the present invention has excellent luminescence ability and is capable of tuning the emission wavelength, thereby realizing an organic light emitting device having high color purity.
이상을 통해 본 발명의 바람직한 실험예에 대하여 설명하였지만, 본 발명은 이에 한정되는 것이 아니고 특허청구범위와 발명의 상세한 설명의 범위 안에서 여러 가지로 변형하여 실시하는 것이 가능하고 이 또한 발명의 범주에 속한다.Although the preferred experimental example of the present invention has been described through the above, the present invention is not limited to this, and it is possible to carry out various modifications within the scope of the claims and the detailed description of the invention, and this also belongs to the scope of the invention. .

Claims (8)

  1. 하기 화학식 1로 표시되는 화합물:Compound represented by the formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2019013897-appb-I000096
    Figure PCTKR2019013897-appb-I000096
    상기 화학식 1에 있어서,In Chemical Formula 1,
    A1 및 A2는 서로 같거나 상이하고, 각각 독립적으로 시아노기; 또는 시아노기로 치환된 페닐기이며,A1 and A2 are the same as or different from each other, and each independently a cyano group; Or a phenyl group substituted with a cyano group,
    R5 및 R6 중 어느 하나 또는 R은 *와 결합하고, Either R5 or R6 or R is combined with *,
    R1 내지 R4; 및 *와 결합하지 않는 R5 및 R6는 서로 같거나 상이하고, 각각 독립적으로 중수소; 할로겐기; 시아노기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 붕소기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 사이클로알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로고리기이거나, 인접한 기와 서로 결합하여 치환 또는 비치환된 고리를 형성하며,R1 to R4; And R5 and R6 which do not bind to * are the same as or different from each other, and each independently deuterium; Halogen group; Cyano group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or combine with adjacent groups to form a substituted or unsubstituted ring,
    Y는 시아노기, 치환 또는 비치환된 알킬기, 치환 또는 비치환된 시클로알킬기 및 치환 또는 비치환된 헤테로아릴기로 이루어진 군으로부터 선택된 1 이상의 치환기로 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 이종원소로 O 또는 S를 포함하는 헤테로아릴기이고,Y is an aryl group substituted or unsubstituted with one or more substituents selected from the group consisting of a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted heteroaryl group; Or a heteroaryl group containing O or S as a substituted or unsubstituted hetero element,
    *와 결합하지 않는 R은 치환 또는 비치환된 아릴기이며,R not bonded to * is a substituted or unsubstituted aryl group,
    n1 내지 n6은 각각 0 내지 4의 정수이고, n1+n2+n3+n4+n5+n6는 1 이상이며,n1 to n6 are each an integer of 0 to 4, n1 + n2 + n3 + n4 + n5 + n6 is 1 or more,
    n1 내지 n6가 각각 2 이상의 정수인 경우 2 이상의 괄호 내의 치환기는 서로 같거나 상이하다.When n1 to n6 are each an integer of 2 or more, the substituents in 2 or more parentheses are the same or different from each other.
  2. 청구항 1에 있어서, The method according to claim 1,
    상기 화학식 1은 하기 화학식 2 또는 3으로 표시되는 것인 화합물:Formula 1 is a compound represented by the following formula 2 or 3:
    [화학식 2][Formula 2]
    Figure PCTKR2019013897-appb-I000097
    Figure PCTKR2019013897-appb-I000097
    [화학식 3][Formula 3]
    Figure PCTKR2019013897-appb-I000098
    Figure PCTKR2019013897-appb-I000098
    상기 화학식 2 및 3에 있어서,In Chemical Formulas 2 and 3,
    R1 내지 R6, n1 내지 n6, Y, A1 및 A2의 정의는 상기 화학식 1에서 정의한 바와 같고, R1 to R6, n1 to n6, Y, A1 and A2 are the same as defined in Formula 1,
    R'는 치환 또는 비치환된 아릴기이다.R 'is a substituted or unsubstituted aryl group.
  3. 청구항 1에 있어서, The method according to claim 1,
    상기 R1 내지 R4; 및 *와 결합하지 않는 R5 및 R6는 서로 같거나 상이하고, 각각 독립적으로 중수소; 시아노기; 치환 또는 비치환된 탄소수 1 내지 20의 알킬기; 또는 치환 또는 비치환된 탄소수 6 내지 30의 아릴기이거나, 인접한 기와 서로 결합하여 치환 또는 비치환된 탄소수 6 내지 30의 방향족 탄화수소 고리를 형성하는 화합물.R1 to R4; And R5 and R6 which do not bind to * are the same as or different from each other, and each independently deuterium; Cyano group; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a compound that combines with an adjacent group to form a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms.
  4. 청구항 1에 있어서, The method according to claim 1,
    상기 화학식 1은 하기 구조들 중 어느 하나로 표시되는 것인 화합물:Formula 1 is a compound represented by any one of the following structures:
    Figure PCTKR2019013897-appb-I000099
    Figure PCTKR2019013897-appb-I000099
    Figure PCTKR2019013897-appb-I000100
    Figure PCTKR2019013897-appb-I000100
    Figure PCTKR2019013897-appb-I000101
    Figure PCTKR2019013897-appb-I000101
    Figure PCTKR2019013897-appb-I000102
    Figure PCTKR2019013897-appb-I000102
    Figure PCTKR2019013897-appb-I000103
    Figure PCTKR2019013897-appb-I000103
    Figure PCTKR2019013897-appb-I000104
    Figure PCTKR2019013897-appb-I000104
    Figure PCTKR2019013897-appb-I000105
    Figure PCTKR2019013897-appb-I000105
    Figure PCTKR2019013897-appb-I000106
    Figure PCTKR2019013897-appb-I000106
    Figure PCTKR2019013897-appb-I000107
    Figure PCTKR2019013897-appb-I000107
    Figure PCTKR2019013897-appb-I000108
    Figure PCTKR2019013897-appb-I000108
    Figure PCTKR2019013897-appb-I000109
    Figure PCTKR2019013897-appb-I000109
    Figure PCTKR2019013897-appb-I000110
    Figure PCTKR2019013897-appb-I000110
    Figure PCTKR2019013897-appb-I000111
    Figure PCTKR2019013897-appb-I000111
    Figure PCTKR2019013897-appb-I000112
    Figure PCTKR2019013897-appb-I000112
    Figure PCTKR2019013897-appb-I000113
    Figure PCTKR2019013897-appb-I000113
    Figure PCTKR2019013897-appb-I000114
    Figure PCTKR2019013897-appb-I000114
    Figure PCTKR2019013897-appb-I000115
    Figure PCTKR2019013897-appb-I000115
    Figure PCTKR2019013897-appb-I000116
    Figure PCTKR2019013897-appb-I000116
    Figure PCTKR2019013897-appb-I000117
    Figure PCTKR2019013897-appb-I000117
    Figure PCTKR2019013897-appb-I000118
    Figure PCTKR2019013897-appb-I000118
    Figure PCTKR2019013897-appb-I000119
    Figure PCTKR2019013897-appb-I000119
    Figure PCTKR2019013897-appb-I000120
    Figure PCTKR2019013897-appb-I000120
    Figure PCTKR2019013897-appb-I000121
    Figure PCTKR2019013897-appb-I000121
    Figure PCTKR2019013897-appb-I000122
    Figure PCTKR2019013897-appb-I000122
    Figure PCTKR2019013897-appb-I000123
    Figure PCTKR2019013897-appb-I000123
    Figure PCTKR2019013897-appb-I000124
    Figure PCTKR2019013897-appb-I000124
    Figure PCTKR2019013897-appb-I000125
    Figure PCTKR2019013897-appb-I000125
    Figure PCTKR2019013897-appb-I000126
    Figure PCTKR2019013897-appb-I000126
    Figure PCTKR2019013897-appb-I000127
    Figure PCTKR2019013897-appb-I000127
    Figure PCTKR2019013897-appb-I000128
    .
    Figure PCTKR2019013897-appb-I000128
    .
  5. 제1 전극; 상기 제1 전극과 대향하여 구비되는 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비되는 1층 이상의 유기물층을 포함하고, 상기 유기물층 중 1층 이상이 청구항 1 내지 4 중 어느 한 항에 따른 화합물을 포함하는 것인 유기발광소자.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 layer of the organic material layer contains the compound according to any one of claims 1 to 4.
  6. 청구항 5에 있어서,The method according to claim 5,
    상기 유기물층은 정공주입층 또는 정공수송층을 포함하고, 상기 정공주입층 또는 정공수송층은 상기 화학식 1로 표시되는 화합물을 포함하는 것인 유기발광소자.The organic material layer comprises a hole injection layer or a hole transport layer, the hole injection layer or hole transport layer is an organic light emitting device comprising a compound represented by the formula (1).
  7. 청구항 5에 있어서,The method according to claim 5,
    상기 유기물층은 전자수송층 또는 전자주입층을 포함하고, 상기 전자수송층 또는 전자주입층은 상기 화학식 1로 표시되는 화합물을 포함하는 것인 유기발광소자.The organic material layer includes an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer comprises an compound represented by the formula (1).
  8. 청구항 5에 있어서,The method according to claim 5,
    상기 유기물층은 발광층을 포함하고, 상기 발광층은 상기 화학식 1로 표시되는 화합물을 포함하는 것인 유기발광소자.The organic material layer includes a light emitting layer, the light emitting layer is an organic light emitting device comprising a compound represented by the formula (1).
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