WO2020197253A1 - 헤테로고리 화합물 및 이를 포함하는 유기 발광 소자 - Google Patents

헤테로고리 화합물 및 이를 포함하는 유기 발광 소자 Download PDF

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WO2020197253A1
WO2020197253A1 PCT/KR2020/004034 KR2020004034W WO2020197253A1 WO 2020197253 A1 WO2020197253 A1 WO 2020197253A1 KR 2020004034 W KR2020004034 W KR 2020004034W WO 2020197253 A1 WO2020197253 A1 WO 2020197253A1
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substituted
unsubstituted
group
formula
hydrogen
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윤홍식
김명곤
김민준
홍완표
김진주
한시현
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주식회사 엘지화학
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Priority to CN202080006131.4A priority Critical patent/CN113015734B/zh
Publication of WO2020197253A1 publication Critical patent/WO2020197253A1/ko

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06—Peri-condensed systems
    • 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
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • Organic light-emitting devices using a third-generation delayed fluorescent material have recently attracted attention following a fluorescent material as a first-generation light emitting material and a phosphorescent material as a second-generation light emitting material.
  • the third-generation delayed fluorescent material is a material that converts triplet excitons into singlet excitons and converts them to light, unlike phosphorescent materials that convert singlet excitons into triplet excitons and converts them into light, and because of this process, they exhibit delayed fluorescence characteristics. Delayed fluorescent materials can theoretically convert both singlet excitons and triplet excitons into light, so 100% internal quantum efficiency is possible, and is expected to be a material that can overcome the limitations of lifespan and efficiency of phosphorescent materials. have.
  • thermally activated delayed fluorescence also referred to as thermally activated delayed fluorescence: hereinafter, appropriately abbreviated as'TADF'
  • RISC' Reverse Intersystem Crossing
  • the lowest singlet level (S1) (hereinafter abbreviated as'singlet energy level') and the lowest triplet energy level (T1) (hereinafter abbreviated as'triplet energy level') It is required that the absolute value ⁇ E ST of the difference with is small.
  • the TADF phenomenon in order to express the TADF phenomenon, it is effective to reduce the ⁇ E ST of the organic compound, and in order to decrease the ⁇ E ST , the highest occupied molecular orbital (HOMO) and the lowest non-occupied molecular orbital (LUMO) in the molecule It is effective to localize (clearly separate) without mixing them.
  • HOMO highest occupied molecular orbital
  • LUMO lowest non-occupied molecular orbital
  • An object of the present invention is to provide an organic light-emitting device including a heterocyclic compound and a heterocyclic compound capable of improving driving voltage, current efficiency, and/or life characteristics of the device.
  • An exemplary embodiment of the present specification provides a heterocyclic compound of Formula 1 below.
  • Y1 is hydrogen; heavy hydrogen; Cyano group; Or a haloalkyl group,
  • Y2 is hydrogen; heavy hydrogen; Cyano group; Or a haloalkyl group,
  • a and B is a group represented by the following formula 2-1, the other is a group represented by the following formula 2-2,
  • X1 to X3 are each independently CH, C-CN or N, and at least one of X1 to X3 is N,
  • Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
  • X4 is S, O, N(R1) or C(R2)(R3),
  • b is 1 or 2
  • if b is 2 Are the same or different from each other
  • R1 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or combine with G1 or adjacent R5 to form a substituted or unsubstituted ring,
  • R2 and R3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or combine with G1 or adjacent R5 to form a substituted or unsubstituted ring, or R2 and R3 combine with each other to form a substituted or unsubstituted ring,
  • R4 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
  • R5 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or combine with adjacent R1, adjacent R2 or adjacent R3 to form a substituted or unsubstituted ring,
  • G1 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or combined with R1, R2 or R3 to form a substituted or unsubstituted ring,
  • G2 to G4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
  • a4 is an integer of 0 to 4, and if a4 is 2 or more, R4 is the same as or different from each other,
  • a5 is 0, 1 or 2
  • R5 is the same as or different from each other.
  • Another exemplary embodiment of the present specification is an organic light-emitting device including a first electrode, a second electrode, and one or more organic material layers disposed between the first electrode and the second electrode, comprising the heterocyclic compound of Formula 1 It provides an organic light emitting device.
  • the heterocyclic compound of the present invention can be used as a delayed fluorescent material in an organic light-emitting device, and when the heterocyclic compound is used in an organic light-emitting device, low driving voltage (V), high current efficiency (cd/A), and high luminance (cd/ m 2 ), high power efficiency and/or high lifespan characteristics can be implemented.
  • FIG. 1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.
  • FIG. 2 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 8, a hole blocking layer 9, an electron injection and transport layer ( 10) and a cathode 4 are shown as an example of an organic light-emitting device.
  • substituted means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent.
  • the position at which the substituent is substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, the position at which the substituent is substituted.
  • the two or more substituents may be the same or different from each other.
  • substituted or unsubstituted refers to deuterium; Halogen group; Cyano group; Alkyl group; Cycloalkyl group; Aryl group; And one or more substituents selected from the group consisting of a heteroaryl group, or two or more substituents selected from the group are substituted or unsubstituted with a substituent connected to each other.
  • examples of the halogen group include fluorine, chlorine, bromine or iodine.
  • the alkyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an 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. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms.
  • alkyl group examples include methyl, ethyl, propyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, n-pentyl, isopentyl, Neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cycloheptyl Methyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl
  • the haloalkyl group is an alkyl group substituted with a halogen group.
  • the cycloalkyl group refers to a cyclic hydrocarbon group, and the number of carbon atoms is not particularly limited, but is preferably 3 to 60, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, there are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.
  • an aryl group means a hydrocarbon ring that is wholly or partially unsaturated and has aromaticity.
  • the number of carbon atoms 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 an exemplary embodiment, the aryl group has 6 to 40 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms.
  • the monocyclic aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto.
  • the polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, a triphenylenyl group, and the like, but is not limited thereto.
  • the substituted fluorenyl group includes all compounds in which two substituents of the pentagonal ring of fluorene are spied to form a ring.
  • the substituted fluorenyl group includes 9,9'-spirobifluorene, spiro[cyclopentane-1,9'-fluorene], spiro[benzo[c]fluorene-7,9-fluorene], etc. However, it is not limited thereto.
  • the heteroaryl group is a substituted or unsubstituted monocyclic or polycyclic that includes one or more of N, O, and S as a hetero atom, and is wholly or partially unsaturated and has aromaticity, and the number of carbon atoms is particularly limited. However, it is preferably 2 to 60 carbon atoms. According to an exemplary embodiment, the heteroaryl group has 2 to 40 carbon atoms. According to another exemplary embodiment, the heteroaryl group has 2 to 30 carbon atoms.
  • heteroaryl groups include thiophenyl group, furanyl group, pyrrolyl group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, triazolyl group, pyridinyl group, bipyridinyl group, pyrimidinyl group, tria Genyl group, triazolyl group, acridinyl group, carbonyl group, acenaphthoquinoxalinyl group, indenoquinazolinyl group, indenoisoquinolinyl group, indenoquinolinyl group, pyridoindolyl group, pyridazinyl group, Pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazin
  • the "adjacent" group means a substituent substituted on an atom directly connected to the atom where the corresponding substituent is substituted, a substituent positioned three-dimensionally closest to the corresponding substituent, or another substituent substituted on the atom where the corresponding substituent is substituted.
  • I can.
  • two substituents substituted at an ortho position in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring may be interpreted as "adjacent" groups to each other.
  • the substituted or unsubstituted ring formed by bonding of adjacent groups to each other may be an aliphatic ring, an aromatic hydrocarbon ring, or a hetero ring, or a condensed ring thereof.
  • the triplet energy level T1 is a difference between the energy level of the ground state and the energy level of the triplet excited state.
  • the singlet energy level S1 is a difference between the energy level of the ground state and the energy level of the singlet excited state.
  • the triplet energy level and the singlet energy level can be measured using a spectroscopic instrument capable of measuring fluorescence and phosphorescence.
  • the triplet energy level is obtained by preparing a solution using toluene or tetrahydrofuran (THF) as a solvent in a cryogenic state using liquid nitrogen, and then irradiating the solution with a light source in the absorption wavelength range of the substance, and singlet from the emission spectrum. Excluding light emission, it can be confirmed by analyzing the triplet emission spectrum. When an electron is excited from a light source, the time that the electron stays in the triplet energy level is much longer than that in the singlet energy level, so that the two components can be separated in a cryogenic state.
  • THF tetrahydrofuran
  • the singlet energy level is measured using a fluorescent device, and unlike the triplet energy level measurement method described above, it may be measured by irradiating a light source at room temperature.
  • HOMO is the highest occupied molecular orbital
  • LUMO is the lowest unoccupied molecular orbital
  • energy level means the energy level. Therefore, even when the energy level is displayed in the negative (-) direction from the vacuum level, the energy level is interpreted to mean the absolute value of the corresponding energy value. For example, when the energy level is'large', it means that the absolute value increases in the negative direction from the vacuum level.
  • expressions such as'deep' or'high' energy level have the same meaning as expressions that energy level is large.
  • the HOMO energy level is measured using UV photoelectron spectroscopy (UPS), which measures the ionization potential of the material by irradiating UV on the surface of the thin film, and at this time, detecting electrons that protrude. It can be measured using cyclic voltammetry (CV), which measures oxidation potential through voltage sweep after dissolving in a solvent together with an electrolyte.
  • UPS UV photoelectron spectroscopy
  • CV cyclic voltammetry
  • An exemplary embodiment of the present specification provides a heterocyclic compound of Formula 1 above.
  • the compound In order for the compound to exhibit a delayed fluorescence phenomenon, it is effective to reduce the difference ( ⁇ E ST ) between the triplet energy level and the singlet energy level of the organic compound, and to decrease ⁇ E ST , the highest occupied molecular orbital in the molecule It is important to localize (clearly separate) the (HOMO) and the least unoccupied molecular orbital (LUMO).
  • the electron acceptor represented by Formula 2-1 and the electron donor represented by Formula 2-2 are connected with dibenzofuran or dibenzothiophene.
  • HOMO is distributed in the electron donor
  • LUMO is distributed in the electron acceptor
  • ⁇ E ST decreases, so that the heterocyclic compound of Formula 1 exhibits delayed fluorescence properties.
  • a and B are substituted on carbons 1 and 4 of dibenzofuran or dibenzothiophene. As A and B are substituted on carbons 1 and 4 of dibenzofuran or dibenzothiophene, A and B are compared to compounds that are not substituted on carbons 1 and 4 of dibenzofuran or dibenzothiophene. Can increase the luminous efficiency of.
  • Y1 and Y2 in Formula 1 are each independently hydrogen; heavy hydrogen; Cyano group; Or it may be a haloalkyl group. At this time, at least one of Y1 and Y2 is deuterium; Cyano group; Or if it is a haloalkyl group, of the heterocyclic compound of Formula 1 Molecular stability is particularly high. When the molecules are energetically stabilized, the lifetime of the organic light emitting device is improved.
  • the emission wavelength of the heterocyclic compound of Formula 1 is 480 nm to 560 nm, preferably 520 nm to 550 nm.
  • Formula 2-2 is represented by any one of the following Formulas 3-1 to 3-6.
  • X4, R4, R5, G1, G2, G3, G4, a4 and a5 are as defined in Formula 2-2.
  • Formula 2-2 is represented by any one of Formulas 4-1 to 4-4 below.
  • X10 is S, O, N(R10) or C(R11)(R12),
  • X11 is S, O, N(R13) or C(R14)(R15),
  • R10 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or combine with G11 to form a substituted or unsubstituted ring,
  • R11 and R12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or combine with G11 to form a substituted or unsubstituted ring, or R11 and R12 combine with each other to form a substituted or unsubstituted ring,
  • R14 and R15 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or combine with G15 to form a substituted or unsubstituted ring, or R14 and R15 combine with each other to form a substituted or unsubstituted ring,
  • G11 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or combined with R10, R11 or R12 to form a substituted or unsubstituted ring,
  • G15 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or combine with R13, R14 or R15 to form a substituted or unsubstituted ring,
  • G12 to G14 and G16 to G18 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
  • R4 and a4 are as defined in Formula 2-2.
  • Formula 2-2 is represented by any one of Formulas 5-1 to 5-9 below.
  • R4, a4 and a5 are as defined in Formula 2-2,
  • R5, R21 and R22 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
  • b5 is 0 or 1
  • a21 is an integer of 0 to 4, and if a21 is 2 or more, R21 is the same as or different from each other,
  • b21 is an integer of 0 to 3, and when b21 is 2 or more, R21 is the same as or different from each other,
  • a22 is an integer of 0 to 4, and when a22 is 2 or more, R22 is the same as or different from each other.
  • At least two of X1 to X3 are N.
  • X1 is N
  • X2 is CH, C-CN or N
  • X3 is CH, C-CN or N.
  • X1 is CH, C-CN or N
  • X2 is N
  • X3 is CH, C-CN or N.
  • X1 is N
  • X2 is CH, C-CN or N
  • X3 is N
  • X1 to X3 are each N.
  • Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group.
  • Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted (C6-C30)aryl group.
  • Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted (C6-C20)aryl group.
  • Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted (C6-C16) aryl group.
  • Ar1 and Ar2 are aryl groups unsubstituted or substituted with deuterium or an aryl group.
  • the substituent of the aryl group is deuterium; Or a substituted or unsubstituted aryl group.
  • the substituent of the aryl group is deuterium; Or (C6-C20) aryl group.
  • the substituent of the aryl group is deuterium; Or (C6-C16) aryl group.
  • Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with deuterium; Or a biphenyl group unsubstituted or substituted with deuterium.
  • Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group; D 5 -phenyl group; Or a biphenyl group.
  • Y1 is hydrogen; Cyano group; Or (C1-C10) haloalkyl group.
  • Y1 is hydrogen; Cyano group; Or (C1-C6) haloalkyl group.
  • Y1 is hydrogen; Cyano group; Or a trifluoromethyl group.
  • Y2 is hydrogen; Cyano group; Or (C1-C10) haloalkyl group.
  • Y2 is hydrogen; Cyano group; Or (C1-C6) haloalkyl group.
  • Y2 is hydrogen; Cyano group; Or a trifluoromethyl group.
  • At least one of Y1 and Y2 is deuterium; Cyano group; Or a haloalkyl group.
  • At least one of Y1 and Y2 is a cyano group; Or a haloalkyl group.
  • At least one of Y1 and Y2 is a cyano group; Or a trifluoroalkyl group.
  • At least one of Y1 and Y2 is a cyano group.
  • R1 is a substituted or unsubstituted aryl group, or combines with G1 or adjacent R5 to form a substituted or unsubstituted ring.
  • R1 is a substituted or unsubstituted (C6-C30)aryl group, or is bonded to G1 or adjacent R5 to form a substituted or unsubstituted (C5-C30) ring.
  • R1 is a substituted or unsubstituted (C6-C20)aryl group, or is bonded to G1 or adjacent R5 to form a substituted or unsubstituted (C5-C20) ring.
  • R1 is a substituted or unsubstituted phenyl group, or combines with G1 or adjacent R5 to form a substituted or unsubstituted indole ring.
  • R1 is a substituted or unsubstituted phenyl group, or combines with G1 or adjacent R5 to form a substituted or unsubstituted pentagonal ring.
  • R1 is a phenyl group, or is bonded to adjacent G1 or adjacent R5 to form an indole ring.
  • R1 is a substituted or unsubstituted phenyl group, or is bonded to G1 or adjacent R5 to form a pentagonal ring in which a benzene ring is condensed.
  • R2 and R3 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group, or combine with each other to form a substituted or unsubstituted ring.
  • R2 and R3 are the same as or different from each other, and each independently a substituted or unsubstituted (C1-C15) alkyl group; Or a substituted or unsubstituted (C6-C30) aryl group, or combine with each other to form a substituted or unsubstituted (C5-C36) ring.
  • R2 and R3 are the same as or different from each other, and each independently a substituted or unsubstituted (C1-C10) alkyl group; Or a substituted or unsubstituted (C6-C20) aryl group, or combine with each other to form a substituted or unsubstituted (C5-C25) ring.
  • R2 and R3 are the same as or different from each other, and each independently a substituted or unsubstituted (C1-C6) alkyl group; Or a substituted or unsubstituted (C6-C12) aryl group, or combine with each other to form a substituted or unsubstituted (C5-C16) ring.
  • R2 and R3 are the same as or different from each other, and each independently a methyl group; Or a phenyl group, R2 and R3 are each a phenyl group, and are bonded to each other to form a fluorene ring.
  • R4 is hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.
  • R4 is hydrogen; A substituted or unsubstituted (C6-C30) aryl group; Or a substituted or unsubstituted (C2-C30) heteroaryl group.
  • R4 is hydrogen; A substituted or unsubstituted (C6-C20) aryl group; Or a substituted or unsubstituted (C2-C20) heteroaryl group.
  • R4 is hydrogen; A substituted or unsubstituted (C6-C12) aryl group; Or a substituted or unsubstituted (C2-C16) heteroaryl group.
  • R4 is hydrogen; Phenyl group; Dibenzofuranyl group; Dibenzothiophenyl group; Or a carbazolyl group.
  • a4 is 0 or 1.
  • R5 is hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or is bonded to each other with adjacent R1, adjacent R2 or adjacent R3 to form a substituted or unsubstituted ring.
  • R5 is hydrogen; A substituted or unsubstituted (C6-C30) aryl group; Or a substituted or unsubstituted (C2-C30) heteroaryl group, or a substituted or unsubstituted (C2-C36) ring by bonding with adjacent R1, adjacent R2 or adjacent R3 to each other.
  • R5 is hydrogen; A substituted or unsubstituted (C6-C20) aryl group; Or a substituted or unsubstituted (C2-C20) heteroaryl group, or by bonding with adjacent R1, adjacent R2 or adjacent R3 to form a substituted or unsubstituted (C2-C25) ring.
  • R5 is hydrogen; A substituted or unsubstituted (C6-C12) aryl group; Or a substituted or unsubstituted (C2-C16) heteroaryl group, or by bonding with adjacent R1, adjacent R2 or adjacent R3 to form a substituted or unsubstituted (C2-C16) ring.
  • R5 is hydrogen; Phenyl group; Dibenzofuranyl group; Dibenzothiophenyl group; Or a carbazolyl group, or combine with adjacent R1 to form an indole ring.
  • G1 is hydrogen or combines with R1 to form a substituted or unsubstituted ring.
  • G1 is hydrogen or combines with R1 to form a substituted or unsubstituted pentagonal ring.
  • G1 is hydrogen or combines with R1 to form an indole ring.
  • G2 is hydrogen
  • G3 is hydrogen
  • G4 is hydrogen
  • G11 is hydrogen or combines with R10 to form a substituted or unsubstituted ring.
  • G11 is hydrogen or combines with R10 to form a substituted or unsubstituted indole ring.
  • G11 is hydrogen or combines with R10 to form a substituted or unsubstituted pentagonal ring.
  • G11 is hydrogen or combines with R10 to form an indole ring.
  • G11 is hydrogen or combines with R10 to form a pentagonal ring in which a benzene ring is condensed.
  • G12 is hydrogen
  • G13 is hydrogen
  • G15 is hydrogen or combines with R13 to form a substituted or unsubstituted ring.
  • G15 is hydrogen or combines with R13 to form a substituted or unsubstituted indole ring.
  • G15 is hydrogen or combines with R13 to form a substituted or unsubstituted pentagonal ring.
  • G15 is hydrogen or combines with R13 to form an indole ring.
  • G15 is hydrogen or combines with R13 to form a pentagonal ring in which a benzene ring is condensed.
  • G16 is hydrogen
  • G17 is hydrogen
  • G18 is hydrogen
  • R10 is a substituted or unsubstituted (C6-C30)aryl group, or combines with G11 to form a substituted or unsubstituted (C5-C30) ring.
  • R10 is a substituted or unsubstituted (C6-C20) aryl group, or combines with G11 to form a substituted or unsubstituted (C5-C20) ring.
  • R10 is a substituted or unsubstituted phenyl group, or combines with G11 to form a substituted or unsubstituted indole ring.
  • R10 is a substituted or unsubstituted phenyl group, or combines with G11 to form a substituted or unsubstituted pentagonal ring.
  • R10 is a phenyl group, or is bonded to each other with G11 to form an indole ring.
  • R10 is a substituted or unsubstituted phenyl group, or combines with G11 to form a pentagonal ring in which a benzene ring is condensed.
  • R13 is a substituted or unsubstituted (C6-C30)aryl group, or combines with G15 to form a substituted or unsubstituted (C5-C30) ring.
  • R13 is a substituted or unsubstituted (C6-C20)aryl group, or combines with G15 to form a substituted or unsubstituted (C5-C20) ring.
  • R13 is a substituted or unsubstituted phenyl group, or combines with G15 to form a substituted or unsubstituted indole ring.
  • R13 is a substituted or unsubstituted phenyl group, or combines with G15 to form a substituted or unsubstituted pentagonal ring.
  • R13 is a phenyl group, or is bonded to G15 to form an indole ring.
  • R13 is a substituted or unsubstituted phenyl group, or combines with G15 to form a pentagonal ring in which a benzene ring is condensed.
  • R11 and R12 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group, or R11 and R12 are bonded to each other to form a substituted or unsubstituted ring.
  • R11 and R12 are the same as or different from each other, and each independently a substituted or unsubstituted (C1-C15)alkyl group; Or a substituted or unsubstituted (C6-C30) aryl group, or R11 and R12 are bonded to each other to form a substituted or unsubstituted (C5-C36) ring.
  • R11 and R12 are the same as or different from each other, and each independently a substituted or unsubstituted (C1-C10) alkyl group; Or a substituted or unsubstituted (C6-C20) aryl group, or R11 and R12 are bonded to each other to form a substituted or unsubstituted (C5-C25) ring.
  • R11 and R12 are the same as or different from each other, and each independently a substituted or unsubstituted (C1-C6) alkyl group; Or a substituted or unsubstituted (C6-C12) aryl group, or R11 and R12 are bonded to each other to form a substituted or unsubstituted (C5-C16) ring.
  • R11 and R12 are the same as or different from each other, and each independently a methyl group; Or a phenyl group, R11 and R12 are each a phenyl group, and are bonded to each other to form a fluorene ring.
  • R14 and R15 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group, or R14 and R15 are bonded to each other to form a substituted or unsubstituted ring.
  • R14 and R15 are the same as or different from each other, and each independently a substituted or unsubstituted (C1-C15)alkyl group; Or a substituted or unsubstituted (C6-C30) aryl group, or R14 and R15 are bonded to each other to form a substituted or unsubstituted (C5-C36) ring.
  • R14 and R15 are the same as or different from each other, and each independently a substituted or unsubstituted (C1-C10) alkyl group; Or a substituted or unsubstituted (C6-C20) aryl group, or R14 and R15 are bonded to each other to form a substituted or unsubstituted (C5-C25) ring.
  • R14 and R15 are the same as or different from each other, and each independently a substituted or unsubstituted (C1-C6) alkyl group; Or a substituted or unsubstituted (C6-C12) aryl group, or R14 and R15 are bonded to each other to form a substituted or unsubstituted (C5-C16) ring.
  • R14 and R15 are the same as or different from each other, and each independently a methyl group; Or a phenyl group, R14 and R15 are each a phenyl group, and are bonded to each other to form a fluorene ring.
  • the heterocyclic compound of Formula 1 is any one selected from the following compounds.
  • the compound of Formula 1 described above can be synthesized by the following method. First, dibenzofuran or dibenzothiophene in which halide is substituted at carbon positions 1 and 4 are prepared. Next, a heteroaryl group (a group of formula 2-1) such as a triazine group is introduced into one halide of the compound through a Suzuki reaction, and a carbazole (group of formula 2-2) is subjected to an SNAr reaction to the other halide. It is introduced as.
  • a heteroaryl group a group of formula 2-1
  • a carbazole group of formula 2-2
  • the method for synthesizing the compound of Formula 1 is not limited to the above method. Some or all of the synthesis steps may be changed to other known synthesis methods, and other known synthesis methods may be used.
  • An exemplary embodiment of the present specification provides an organic light-emitting device including the heterocyclic compound of Formula 1 above.
  • the organic material layer includes an emission layer, and the emission layer includes the heterocyclic compound of Formula 1 described above.
  • the organic material layer includes an emission layer, the emission layer includes a dopant, and the dopant includes the heterocyclic compound of Formula 1 above.
  • the light emitting layer may be composed of only the heterocyclic compound of Formula 1 described above, or may further include other materials other than the heterocyclic compound of Formula 1 above.
  • the heterocyclic compound of Formula 1 may be used as a host or may be used together with other host materials to serve as a dopant.
  • the heterocyclic compound of Formula 1 is used as a dopant.
  • the organic material layer includes an emission layer, and the emission layer comprises 1 part by weight to 100 parts by weight based on 100 parts by weight of the total amount of the emission layer of the heterocyclic compound of Formula 1; It is preferably included in an amount of 20 to 60 parts by weight.
  • the emission layer including the heterocyclic compound of Formula 1 further includes a host.
  • the organic material layer includes an emission layer, and the organic material layer includes a host and a heterocyclic compound of Formula 1 above.
  • the host may be a phosphorescent host or a fluorescent host.
  • the light emitting layer including the heterocyclic compound of Formula 1 is a green light emitting layer.
  • the mechanism by which light emission can occur in the light emitting layer is not limited and may vary depending on the compound used for the light emitting layer.
  • holes and electrons move through the host to the heterocyclic compound (dopant) of Formula 1, and excitons are generated in the triplet and singlet in the dopant in a 3:1 ratio, and then the triplet of the dopant is The generated exciton is transferred to the singlet of the dopant to emit light, and the exciton generated in the singlet can emit light as it is in the singlet.
  • a host acting only as a matrix material is included in the emission layer, and holes; Electronic; Alternatively, holes and electrons may be injected as a dopant without passing through the host to form excitons in the triplet and the singlet.
  • this is only an example of a light-emitting mechanism, and light emission may occur by other light-emitting mechanisms.
  • the difference ( ⁇ E ST ) between the singlet energy level (S1) and the triplet energy level (T1) of the heterocyclic compound of Formula 1 is 0 eV or more and 0.3 eV or less; 0 eV or more and 0.2 eV or less; Or 0 eV or more and 0.1 eV or less.
  • the exciton of the triplet energy level is singlet energy by crossover (RISC)
  • RISC singlet energy by crossover
  • the triplet energy level (T1) of the heterocyclic compound of Formula 1 is 2.1 eV to 2.8 eV.
  • the triplet energy level (T1 H ) of the host is 2.4 eV to 3.2 eV.
  • the triplet energy level (T1 H ) of the host is greater than the triplet energy level (T1) of the heterocyclic compound of Formula 1 above.
  • the singlet energy level (S1 H ) of the host is greater than the singlet energy level (S1) of the heterocyclic compound of Formula 1 above.
  • the host material includes a condensed aromatic ring derivative or a heterocyclic-containing compound.
  • condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene derivatives, and fluoranthene derivatives
  • heterocyclic compounds include carbazole derivatives, benzoimidazole derivatives, and dibenzo. Furan derivatives, ladder furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
  • the host material may be any one selected from the following structures, but this is only an example, and any compound suitable for expressing the delayed fluorescence characteristic of the dopant of the present invention may be used without limitation.
  • the organic material layer includes an emission layer, and the emission layer includes a heterocyclic compound of Formula 1; And a fluorescent emitter.
  • the fluorescent emitter is included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the heterocyclic compound of Formula 1.
  • a fluorescent material such as an anthracene compound, a pyrene compound, and a boron compound may be used, but is not limited thereto.
  • the triplet energy level of the fluorescent emitter is lower than the triplet energy level of the compound represented by Chemical Formula 1.
  • the compound of Formula 1 described above can be prepared using materials and reaction conditions known in the art.
  • the organic light-emitting device of the present invention 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 above-described compound.
  • the organic light-emitting device may be a normal type organic light-emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate.
  • the organic light emitting device may be an inverted type organic light emitting device in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate.
  • 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, for example, a stacked structure as described below, but is not limited thereto.
  • FIGS. 1 and 2 the structure of an organic light emitting device according to an exemplary embodiment of the present specification is illustrated in FIGS. 1 and 2.
  • the heterocyclic compound of Formula 1 may be included in the emission layer.
  • the heterocyclic compound of Formula 1 may be included in the emission layer.
  • the organic light-emitting device of the present specification may be manufactured by materials and methods known in the art, except that at least one of the organic material layers includes the heterocyclic compound of Formula 1 above.
  • the organic light emitting device of the present specification may be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or alloy thereof is deposited on the substrate. It can be manufactured by forming an anode, forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to this method, an organic light-emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
  • PVD physical vapor deposition
  • the heterocyclic compound of Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device.
  • the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.
  • an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate.
  • the manufacturing method is not limited thereto.
  • the cathode material a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer.
  • the cathode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of a metal and an oxide such as ZnO:Al or SNO 2 :Sb; Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto.
  • the cathode material is a material having a small work function to facilitate electron injection into the organic material layer.
  • the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO 2 /Al, but are not limited thereto.
  • the hole injection layer is a layer that injects holes from the electrode, and has the ability to transport holes as a hole injection material, so that it has a hole injection effect at the anode, an excellent hole injection effect for a light emitting layer or a light emitting material, and is generated from the light emitting layer.
  • a compound that prevents the movement of excitons to the electron injection layer or the electron injection material and has excellent thin film formation ability is preferable.
  • the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer.
  • hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances.
  • the hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the emission layer.
  • the hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the emission layer or an adjacent layer. Materials with high mobility are suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer including a conjugated portion and a non-conjugated portion, but are not limited thereto.
  • a hole buffer layer may be additionally provided between the hole injection layer and the hole transport layer.
  • the hole buffer layer may include a hole injection or transport material known in the art.
  • the electron blocking layer is a layer that prevents electrons from flowing into the light emitting layer and controls the flow of holes flowing into the light emitting layer to control the performance of the entire device.
  • the electron blocking material is preferably a compound having the ability to prevent the inflow of electrons from the emission layer to the anode and to control the flow of holes injected into the emission layer or the emission material.
  • an arylamine-based organic material may be used as the electron blocking layer, but is not limited thereto.
  • the light-emitting material a material capable of emitting light in a visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency against fluorescence or phosphorescence is preferable.
  • Specific examples include 8-hydroxyquinoline aluminum complex (Alq 3 ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzothiazole and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.
  • the emission layer may include a host material and a dopant material.
  • Host materials include condensed aromatic ring derivatives or heterocyclic-containing compounds.
  • condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds
  • heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, and ladders. Type furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
  • Examples of the dopant material for the light emitting layer include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes.
  • aromatic amine derivative as a condensed aromatic ring derivative having a substituted or unsubstituted arylamine group, pyrene, anthracene, chrysene, periflanthene and the like having an arylamine group may be used.
  • As the styrylamine compound a compound in which at least one arylvinyl group is substituted with a substituted or unsubstituted arylamine may be used.
  • styrylamine compound examples include, but are not limited to, styrylamine, styryldiamine, styryltriamine, and styryltetraamine.
  • the metal complex may be an iridium complex or a platinum complex, but is not limited thereto.
  • the hole blocking layer is a layer that prevents holes from flowing into the cathode from the emission layer and controls the electrons flowing into the emission layer to control the performance of the entire device.
  • the hole blocking material is preferably a compound having the ability to prevent the inflow of holes from the emission layer to the cathode and to control electrons injected into the emission layer or the emission material.
  • As the electron controlling material a suitable material may be used according to the configuration of the organic material layer used in the device.
  • the hole blocking layer is located between the light emitting layer and the cathode, and is preferably provided in direct contact with the light emitting layer.
  • the electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the emission layer.
  • a material capable of receiving electrons from the cathode and transferring them to the emission layer is a material having high mobility for electrons. Suitable. Specific examples include Al complex of 8-hydroxyquinoline; Complexes containing Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.
  • the electron transport layer can be used with any desired cathode material as used according to the prior art.
  • suitable cathode materials are conventional materials that have a low work function and are followed by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium and samarium, and in each case, an aluminum layer or a silver layer follows.
  • the electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect for the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer
  • a compound that prevents migration to a layer and is excellent in thin film formation ability is preferable.
  • Complex compounds and nitrogen-containing 5-membered ring derivatives but are not limited thereto.
  • the metal complex compound examples include lithium 8-hydroxyquinolinato, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is not limited to this.
  • the organic light emitting device may be a top emission type, a bottom emission type, or a double-sided emission type depending on the material used.
  • the compound represented by Formula 1 can be prepared from the process of introducing a borate to halide-substituted dibenzofuran or dibenzothiophene, introducing a triazine group through Suzuki coupling, and then introducing an expanded carbazole group. .
  • the compounds of the specific examples were synthesized step by step through the following process.
  • the triplet value is 2.4 eV
  • a green organic light-emitting device was prepared by including the above host material (m-CBP) and the compound 4CzIPN having TADF (delayed fluorescence) properties with ⁇ E ST (difference between singlet energy level and triplet energy level) less than 0.3 eV in the emission layer. And evaluated the properties.
  • a glass substrate coated with a thin film of ITO (Indium Tin Oxide) to a thickness of 1,000 ⁇ was placed in distilled water dissolved in a detergent and washed with ultrasonic waves.
  • ITO Indium Tin Oxide
  • Fischer Co. product was used as a detergent
  • distilled water secondarily filtered with a filter made by Millipore Co. was used as distilled water.
  • ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner.
  • the substrate was transported to a vacuum evaporator.
  • HAT-CN hexaazatriphenylene-hexanitrile
  • a hole transport layer (300 ⁇ ) was formed by vacuum depositing the following compound NPB on the hole injection layer.
  • the electron blocking layer was formed by vacuum depositing the following compound EB1 with a film thickness of 100 ⁇ on the hole transport layer.
  • a hole blocking layer was formed by vacuum depositing the following compound HB1 with a film thickness of 100 ⁇ on the emission layer.
  • the following compound ET1 and the compound LiQ were vacuum-deposited at a weight ratio of 1:1 to form an electron injection and transport layer with a thickness of 300 ⁇ .
  • Lithium fluoride (LiF) at a thickness of 12 ⁇ and aluminum at a thickness of 2,000 ⁇ were sequentially deposited on the electron injection and transport layer to form a negative electrode.
  • the deposition rate of organic matter was maintained from 0.4 ⁇ /sec to 0.7 ⁇ /sec, lithium fluoride of the negative electrode was maintained at a deposition rate of 0.3 ⁇ /sec and aluminum was maintained at a deposition rate of 2 ⁇ /sec. - 7 torr to 5x10 - holding a 6 torr, was produced in the organic light emitting device.
  • An organic light-emitting device was manufactured in the same manner as in Comparative Example 1-1, except that the compound of Table 1 was used instead of the compound 4CzIPN in Comparative Example 1-1.
  • An organic light-emitting device was manufactured in the same manner as in Comparative Example 1-1, except that compounds of the following T1 to T4 were used instead of the compound 4CzIPN in Comparative Example 1-1.
  • Example 1-1 One 4.1 21 (0.20, 0.66) 97 Example 1-2 2 4.1 20 (0.20, 0.67) 99 Example 1-3 3 4.0 20 (0.21, 0.67) 95 Example 1-4 4 4.2 22 (0.21, 0.66) 96 Example 1-5 5 4.1 21 (0.20, 0.66) 98 Example 1-6 6 4.1 21 (0.21, 0.67) 99 Example 1-7 7 4.2 20 (0.20, 0.66) 92 Example 1-8 8 4.1 21 (0.21, 0.67) 96 Example 1-9 9 4.1 22 (0.20, 0.67) 94 Example 1-10 10 4.0 20 (0.20, 0.66) 93 Example 1-11 11 4.1 21 (0.21, 0.67) 97 Example 1-12 12 4.1 20 (0.20, 0.66) 92 Example 1-13 13 4.0 21 (0.21, 0.66) 99 Example 1-14 14 4.2 22 (0.21, 0.66) 98 Example 1-15 15 4.1
  • the compound according to the present invention has excellent light-emitting ability and high color purity, so that it can be applied to a delayed fluorescent organic light-emitting device.
  • a glass substrate coated with a thin film of ITO (Indium Tin Oxide) to a thickness of 1,000 ⁇ was placed in distilled water dissolved in a detergent and washed with ultrasonic waves.
  • ITO Indium Tin Oxide
  • Fischer Co. product was used as a detergent
  • distilled water secondarily filtered with a filter made by Millipore Co. was used as distilled water.
  • ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner.
  • the substrate was transported to a vacuum evaporator.
  • HAT-CN hexaazatriphenylene-hexanitrile
  • a hole transport layer (300 ⁇ ) was formed by vacuum depositing the following compound NPB on the hole injection layer.
  • the electron blocking layer was formed by vacuum depositing the following compound EB1 with a film thickness of 100 ⁇ on the hole transport layer.
  • a hole blocking layer was formed by vacuum depositing the following compound HB1 with a film thickness of 100 ⁇ on the emission layer.
  • the following compound ET1 and the compound LiQ were vacuum-deposited at a weight ratio of 1:1 to form an electron injection and transport layer with a thickness of 300 ⁇ .
  • Lithium fluoride (LiF) at a thickness of 12 ⁇ and aluminum at a thickness of 2,000 ⁇ were sequentially deposited on the electron injection and transport layer to form a cathode.
  • the deposition rate of organic matter was maintained at 0.4 ⁇ /sec to 0.7 ⁇ /sec, and the deposition rate of lithium fluoride at the negative electrode was 0.3 ⁇ /sec and 2 ⁇ /sec for aluminum, and the degree of vacuum during deposition was 2 ⁇ 10 ⁇ 7 torr to 5x10 - holding a 6 torr, was produced in the organic light emitting device.
  • An organic light-emitting device was manufactured in the same manner as in Comparative Example 2-1, except that the compound of Table 2 below was used instead of the compound 4CzIPN in Comparative Example 2-1.
  • An organic light-emitting device was manufactured in the same manner as in Comparative Example 2-1, except that the compound of Table 2 below was used instead of the compound 4CzIPN in Comparative Example 2-1.
  • the CIE color coordinates measured at the 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 enables tuning of luminescence wavelength, thereby enabling the implementation of an organic light-emitting device of high color purity.
  • the HOMO and LUMO energy levels were confirmed by dissolving the measured compound in dimethylformamide (DMF) at a concentration of 5 mM and the electrolyte at 0.1 M, and comparing the oxidation and reduction potentials through CV instrument measurement and comparing the ferrocene compound as a reference. .
  • DMF dimethylformamide
  • the HOMO energy level of the compound and the LUMO energy level are the circulating voltage comparing the oxidation and reduction potentials of a dimethylformamide (DMF) solution in which the measured compound is dissolved at a concentration of 5 mM and the electrolyte is dissolved at a concentration of 0.1 M based on a ferrocene compound. It was measured by cyclic voltammetry (CV). Specific measurement conditions are as follows.
  • Measurement solution Dimethylformamide (DMF) solution in which the measurement compound is dissolved in a concentration of 5 mM and an electrolyte (KNO 3 , Aldrich) is dissolved in a concentration of 0.1 M
  • the HOMO energy level (E(HOMO)) and the LUMO energy level (E(LUMO)) were calculated through the following equations (1) and (2).
  • V solvent is the energy level of the solvent
  • E 1/2 (solvent) is the half-wave level of the solvent
  • E onset ox is the starting point of oxidation
  • E onset red is the starting point of reduction.
  • the triplet energy level (T1) was measured in a cryogenic state using the characteristics of the triplet exciton with a long life. Specifically, after dissolving the compound in a toluene solvent to prepare a sample having a concentration of 10 -5 M, the sample was put in a quartz kit and cooled to 77 K, and a 300 nm light source was irradiated to the sample for phosphorescence measurement to change the wavelength while Measure the spectrum. For the measurement of the spectrum, a spectrophotometer (FP-8600 spectrophotometer, JASCO) was used.
  • the vertical axis of the phosphorescence spectrum was made into phosphorescence intensity, and the horizontal axis was made into wavelength.
  • Draw a tangent to the rise of the short wavelength side of the phosphorescent spectrum find the wavelength value ( ⁇ edge1 (nm)) of the intersection of the tangent and the horizontal axis, and substitute this wavelength value into the following equation (3) to calculate triplet energy. I did.
  • the tangent to the rise on the short wavelength side of the phosphorescence spectrum is drawn as follows. First, the maximum value of the shortest wavelength side among the maximum values of the spectrum is checked. At this time, the maximum point having a peak intensity of 15% or less of the maximum peak intensity of the spectrum is not included in the maximum value of the shortest wavelength side described above. The tangent line at each point on the spectrum curve from the short wavelength side of the phosphorescence spectrum to the maximum value is considered. Among these tangents, the tangent with the largest inclination value (that is, the tangent to the inflection point) is taken as the tangent to the rise of the short wavelength side of the phosphorescent spectrum.
  • the singlet energy level (S1) was measured by the following method.
  • a 10 -5 M toluene solution of the compound to be measured was prepared and placed in a quartz cell, and the emission spectrum (vertical axis: luminescence intensity, horizontal axis: wavelength) of the 300 nm light source of the sample was measured at room temperature (300 K).
  • a tangent line was drawn with respect to the rise on the short wavelength side of the emission spectrum, and the singlet energy was calculated by substituting the wavelength value ( ⁇ edge2 (nm)) of the intersection of the tangent line and the horizontal axis into the following equation (4).
  • the emission spectrum was measured using a JASCO spectrophotometer (FP-8600 spectrophotometer).
  • the tangent to the rise on the short wavelength side of the emission spectrum is drawn as follows. First, the maximum value of the shortest wavelength side among the maximum values of the spectrum is checked. The tangent line at each point on the spectrum curve from the short wavelength side of the emission spectrum to the maximum value is considered. Among these tangent lines, the tangent line with the largest inclination value (that is, the tangent line at the inflection point) is taken as the tangent to the rise of the short wavelength side of the emission spectrum. The maximum point having a peak intensity of 15% or less of the maximum peak intensity of the spectrum is not included in the maximum value on the shortest wavelength side described above.
  • T1 triplet energy level
  • S1 singlet energy level
  • HOMO energy level HOMO energy level
  • LUMO energy level LUMO energy level
  • ⁇ E ST is the difference between the singlet energy level and the triplet energy level.
  • compounds 1 to 16 used in the examples of the present application all have ⁇ E ST of 0.3 eV or less and are suitable as delayed fluorescent materials.
  • Compounds T2, T3, T4 and 4CzIPN used as comparative examples also correspond to delayed fluorescent materials with ⁇ E ST of 0.3 eV or less, but as shown in Tables 1 and 2, compounds 1 to 16 have characteristics in terms of voltage and efficiency. It could be seen that all improved.

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PCT/KR2020/004034 2019-03-25 2020-03-25 헤테로고리 화합물 및 이를 포함하는 유기 발광 소자 WO2020197253A1 (ko)

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