WO2021080254A1 - Novel compound and organic light emitting device comprising same - Google Patents

Novel compound and organic light emitting device comprising same Download PDF

Info

Publication number
WO2021080254A1
WO2021080254A1 PCT/KR2020/014151 KR2020014151W WO2021080254A1 WO 2021080254 A1 WO2021080254 A1 WO 2021080254A1 KR 2020014151 W KR2020014151 W KR 2020014151W WO 2021080254 A1 WO2021080254 A1 WO 2021080254A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
compound
substituted
layer
unsubstituted
Prior art date
Application number
PCT/KR2020/014151
Other languages
French (fr)
Korean (ko)
Inventor
차용범
홍성길
이성재
이재구
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020200131020A external-priority patent/KR102397832B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN202080053544.8A priority Critical patent/CN114174287B/en
Publication of WO2021080254A1 publication Critical patent/WO2021080254A1/en

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • 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
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers

Definitions

  • the present invention relates to a novel compound and an organic light emitting device using the same.
  • the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy by using an organic material.
  • An organic light-emitting device using the organic light-emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.
  • An organic light-emitting device generally has a structure including an anode and a cathode, and an organic material layer between the anode and the cathode.
  • the organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device.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.
  • holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. When it falls back to the ground, it glows.
  • Patent Document 0001 Korean Patent Publication No. 10-2013-073537
  • the present invention relates to a novel compound and an organic light emitting device comprising the same.
  • the present invention provides a compound represented by the following formula (1):
  • X 1 to X 3 are each independently N or CH, provided that at least one of X 1 to X 3 is N,
  • L 1 to L 3 are each independently a single bond; Or a substituted or unsubstituted C 6-60 arylene,
  • Ar 1 and Ar 2 are each independently hydrogen; heavy hydrogen; Adamantyl; Substituted or unsubstituted C 6-60 aryl; Substituted or unsubstituted C 7-60 arylalkyl; Substituted or unsubstituted C 7-60 arylalkenyl; Or substituted or unsubstituted C 2-60 heteroaryl including any one or more selected from the group consisting of N, O and S, provided that at least one of Ar 1 and Ar 2 is adamantyl,
  • R 1 and R 2 are hydrogen; heavy hydrogen; Or substituted or unsubstituted C 1-60 alkyl,
  • n is an integer from 0 to 8
  • n is an integer from 0 to 7.
  • the present invention 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, wherein at least one of the organic material layers includes the compound of the present invention.
  • the compound represented by Chemical Formula 1 may be used as a material for an organic material layer of an organic light-emitting device, and may improve efficiency, low driving voltage, and/or lifetime characteristics in the organic light-emitting device.
  • the compound represented by Chemical Formula 1 may be used as a material for the hole blocking layer.
  • FIG. 1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a light emitting layer 4, a hole blocking layer 9, and a cathode 6.
  • FIG. 2 shows a substrate 1, an anode 2, a hole injection layer 7, a hole transport layer 3, an electron suppression layer 8, a light emitting layer 4, a hole blocking layer 9, an electron injection and transport layer ( 5) and a cathode 6 are shown as an example of an organic light-emitting device.
  • substituted or unsubstituted refers to deuterium (D); Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O, and S atoms, or substituted or unsubstituted
  • a substituent to which two or more substituents are connected may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.
  • the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
  • the ester group may be substituted with a C1-C25 linear, branched or cyclic alkyl group or an aryl group having 6 to 25 carbon atoms in the oxygen of the ester group.
  • it may be a compound of the following structural formula, but is not limited thereto.
  • the number of carbon atoms of the imide group is not particularly limited, but it is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
  • the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.
  • the boron group specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, a phenyl boron group, and the like, but is not limited thereto.
  • examples of the halogen group include fluorine, chlorine, bromine or iodine.
  • the alkyl group may be linear or branched, 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, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cycloheptylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhex
  • the alkenyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms.
  • Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.
  • 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.
  • 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 an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms.
  • the aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group is not limited thereto.
  • the polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.
  • the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.
  • the fluorenyl group is substituted, Can be, etc. However, it is not limited thereto.
  • the heterocyclic group is a heterocyclic group containing at least one of O, N, Si, and S as a heterogeneous element, and the number of carbons is not particularly limited, but it is preferably 2 to 60 carbon atoms.
  • heterocyclic group examples include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group , Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , Carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenan
  • the aryl group among the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the example of the aryl group described above.
  • the alkyl group among the aralkyl group, the alkylaryl group and the alkylamine group is the same as the example of the aforementioned alkyl group.
  • the description of the aforementioned heterocyclic group may be applied.
  • the alkenyl group of the aralkenyl group is the same as the example of the alkenyl group described above.
  • the description of the aryl group described above may be applied except that the arylene is a divalent group.
  • the description of the aforementioned heterocyclic group may be applied except that the heteroarylene is a divalent group.
  • the hydrocarbon ring is not a monovalent group, and the description of the aryl group or cycloalkyl group described above may be applied except that the hydrocarbon ring is formed by bonding of two substituents.
  • the heterocycle is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied, except that two substituents are bonded to each other.
  • the present invention provides a compound represented by Chemical Formula 1.
  • the compound represented by Formula 1 is a compound in which a triazine-based substituent (including pyridine, pyrimidine, and triazine) is bonded to a core structure in which xanthene and fluorene are spiro bonded, and is one of the additional substituents of the triazine-based substituent. ). These compounds may exhibit improved hole-electron bonding and improved thermal stability compared to compounds substituted with triazine-based substituents having no adamantyl group. Accordingly, the organic light-emitting device employing the compound can exhibit characteristics such as high efficiency, low driving voltage, and long life.
  • the compound represented by Formula 1 is specifically as follows:
  • X 1 to X 3 are each independently N or CH, provided that at least one of X 1 to X 3 is N,
  • L 1 to L 3 are each independently a single bond; Or a substituted or unsubstituted C 6-60 arylene,
  • Ar 1 and Ar 2 are each independently hydrogen; heavy hydrogen; Adamantyl; Substituted or unsubstituted C 6-60 aryl; Substituted or unsubstituted C 7-60 arylalkyl; Substituted or unsubstituted C 7-60 arylalkenyl; Or substituted or unsubstituted C 2-60 heteroaryl including any one or more selected from the group consisting of N, O and S, provided that at least one of Ar 1 and Ar 2 is adamantyl,
  • R 1 and R 2 are hydrogen; heavy hydrogen; Or substituted or unsubstituted C 1-60 alkyl,
  • n is an integer from 0 to 8
  • n is an integer from 0 to 7.
  • the compound represented by Formula 1 is a compound represented by Formulas 1-1 to 1-3:
  • X 1 , X 2 , X 3 , L 1 , L 2 , L 3 , Ar 1 , Ar 2 , R 1 , R 2 , m and n are as previously defined.
  • L 1 to L 3 are each independently a single bond; Phenylene unsubstituted or substituted with deuterium; Biphenylylene unsubstituted or substituted with deuterium; Terphenylylene unsubstituted or substituted with deuterium; Fluorenylene unsubstituted or substituted with deuterium; Or naphthylene unsubstituted or substituted with deuterium.
  • L 1 to L 3 are each independently a single bond; Phenylene; Biphenylylene or naphthylene.
  • Ar 1 and Ar 2 are each independently deuterium; Adamantyl; Or any one selected from the group consisting of, provided that at least one of Ar 1 and Ar 2 is adamantyl:
  • X is O; S or NR,
  • R is substituted or unsubstituted C 6-12 aryl
  • R '1 and R' 2 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 1-10 alkyl; Or substituted or unsubstituted C 6-12 aryl.
  • R is phenyl
  • R '1 and R' 2 are, each independently methyl.
  • R 1 and R 2 are each independently hydrogen; Or deuterium.
  • n and n are each independently 0 or 1.
  • the compound represented by Formula 1 may be any one selected from the group consisting of:
  • the compound represented by Formula 1 can be prepared through the following Scheme 1.
  • Scheme 1 is a Suzuki coupling reaction, preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction may be changed as known in the art.
  • the position of each substituent can be prepared by appropriately changing the structure of the starting material with reference to Scheme 1.
  • the method for preparing the compound represented by Formula 1 may be more specific in Preparation Examples to be described later.
  • the present invention provides an organic light-emitting device including the compound represented by Formula 1 above.
  • the present invention provides 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 of the organic material layers includes a compound represented by Formula 1 .
  • the organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multilayer structure in which two or more organic material layers are stacked.
  • the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, and the like as an organic material layer.
  • the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.
  • the organic material layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes, and the hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 above. Including the indicated compound.
  • the organic material layer may include an emission layer, and the emission layer includes a compound represented by Formula 1.
  • the organic material layer may include a hole blocking layer, and the hole blocking layer includes a compound represented by Formula 1 above.
  • the organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multilayer structure in which two or more organic material layers are stacked.
  • the organic light emitting device of the present invention further includes a hole injection layer and a hole transport layer between the first electrode and the emission layer, and an electron transport layer and an electron injection layer between the emission layer and the second electrode in addition to the emission layer as an organic material layer. It can have a structure to do.
  • the structure of the organic light emitting device is not limited thereto, and may include a smaller number or a larger number of organic layers.
  • the first electrode is an anode and the second electrode is a cathode, and an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate (normal type). It may be a device.
  • the first electrode is a cathode and the second electrode is an anode, and a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. It may be a light emitting device.
  • FIGS. 1 and 2 the structure of an organic light-emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.
  • FIG. 1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a light emitting layer 4, a hole blocking layer 9, and a cathode 6.
  • the compound represented by Formula 1 may be included in the hole blocking layer.
  • the compound represented by Formula 1 may be included in the hole blocking layer.
  • the organic light-emitting device according to the present invention may be manufactured by materials and methods known in the art, except that at least one of the organic material layers includes the compound represented by Chemical Formula 1.
  • the organic material layers may be formed of the same material or different materials.
  • the organic light emitting device may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate.
  • a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation
  • the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate.
  • an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon it can be prepared by depositing a material that can be used as a cathode thereon.
  • 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.
  • the compound represented by Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device.
  • the solution 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 (WO 2003/012890).
  • the manufacturing method is 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 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); Combinations of metals and oxides 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 multilayered 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 an 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, 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. It is preferable that 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, and has high mobility for holes. The material is suitable.
  • a compound represented by Formula 1 may be used, or an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion may be used, but the present invention is not limited thereto. .
  • the electron inhibiting layer (or electron blocking layer) is formed on the hole transport layer and is preferably provided in contact with the light emitting layer to adjust hole mobility and prevent excessive movement of electrons, thereby increasing the probability of hole-electron coupling. It refers to a layer that serves to improve the efficiency of an organic light emitting device by giving it.
  • the electron-suppression layer includes an electron-blocking material, and examples of such an electron-blocking material may include a compound represented by Formula 1 or an arylamine-based organic material, but are not limited thereto.
  • the light-emitting material a material capable of emitting light in a visible light 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 for fluorescence or phosphorescence is preferable.
  • the emission layer may include a host material and a dopant material.
  • the host material may further include a condensed aromatic ring derivative or a heterocyclic compound.
  • 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, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
  • Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes.
  • the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periflanthene and the like having an arylamino group
  • the styrylamine compound is substituted or unsubstituted
  • the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periflanthene and the like having an arylamino group
  • the styrylamine compound is substituted or unsubstituted
  • at least one arylvinyl group is substituted on the arylamine, one or two or more substituents selected from
  • styrylamine styryldiamine
  • styryltriamine styryltetraamine
  • metal complex examples include an iridium complex and a platinum complex, but are not limited thereto.
  • the hole blocking layer (or hole inhibiting layer) is formed on the emission layer and is preferably provided in contact with the emission layer to control electron mobility and prevent excessive movement of holes, thereby increasing the probability of hole-electron bonding. It refers to a layer that serves to improve the efficiency of the device.
  • the hole blocking layer includes a hole blocking material, and a compound represented by Formula 1 of the present invention may be used.
  • additionally usable hole-blocking substances include sub-gene derivatives including triazine; Triazole derivatives; Oxadiazole derivatives; Phenanthroline derivatives; A compound into which an electron withdrawing group is introduced, such as a phosphine oxide derivative, may be used, but is not limited thereto.
  • the electron injection and transport layer is a layer that simultaneously serves as an electron transport layer and an electron injection layer for injecting electrons from an electrode and transporting received electrons to the emission layer, and is formed on the emission layer or the hole blocking layer.
  • an electron injection and transport material a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high mobility for electrons is suitable.
  • specific electron injection and transport materials include Al complex of 8-hydroxyquinoline; Complexes containing Alq 3; Organic radical compounds; Hydroxyflavone-metal complex; Triazine derivatives and the like, but are not limited thereto.
  • fluorenone anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and their derivatives, metal complex compounds , Or nitrogen-containing 5-membered cyclic derivatives may be used together, but the present invention is not limited thereto.
  • the electron injection and transport layer may also be formed as separate layers such as an electron injection layer and an electron transport layer.
  • the electron transport layer is formed on the emission layer or the hole blocking layer, and the electron injection and transport material described above may be used as the electron transport material included in the electron transport layer.
  • the electron injection layer is formed on the electron transport layer, and electron injection materials included in the electron injection layer include LiF, NaCl, CsF, Li 2 O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, Thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and the like, their derivatives, metal complex compounds, and nitrogen-containing 5-membered ring derivatives.
  • electron injection materials included in the electron injection layer include LiF, NaCl, CsF, Li 2 O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, Thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and the
  • 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 thereto.
  • 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 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.
  • the reactant was poured into a mixed solution of 15 ml of diethyl ether and 25 ml of 2N hydrochloric acid aqueous solution, and then stirred for 30 minutes to filter the resulting solid, washed with water and diethyl ether, and dried. 2.5 g of the dried solid sample was taken and dissolved in 50 ml of acetic acid, and then a catalytic amount (10 drops) of concentrated sulfuric acid was added and refluxed for 3 hours. Thereafter, the resulting solid compound was filtered, washed with acetic acid, and dried to obtain a white solid compound A-1 (18.22 g, yield: 62%).
  • formula A-1 (18.22 g, 49.65 mmol), pinacol diboron (13.86 g, 54.61 mmol) and potassium acetate (14.61 g, 148.94 mmol) were mixed in a nitrogen atmosphere, and added to dioxane (480 ml). And heated while stirring. In a refluxed state, bis(dibenzylidineacetone)palladium (0.38 g, 1.49 mmol) and tricyclohexylphosphine (0.39 g, 2.99 mmol) were added, followed by heating and stirring for 12 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered.
  • Example 1-1 Fabrication of an organic light emitting device
  • a glass substrate coated with a thin film of ITO (indium tin oxide) having a thickness of 1,000 ⁇ was put in distilled water dissolved in a detergent and washed with ultrasonic waves.
  • ITO indium tin oxide
  • a product made by Fischer Co. was used as a detergent, and distilled water secondarily filtered with a filter manufactured 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.
  • a hole injection layer was formed by thermally vacuum evaporating a compound of the following compound HI1 and the following compound HI2 to a thickness of 100 ⁇ in a ratio of 98:2 (molar ratio) on the prepared ITO transparent electrode, which is an anode.
  • a hole transport layer was formed by vacuum depositing a compound (1150 ⁇ ) represented by the following formula HT1 on the hole injection layer.
  • an electron suppressing layer was formed by vacuum depositing a compound of EB1 with a film thickness of 50 ⁇ on the hole transport layer.
  • a light emitting layer was formed by vacuum depositing a compound represented by the following formula BH and a compound represented by the following formula BD with a film thickness of 200 ⁇ on the electron suppressing layer at a weight ratio of 25:1.
  • a hole blocking layer was formed by vacuum depositing a compound represented by Compound 1 synthesized in Preparation Example 1 with a film thickness of 50 ⁇ on the emission layer.
  • a compound represented by the following formula ET1 and a compound represented by the following formula LiQ were vacuum-deposited at a weight ratio of 1:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 310 ⁇ .
  • Lithium fluoride (LiF) in a thickness of 12 ⁇ and aluminum in a thickness of 1,000 ⁇ were sequentially deposited on the electron injection and transport layer to form a negative electrode.
  • the deposition rate of the organic material was maintained at 0.4 ⁇ 0.7 ⁇ /sec
  • the deposition rate of lithium fluoride at the cathode was 0.3 ⁇ /sec
  • the deposition rate of aluminum was 2 ⁇ /sec
  • the vacuum degree during deposition was 2x10 -7 ⁇ Maintaining 5x10 -6 torr, an organic light emitting device was manufactured.
  • An organic light-emitting device was manufactured in the same manner as in Example 1-1, except that the compound shown in Table 1 was used instead of the compound of Preparation Example 1.
  • An organic light-emitting device was manufactured in the same manner as in Example 1-1, except that the compound shown in Table 1 was used instead of the compound of Preparation Example 1.
  • the compounds of HB1, HB2, and HB3 used in Table 1 are as follows.
  • T95 refers to the time it takes for the luminance to decrease from the initial luminance (1600 nit) to 95%.
  • Example 1-1 Manufacturing Example 1 4.45 6.48 (0.146, 0.046) 250 Example 1-2 Manufacturing Example 2 4.46 6.46 (0.144, 0.047) 255 Example 1-3 Manufacturing Example 3 4.54 6.34 (0.146, 0.045) 235 Example 1-4 Manufacturing Example 4 4.69 6.21 (0.144, 0.045) 225 Example 1-5 Manufacturing Example 5 4.58 6.38 (0.146, 0.046) 235 Example 1-6 Manufacturing Example 6 4.47 6.39 (0.146, 0.047) 250 Example 1-7 Manufacturing Example 7 4.56 6.39 (0.146, 0.046) 245 Example 1-8 Manufacturing Example 8 4.51 6.22 (0.146, 0.047) 230 Example 1-9 Manufacturing Example 9 4.50 6.33 (0.144, 0.046) 235 Example 1-10 Manufacturing Example 10 4.55 6.34 (0.146, 0.046) 245 Example 1
  • the organic light-emitting device using the compound of the present invention as a hole blocking layer exhibited excellent characteristics in terms of efficiency, driving voltage, and stability of the organic light-emitting device.
  • the organic light-emitting device using the compound of the present invention is HB1, HB2 in which the triazine-based substituents containing at least one adamantyl group are not substituted in the core structure in which xanthene and fluorene are spiro bonded.
  • HB1 the organic light-emitting device using the compound of the present invention
  • HB2 the triazine-based substituents containing at least one adamantyl group are not substituted in the core structure in which xanthene and fluorene are spiro bonded.
  • substrate 2 anode
  • hole transport layer 4 light emitting layer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The present invention provides a novel compound and an organic light emitting device comprising same.

Description

신규한 화합물 및 이를 이용한 유기발광 소자Novel compound and organic light emitting device using the same
관련 출원(들)과의 상호 인용Cross-reference with related application(s)
본 출원은 2019년 10월 21일자 한국 특허 출원 제 10-2019-0130848호 및 2020년 10월 12일자 한국 특허 출원 제 10-2020-0131020호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원들의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0130848 filed October 21, 2019 and Korean Patent Application No. 10-2020-0131020 filed October 12, 2020. All contents disclosed in the literature are included as part of this specification.
본 발명은 신규한 화합물 및 이를 이용한 유기발광 소자에 관한 것이다. The present invention relates to a novel compound and an organic light emitting device using the same.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기 발광 소자는 넓은 시야각, 우수한 콘트라스트, 빠른 응답 시간을 가지며, 휘도, 구동 전압 및 응답 속도 특성이 우수하여 많은 연구가 진행되고 있다. In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy by using an organic material. An organic light-emitting device using the organic light-emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.
유기 발광 소자는 일반적으로 양극과 음극 및 상기 양극과 음극 사이에 유기물 층을 포함하는 구조를 가진다. 상기 유기물 층은 유기 발광 소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층 등으로 이루어질 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. An organic light-emitting device generally has a structure including an anode and a cathode, and an organic material layer between the anode and the cathode. The organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device.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. In the structure of such an organic light emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. When it falls back to the ground, it glows.
상기와 같은 유기 발광 소자에 사용되는 유기물에 대하여 새로운 재료의 개발이 지속적으로 요구되고 있다.Development of new materials for organic materials used in organic light emitting devices as described above is continuously required.
선행기술문헌Prior art literature
특허문헌Patent Literature
(특허문헌 0001) 한국특허 공개번호 제10-2013-073537호(Patent Document 0001) Korean Patent Publication No. 10-2013-073537
본 발명은 신규한 화합물 및 이를 포함하는 유기 발광 소자에 관한 것이다. The present invention relates to a novel compound and an organic light emitting device comprising the same.
본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다:The present invention provides a compound represented by the following formula (1):
[화학식 1][Formula 1]
Figure PCTKR2020014151-appb-img-000001
Figure PCTKR2020014151-appb-img-000001
상기 화학식 1에서,In Formula 1,
X 1 내지 X 3는 각각 독립적으로, N 또는 CH이고, 단, X 1 내지 X 3 중 하나 이상이 N이고, X 1 to X 3 are each independently N or CH, provided that at least one of X 1 to X 3 is N,
L 1 내지 L 3는 각각 독립적으로, 단일 결합; 또는 치환 또는 비치환된 C 6-60 아릴렌이고,L 1 to L 3 are each independently a single bond; Or a substituted or unsubstituted C 6-60 arylene,
Ar 1 및 Ar 2는 각각 독립적으로, 수소; 중수소; 아다만틸; 치환 또는 비치환된 C 6-60 아릴; 치환 또는 비치환된 C 7-60 아릴알킬; 치환 또는 비치환된 C 7-60 아릴알케닐; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C 2-60 헤테로아릴이고, 단, Ar 1 및 Ar 2 중 하나 이상은 아다만틸이고, Ar 1 and Ar 2 are each independently hydrogen; heavy hydrogen; Adamantyl; Substituted or unsubstituted C 6-60 aryl; Substituted or unsubstituted C 7-60 arylalkyl; Substituted or unsubstituted C 7-60 arylalkenyl; Or substituted or unsubstituted C 2-60 heteroaryl including any one or more selected from the group consisting of N, O and S, provided that at least one of Ar 1 and Ar 2 is adamantyl,
R 1 및 R 2는 수소; 중수소; 또는 치환 또는 비치환된 C 1-60 알킬이고,R 1 and R 2 are hydrogen; heavy hydrogen; Or substituted or unsubstituted C 1-60 alkyl,
m은 0 내지 8의 정수이고,m is an integer from 0 to 8,
n은 0 내지 7의 정수이다.n is an integer from 0 to 7.
또한, 본 발명은 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 전술한 본 발명의 화합물을 포함하는 유기 발광 소자를 제공한다.In addition, the present invention 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, wherein at least one of the organic material layers includes the compound of the present invention.
상술한 화학식 1로 표시되는 화합물은 유기 발광 소자의 유기물 층의 재료로서 사용될 수 있으며, 유기 발광 소자에서 효율의 향상, 낮은 구동전압 및/또는 수명 특성을 향상시킬 수 있다. 특히, 상술한 화학식 1로 표시되는 화합물은 정공저지층 재료로 사용될 수 있다.The compound represented by Chemical Formula 1 may be used as a material for an organic material layer of an organic light-emitting device, and may improve efficiency, low driving voltage, and/or lifetime characteristics in the organic light-emitting device. In particular, the compound represented by Chemical Formula 1 may be used as a material for the hole blocking layer.
도 1은 기판(1), 양극(2), 발광층(4), 정공저지층(9) 및 음극(6)으로 이루어진 유기 발광 소자의 예를 도시한 것이다.FIG. 1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a light emitting layer 4, a hole blocking layer 9, and a cathode 6.
도 2는 기판(1), 양극(2), 정공주입층(7), 정공수송층(3), 전자억제층(8), 발광층(4), 정공저지층(9), 전자주입 및 수송층(5) 및 음극(6)으로 이루어진 유기 발광 소자의 예를 도시한 것이다.2 shows a substrate 1, an anode 2, a hole injection layer 7, a hole transport layer 3, an electron suppression layer 8, a light emitting layer 4, a hole blocking layer 9, an electron injection and transport layer ( 5) and a cathode 6 are shown as an example of an organic light-emitting device.
이하, 본 발명의 이해 돕기 위하여 보다 상세히 설명한다.Hereinafter, in order to help understand the present invention, it will be described in more detail.
(용어의 설명)(Explanation of terms)
본 명세서에서,
Figure PCTKR2020014151-appb-img-000002
및
Figure PCTKR2020014151-appb-img-000003
는 다른 치환기에 연결되는 결합을 의미한다. In this specification,
Figure PCTKR2020014151-appb-img-000002
And
Figure PCTKR2020014151-appb-img-000003
Means a bond connected to another substituent.
본 명세서에서 "치환 또는 비치환된" 이라는 용어는 중수소(D); 할로겐기; 니트릴기; 니트로기; 히드록시기; 카보닐기; 에스테르기; 이미드기; 아미노기; 포스핀옥사이드기; 알콕시기; 아릴옥시기; 알킬티옥시기; 아릴티옥시기; 알킬술폭시기; 아릴술폭시기; 실릴기; 붕소기; 알킬기; 사이클로알킬기; 알케닐기; 아릴기; 아르알킬기; 아르알케닐기; 알킬아릴기; 알킬아민기; 아랄킬아민기; 헤테로아릴아민기; 아릴아민기; 아릴포스핀기; 또는 N, O 및 S 원자 중 1개 이상을 포함하는 헤테로고리기로 이루어진 군에서 선택된 1개 이상의 치환기로 치환 또는 비치환되거나, 상기 예시된 치환기 중 2 이상의 치환기가 연결된 치환 또는 비치환된 것을 의미한다. 예컨대, "2 이상의 치환기가 연결된 치환기"는 비페닐기일 수 있다. 즉, 비페닐기는 아릴기일 수도 있고, 2개의 페닐기가 연결된 치환기로 해석될 수 있다.In the present specification, the term "substituted or unsubstituted" refers to deuterium (D); Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O, and S atoms, or substituted or unsubstituted with two or more substituents connected among the above-exemplified substituents. . For example, "a substituent to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.
본 명세서에서 카보닐기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 40인 것이 바람직하다. 구체적으로 하기와 같은 구조의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
Figure PCTKR2020014151-appb-img-000004
Figure PCTKR2020014151-appb-img-000004
본 명세서에 있어서, 에스테르기는 에스테르기의 산소가 탄소수 1 내지 25의 직쇄, 분지쇄 또는 고리쇄 알킬기 또는 탄소수 6 내지 25의 아릴기로 치환될 수 있다. 구체적으로, 하기 구조식의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the ester group may be substituted with a C1-C25 linear, branched or cyclic alkyl group or an aryl group having 6 to 25 carbon atoms in the oxygen of the ester group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.
Figure PCTKR2020014151-appb-img-000005
Figure PCTKR2020014151-appb-img-000005
본 명세서에 있어서, 이미드기의 탄소수는 특별히 한정되지 않으나, 탄소수 1 내지 25인 것이 바람직하다. 구체적으로 하기와 같은 구조의 화합물이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
Figure PCTKR2020014151-appb-img-000006
Figure PCTKR2020014151-appb-img-000006
본 명세서에 있어서, 실릴기는 구체적으로 트리메틸실릴기, 트리에틸실릴기, t-부틸디메틸실릴기, 비닐디메틸실릴기, 프로필디메틸실릴기, 트리페닐실릴기, 디페닐실릴기, 페닐실릴기 등이 있으나 이에 한정되지 않는다. In the present specification, the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.
본 명세서에 있어서, 붕소기는 구체적으로 트리메틸붕소기, 트리에틸붕소기, t-부틸디메틸붕소기, 트리페닐붕소기, 페닐붕소기 등이 있으나 이에 한정되지 않는다.In the present specification, the boron group specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, a phenyl boron group, and the like, but is not limited thereto.
본 명세서에 있어서, 할로겐기의 예로는 불소, 염소, 브롬 또는 요오드가 있다.In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.
본 명세서에 있어서, 상기 알킬기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나 1 내지 40인 것이 바람직하다. 일 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 20이다. 또 하나의 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 10이다. 또 하나의 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 6이다. 알킬기의 구체적인 예로는 메틸, 에틸, 프로필, n-프로필, 이소프로필, 부틸, n-부틸, 이소부틸, tert-부틸, sec-부틸, 1-메틸-부틸, 1-에틸-부틸, 펜틸, n-펜틸, 이소펜틸, 네오펜틸, tert-펜틸, 헥실, n-헥실, 1-메틸펜틸, 2-메틸펜틸, 4-메틸-2-펜틸, 3,3-디메틸부틸, 2-에틸부틸, 헵틸, n-헵틸, 1-메틸헥실, 사이클로펜틸메틸,사이클로헥틸메틸, 옥틸, n-옥틸, tert-옥틸, 1-메틸헵틸, 2-에틸헥실, 2-프로필펜틸, n-노닐, 2,2-디메틸헵틸, 1-에틸-프로필, 1,1-디메틸-프로필, 이소헥실, 2-메틸펜틸, 4-메틸헥실, 5-메틸헥실 등이 있으나, 이들에 한정되지 않는다.In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 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. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cycloheptylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.
본 명세서에 있어서, 상기 알케닐기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나, 2 내지 40인 것이 바람직하다. 일 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 20이다. 또 하나의 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 10이다. 또 하나의 실시상태에 따르면, 상기 알케닐기의 탄소수는 2 내지 6이다. 구체적인 예로는 비닐, 1-프로페닐, 이소프로페닐, 1-부테닐, 2-부테닐, 3-부테닐, 1-펜테닐, 2-펜테닐, 3-펜테닐, 3-메틸-1-부테닐, 1,3-부타디에닐, 알릴, 1-페닐비닐-1-일, 2-페닐비닐-1-일, 2,2-디페닐비닐-1-일, 2-페닐-2-(나프틸-1-일)비닐-1-일, 2,2-비스(디페닐-1-일)비닐-1-일, 스틸베닐기, 스티레닐기 등이 있으나 이들에 한정되지 않는다.In the present specification, the alkenyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.
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 사이클로프로필, 사이클로부틸, 사이클로펜틸, 3-메틸사이클로펜틸, 2,3-디메틸사이클로펜틸, 사이클로헥실, 3-메틸사이클로헥실, 4-메틸사이클로헥실, 2,3-디메틸사이클로헥실, 3,4,5-트리메틸사이클로헥실, 4-tert-부틸사이클로헥실, 사이클로헵틸, 사이클로옥틸 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, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are 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 30이다. 일 실시상태에 따르면, 상기 아릴기의 탄소수는 6 내지 20이다. 상기 아릴기가 단환식 아릴기로는 페닐기, 바이페닐기, 터페닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다. 상기 다환식 아릴기로는 나프틸기, 안트라세닐기, 페난트릴기, 파이레닐기, 페릴레닐기, 크라이세닐기, 플루오레닐기 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 an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.
본 명세서에 있어서, 플루오레닐기는 치환될 수 있고, 치환기 2개가 서로 결합하여 스피로 구조를 형성할 수 있다. 상기 플루오레닐기가 치환되는 경우,
Figure PCTKR2020014151-appb-img-000007
등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,
Figure PCTKR2020014151-appb-img-000007
Can be, etc. However, it is not limited thereto.
본 명세서에 있어서, 헤테로고리기는 이종 원소로 O, N, Si 및 S 중 1개 이상을 포함하는 헤테로고리기로서, 탄소수는 특별히 한정되지 않으나, 탄소수 2 내지 60인 것이 바람직하다. 헤테로고리기의 예로는 티오펜기, 퓨란기, 피롤기, 이미다졸기, 티아졸기, 옥사졸기, 옥사디아졸기, 트리아졸기, 피리딜기, 비피리딜기, 피리미딜기, 트리아진기, 아크리딜기, 피리다진기, 피라지닐기, 퀴놀리닐기, 퀴나졸린기, 퀴녹살리닐기, 프탈라지닐기, 피리도 피리미디닐기, 피리도 피라지닐기, 피라지노 피라지닐기, 이소퀴놀린기, 인돌기, 카바졸기, 벤조옥사졸기, 벤조이미다졸기, 벤조티아졸기, 벤조카바졸기, 벤조티오펜기, 디벤조티오펜기, 벤조퓨라닐기, 페난쓰롤린기(phenanthroline), 티아졸릴기, 이소옥사졸릴기, 옥사디아졸릴기, 티아디아졸릴기, 벤조티아졸릴기, 페노티아지닐기 및 디벤조퓨라닐기 등이 있으나, 이들에만 한정되는 것은 아니다.In the present specification, the heterocyclic group is a heterocyclic group containing at least one of O, N, Si, and S as a heterogeneous element, and the number of carbons is not particularly limited, but it is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group , Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , Carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl Group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, but are not limited thereto.
본 명세서에 있어서, 아르알킬기, 아르알케닐기, 알킬아릴기, 아릴아민기 중의 아릴기는 전술한 아릴기의 예시와 같다. 본 명세서에 있어서, 아르알킬기, 알킬아릴기, 알킬아민기 중 알킬기는 전술한 알킬기의 예시와 같다. 본 명세서에 있어서, 헤테로아릴아민 중 헤테로아릴은 전술한 헤테로고리기에 관한 설명이 적용될 수 있다. 본 명세서에 있어서, 아르알케닐기 중 알케닐기는 전술한 알케닐기의 예시와 같다. 본 명세서에 있어서, 아릴렌은 2가기인 것을 제외하고는 전술한 아릴기에 관한 설명이 적용될 수 있다. 본 명세서에 있어서, 헤테로아릴렌은 2가기인 것을 제외하고는 전술한 헤테로고리기에 관한 설명이 적용될 수 있다. 본 명세서에 있어서, 탄화수소 고리는 1가기가 아니고, 2개의 치환기가 결합하여 형성한 것을 제외하고는 전술한 아릴기 또는 사이클로알킬기에 관한 설명이 적용될 수 있다. 본 명세서에 있어서, 헤테로고리는 1가기가 아니고, 2개의 치환기가 결합하여 형성한 것을 제외하고는 전술한 헤테로고리기에 관한 설명이 적용될 수 있다.In the present specification, the aryl group among the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group and the alkylamine group is the same as the example of the aforementioned alkyl group. In the present specification, for heteroaryl among heteroarylamines, the description of the aforementioned heterocyclic group may be applied. In the present specification, the alkenyl group of the aralkenyl group is the same as the example of the alkenyl group described above. In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group. In the present specification, the description of the aforementioned heterocyclic group may be applied except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aryl group or cycloalkyl group described above may be applied except that the hydrocarbon ring is formed by bonding of two substituents. In the present specification, the heterocycle is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied, except that two substituents are bonded to each other.
(화합물)(compound)
본 발명은 상기 화학식 1로 표시되는 화합물을 제공한다. 화학식 1로 표시되는 화합물은 잔텐과 플루오렌이 스피로결합된 코어 구조에 트리아진계 치환기(피리딘, 피리미딘, 트리아진 포함)가 결합된 화합물로, 트리아진계 치환기의 추가 치환기 중 하나로 아다만틸 (adamantyl)기를 갖는다. 이러한 화합물은 아다만틸기를 갖지 않는 트리아진계 치환기로 치환된 화합물에 비하여 향상된 정공-전자간 결합 및 개선된 열안정성을 나타낼 수 있다. 이로써, 상기 화합물을 채용한 유기 발광 소자는 고효율, 저 구동 전압 및 장수명 등의 특성을 나타낼 수 있다. 화학식 1로 표시되는 화합물은 구체적으로 하기와 같다:The present invention provides a compound represented by Chemical Formula 1. The compound represented by Formula 1 is a compound in which a triazine-based substituent (including pyridine, pyrimidine, and triazine) is bonded to a core structure in which xanthene and fluorene are spiro bonded, and is one of the additional substituents of the triazine-based substituent. ). These compounds may exhibit improved hole-electron bonding and improved thermal stability compared to compounds substituted with triazine-based substituents having no adamantyl group. Accordingly, the organic light-emitting device employing the compound can exhibit characteristics such as high efficiency, low driving voltage, and long life. The compound represented by Formula 1 is specifically as follows:
[화학식 1][Formula 1]
Figure PCTKR2020014151-appb-img-000008
Figure PCTKR2020014151-appb-img-000008
상기 화학식 1에서,In Formula 1,
X 1 내지 X 3는 각각 독립적으로, N 또는 CH이고, 단, X 1 내지 X 3 중 하나 이상이 N이고, X 1 to X 3 are each independently N or CH, provided that at least one of X 1 to X 3 is N,
L 1 내지 L 3는 각각 독립적으로, 단일 결합; 또는 치환 또는 비치환된 C 6-60 아릴렌이고,L 1 to L 3 are each independently a single bond; Or a substituted or unsubstituted C 6-60 arylene,
Ar 1 및 Ar 2는 각각 독립적으로, 수소; 중수소; 아다만틸; 치환 또는 비치환된 C 6-60 아릴; 치환 또는 비치환된 C 7-60 아릴알킬; 치환 또는 비치환된 C 7-60 아릴알케닐; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C 2-60 헤테로아릴이고, 단, Ar 1 및 Ar 2 중 하나 이상은 아다만틸이고, Ar 1 and Ar 2 are each independently hydrogen; heavy hydrogen; Adamantyl; Substituted or unsubstituted C 6-60 aryl; Substituted or unsubstituted C 7-60 arylalkyl; Substituted or unsubstituted C 7-60 arylalkenyl; Or substituted or unsubstituted C 2-60 heteroaryl including any one or more selected from the group consisting of N, O and S, provided that at least one of Ar 1 and Ar 2 is adamantyl,
R 1 및 R 2는 수소; 중수소; 또는 치환 또는 비치환된 C 1-60 알킬이고,R 1 and R 2 are hydrogen; heavy hydrogen; Or substituted or unsubstituted C 1-60 alkyl,
m은 0 내지 8의 정수이고,m is an integer from 0 to 8,
n은 0 내지 7의 정수이다.n is an integer from 0 to 7.
바람직하게는, 상기 화학식 1로 표시되는 화합물은, 하기 화학식 1-1 내지 화학식 1-3으로 표시되는 화합물이다:Preferably, the compound represented by Formula 1 is a compound represented by Formulas 1-1 to 1-3:
[화학식 1-1][Formula 1-1]
Figure PCTKR2020014151-appb-img-000009
Figure PCTKR2020014151-appb-img-000009
[화학식 1-2][Formula 1-2]
Figure PCTKR2020014151-appb-img-000010
Figure PCTKR2020014151-appb-img-000010
[화학식 1-3][Formula 1-3]
Figure PCTKR2020014151-appb-img-000011
Figure PCTKR2020014151-appb-img-000011
상기 화학식 1-1 내지 1-3에서, In Formulas 1-1 to 1-3,
X 1, X 2, X 3, L 1, L 2, L 3, Ar 1, Ar 2, R 1, R 2, m 및 n은 앞서 정의한 바와 같다.X 1 , X 2 , X 3 , L 1 , L 2 , L 3 , Ar 1 , Ar 2 , R 1 , R 2 , m and n are as previously defined.
바람직하게는, L 1 내지 L 3는 각각 독립적으로, 단일 결합; 중수소로 치환 또는 비치환된 페닐렌; 중수소로 치환 또는 비치환된 비페닐릴렌; 중수소로 치환 또는 비치환된 터페닐릴렌; 중수소로 치환 또는 비치환된 플루오레닐렌; 또는 중수소로 치환 또는 비치환된 나프틸렌이다.Preferably, L 1 to L 3 are each independently a single bond; Phenylene unsubstituted or substituted with deuterium; Biphenylylene unsubstituted or substituted with deuterium; Terphenylylene unsubstituted or substituted with deuterium; Fluorenylene unsubstituted or substituted with deuterium; Or naphthylene unsubstituted or substituted with deuterium.
또는, 바람직하게는, L 1 내지 L 3는 각각 독립적으로, 단일 결합; 페닐렌; 비페닐릴렌 또는 나프틸렌이다.Or, preferably, L 1 to L 3 are each independently a single bond; Phenylene; Biphenylylene or naphthylene.
바람직하게는, Ar 1 및 Ar 2는 각각 독립적으로, 중수소; 아다만틸; 또는 하기로 구성되는 군으로부터 선택되는 어느 하나이며, 단, Ar 1 및 Ar 2 중 하나는 이상은 아다만틸이다:Preferably, Ar 1 and Ar 2 are each independently deuterium; Adamantyl; Or any one selected from the group consisting of, provided that at least one of Ar 1 and Ar 2 is adamantyl:
Figure PCTKR2020014151-appb-img-000012
Figure PCTKR2020014151-appb-img-000012
상기에서, Above,
X는 O; S 또는 NR이고,X is O; S or NR,
R은 치환 또는 비치환된 C 6-12 아릴이고,R is substituted or unsubstituted C 6-12 aryl,
R' 1 및 R' 2는 각각 독립적으로, 수소; 중수소; 치환 또는 비치환된 C 1-10 알킬; 또는 치환 또는 비치환된 C 6-12 아릴이다.R '1 and R' 2 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 1-10 alkyl; Or substituted or unsubstituted C 6-12 aryl.
바람직하게는, R은 페닐이다.Preferably, R is phenyl.
바람직하게는, R' 1 및 R' 2는 각각 독립적으로, 메틸이다.Preferably, R '1 and R' 2 are, each independently methyl.
바람직하게는, R 1 및 R 2는 각각 독립적으로, 수소; 또는 중수소이다.Preferably, R 1 and R 2 are each independently hydrogen; Or deuterium.
바람직하게는, m 및 n은 각각 독립적으로 0 또는 1이다.Preferably, m and n are each independently 0 or 1.
바람직하게는, 상기 화학식 1로 표시되는 화합물은, 하기로 구성되는 군으로부터 선택되는 어느 하나일 수 있다:Preferably, the compound represented by Formula 1 may be any one selected from the group consisting of:
Figure PCTKR2020014151-appb-img-000013
Figure PCTKR2020014151-appb-img-000013
Figure PCTKR2020014151-appb-img-000014
Figure PCTKR2020014151-appb-img-000014
Figure PCTKR2020014151-appb-img-000015
Figure PCTKR2020014151-appb-img-000015
Figure PCTKR2020014151-appb-img-000016
Figure PCTKR2020014151-appb-img-000016
Figure PCTKR2020014151-appb-img-000017
Figure PCTKR2020014151-appb-img-000017
Figure PCTKR2020014151-appb-img-000018
Figure PCTKR2020014151-appb-img-000018
Figure PCTKR2020014151-appb-img-000019
Figure PCTKR2020014151-appb-img-000019
Figure PCTKR2020014151-appb-img-000020
Figure PCTKR2020014151-appb-img-000020
Figure PCTKR2020014151-appb-img-000021
Figure PCTKR2020014151-appb-img-000021
Figure PCTKR2020014151-appb-img-000022
Figure PCTKR2020014151-appb-img-000022
Figure PCTKR2020014151-appb-img-000023
Figure PCTKR2020014151-appb-img-000023
Figure PCTKR2020014151-appb-img-000024
Figure PCTKR2020014151-appb-img-000024
Figure PCTKR2020014151-appb-img-000025
Figure PCTKR2020014151-appb-img-000025
Figure PCTKR2020014151-appb-img-000026
Figure PCTKR2020014151-appb-img-000026
Figure PCTKR2020014151-appb-img-000027
Figure PCTKR2020014151-appb-img-000027
Figure PCTKR2020014151-appb-img-000028
Figure PCTKR2020014151-appb-img-000028
Figure PCTKR2020014151-appb-img-000029
Figure PCTKR2020014151-appb-img-000029
Figure PCTKR2020014151-appb-img-000030
Figure PCTKR2020014151-appb-img-000030
Figure PCTKR2020014151-appb-img-000031
Figure PCTKR2020014151-appb-img-000031
Figure PCTKR2020014151-appb-img-000032
Figure PCTKR2020014151-appb-img-000032
Figure PCTKR2020014151-appb-img-000033
Figure PCTKR2020014151-appb-img-000033
Figure PCTKR2020014151-appb-img-000034
.
Figure PCTKR2020014151-appb-img-000034
.
Figure PCTKR2020014151-appb-img-000035
Figure PCTKR2020014151-appb-img-000035
Figure PCTKR2020014151-appb-img-000036
Figure PCTKR2020014151-appb-img-000036
Figure PCTKR2020014151-appb-img-000037
Figure PCTKR2020014151-appb-img-000037
Figure PCTKR2020014151-appb-img-000038
Figure PCTKR2020014151-appb-img-000038
Figure PCTKR2020014151-appb-img-000039
Figure PCTKR2020014151-appb-img-000039
Figure PCTKR2020014151-appb-img-000040
Figure PCTKR2020014151-appb-img-000040
Figure PCTKR2020014151-appb-img-000041
Figure PCTKR2020014151-appb-img-000041
Figure PCTKR2020014151-appb-img-000042
.
Figure PCTKR2020014151-appb-img-000042
.
상기 화학식 1로 표시되는 화합물은 하기 반응식 1을 거쳐 제조할 수 있다. The compound represented by Formula 1 can be prepared through the following Scheme 1.
[반응식 1][Scheme 1]
Figure PCTKR2020014151-appb-img-000043
Figure PCTKR2020014151-appb-img-000043
상기 반응식 1에서, X를 제외한 다른 치환기에 대한 정의는 앞서 설명한 바와 같고, X는 할로겐이고, 바람직하게는 브로모, 또는 클로로이다.In Reaction Scheme 1, definitions for other substituents other than X are as described above, and X is halogen, preferably bromo or chloro.
상기 반응식 1은 스즈키 커플링 반응으로 팔라듐 촉매와 염기 존재 하에 수행하는 것이 바람직하며, 스즈키 커플링 반응을 위한 반응기는 당업계에 알려진 바에 따라 변경이 가능하다. Scheme 1 is a Suzuki coupling reaction, preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction may be changed as known in the art.
상기 화학식 1로 표시되는 화합물에서, 각 치환기의 위치는 상기 반응식 1을 참조하여 적절하게 출발물질의 구조를 변화시킴으로써 제조할 수 있다. 이러한 상기 화학식 1로 표시되는 화합물의 제조 방법은 후술할 제조예에서 보다 구체화될 수 있다.In the compound represented by Formula 1, the position of each substituent can be prepared by appropriately changing the structure of the starting material with reference to Scheme 1. The method for preparing the compound represented by Formula 1 may be more specific in Preparation Examples to be described later.
(유기 발광 소자)(Organic Light-Emitting Element)
한편, 본 발명은 상기 화학식 1로 표시되는 화합물을 포함하는 유기 발광 소자를 제공한다. 일례로, 본 발명은 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 상기 화학식 1로 표시되는 화합물을 포함하는, 유기 발광 소자를 제공한다. Meanwhile, the present invention provides an organic light-emitting device including the compound represented by Formula 1 above. For example, the present invention provides 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 of the organic material layers includes a compound represented by Formula 1 .
본 발명의 유기 발광 소자의 유기물층은 단층 구조로 이루어질 수도 있으나, 2층 이상의 유기물층이 적층된 다층 구조로 이루어질 수 있다. 예컨대, 본 발명의 유기 발광 소자는 유기물층으로서 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층, 정공저지층 등을 포함하는 구조를 가질 수 있다. 그러나 유기 발광 소자의 구조는 이에 한정되지 않고 더 적은 수의 유기층을 포함할 수 있다.The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, and the like as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.
또한, 상기 유기물 층은 정공주입층, 정공수송층, 또는 정공 주입과 수송을 동시에 하는 층을 포함할 수 있고, 상기 정공주입층, 정공수송층, 또는 정공 주입과 수송을 동시에 하는 층은 상기 화학식 1로 표시되는 화합물을 포함한다. In addition, the organic material layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes, and the hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 above. Including the indicated compound.
또한, 상기 유기물층은 발광층을 포함할 수 있고, 상기 발광층은 상기 화학식 1로 표시되는 화합물을 포함한다. In addition, the organic material layer may include an emission layer, and the emission layer includes a compound represented by Formula 1.
또한, 상기 유기물층은 정공저지층을 포함할 수 있고, 상기 정공저지층은 상기 화학식 1로 표시되는 화합물을 포함한다. In addition, the organic material layer may include a hole blocking layer, and the hole blocking layer includes a compound represented by Formula 1 above.
본 발명의 유기 발광 소자의 유기물 층은 단층 구조로 이루어질 수도 있으나, 2층 이상의 유기물층이 적층된 다층 구조로 이루어질 수 있다. 예컨대, 본 발명의 유기 발광 소자는 유기물 층으로서 발광층 이외에, 상기 제1전극과 상기 발광층 사이의 정공주입층 및 정공수송층, 및 상기 발광층과 상기 제2전극 사이의 전자수송층 및 전자주입층을 더 포함하는 구조를 가질 수 있다. 그러나 유기 발광 소자의 구조는 이에 한정되지 않고 더 적은 수 또는 더 많은 수의 유기층을 포함할 수 있다.The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention further includes a hole injection layer and a hole transport layer between the first electrode and the emission layer, and an electron transport layer and an electron injection layer between the emission layer and the second electrode in addition to the emission layer as an organic material layer. It can have a structure to do. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number or a larger number of organic layers.
또한, 본 발명에 따른 유기 발광 소자는, 상기 제1 전극이 양극이고 상기 제2 전극은 음극인, 기판 상에 양극, 1층 이상의 유기물층 및 음극이 순차적으로 적층된 구조(normal type)의 유기 발광 소자일 수 있다. 또한, 본 발명에 따른 유기 발광 소자는, 상기 제1 전극이 음극이고 상기 제2 전극은 양극인, 기판 상에 음극, 1층 이상의 유기물층 및 양극이 순차적으로 적층된 역방향 구조(inverted type)의 유기 발광 소자일 수 있다. 예컨대, 본 발명의 일실시예에 따른 유기 발광 소자의 구조는 도 1 및 2에 예시되어 있다.In addition, in the organic light emitting device according to the present invention, the first electrode is an anode and the second electrode is a cathode, and an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate (normal type). It may be a device. In addition, in the organic light emitting device according to the present invention, the first electrode is a cathode and the second electrode is an anode, and a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. It may be a light emitting device. For example, the structure of an organic light-emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.
도 1은 기판(1), 양극(2), 발광층(4), 정공저지층(9) 및 음극(6)으로 이루어진 유기 발광 소자의 예를 도시한 것이다. 이와 같은 구조에 있어서, 상기 화학식 1로 표시되는 화합물은 상기 정공저지층에 포함될 수 있다.FIG. 1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a light emitting layer 4, a hole blocking layer 9, and a cathode 6. In such a structure, the compound represented by Formula 1 may be included in the hole blocking layer.
도 2는 기판(1), 양극(2), 정공주입층(7), 정공수송층(3), 전자억제층(8), 발광층(4), 정공저지층(9), 전자주입 및 수송층(5) 및 음극(6)으로 이루어진 유기 발광 소자의 예를 도시한 것이다. 이와 같은 구조에 있어서, 상기 화학식 1로 표시되는 화합물은 상기 정공저지층에 포함될 수 있다.2 shows a substrate 1, an anode 2, a hole injection layer 7, a hole transport layer 3, an electron suppression layer 8, a light emitting layer 4, a hole blocking layer 9, an electron injection and transport layer ( 5) and a cathode 6 are shown as an example of an organic light-emitting device. In such a structure, the compound represented by Formula 1 may be included in the hole blocking layer.
본 발명에 따른 유기 발광 소자는, 상기 유기물층 중 1층 이상이 상기 화학식 1로 표시되는 화합물을 포함하는 것을 제외하고는 당 기술분야에 알려져 있는 재료와 방법으로 제조될 수 있다. 또한, 상기 유기 발광 소자가 복수개의 유기물층을 포함하는 경우, 상기 유기물층은 동일한 물질 또는 다른 물질로 형성될 수 있다. The organic light-emitting device according to the present invention may be manufactured by materials and methods known in the art, except that at least one of the organic material layers includes the compound represented by Chemical Formula 1. In addition, when the organic light-emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.
예컨대, 본 발명에 따른 유기 발광 소자는 기판 상에 제1 전극, 유기물층 및 제2 전극을 순차적으로 적층시켜 제조할 수 있다. 이때, 스퍼터링법(sputtering)이나 전자빔 증발법(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 정공 주입층, 정공 수송층, 발광층 및 전자수송층을 포함하는 유기물층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시켜 제조할 수 있다. 이와 같은 방법 외에도, 기판 상에 음극 물질부터 유기물층, 양극 물질을 차례로 증착시켜 유기 발광 소자를 만들 수 있다. For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. And, after forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, it can be prepared by 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.
또한, 상기 화학식 1로 표시되는 화합물은 유기 발광 소자의 제조시 진공 증착법 뿐만 아니라 용액 도포법에 의하여 유기물층으로 형성될 수 있다. 여기서, 용액 도포법이라 함은 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯 프린팅, 스크린 프린팅, 스프레이법, 롤 코팅 등을 의미하지만, 이들만으로 한정되는 것은 아니다.In addition, the compound represented by Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution 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.
이와 같은 방법 외에도, 기판 상에 음극 물질로부터 유기물층, 양극 물질을 차례로 증착시켜 유기 발광 소자를 제조할 수 있다(WO 2003/012890). 다만, 제조 방법이 이에 한정되는 것은 아니다. In addition to such a method, 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 (WO 2003/012890). However, the manufacturing method is not limited thereto.
일례로, 상기 제1 전극은 양극이고, 상기 제2 전극은 음극이거나, 또는 상기 제1 전극은 음극이고, 상기 제2 전극은 양극이다.For example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode, and the second electrode is an anode.
상기 양극 물질로는 통상 유기물층으로 정공 주입이 원활할 수 있도록 일함수가 큰 물질이 바람직하다. 상기 양극 물질의 구체적인 예로는 바나듐, 크롬, 구리, 아연, 금과 같은 금속 또는 이들의 합금; 아연 산화물, 인듐 산화물, 인듐주석 산화물(ITO), 인듐아연 산화물(IZO)과 같은 금속 산화물; ZnO:Al 또는 SnO 2: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. As the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the 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); Combinations of metals and oxides 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.
상기 음극 물질로는 통상 유기물층으로 전자 주입이 용이하도록 일함수가 작은 물질인 것이 바람직하다. 상기 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 LiO 2/Al과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다. It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multilayered materials such as LiF/Al or LiO 2 /Al, but are not limited thereto.
상기 정공주입층은 전극으로부터 정공을 주입하는 층으로, 정공 주입 물질로는 정공을 수송하는 능력을 가져 양극에서의 정공 주입효과, 발광층 또는 발광재료에 대하여 우수한 정공 주입 효과를 갖고, 발광층에서 생성된 여기자의 전자주입층 또는 전자주입재료에의 이동을 방지하며, 또한, 박막 형성 능력이 우수한 화합물이 바람직하다. 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(porphyrin), 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 한정 되는 것은 아니다. The hole injection layer is a layer that injects holes from an 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, 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. It is preferable that 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. Specific examples of 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. Organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.
상기 정공수송층은 정공주입층으로부터 정공을 수취하여 발광층까지 정공을 수송하는 층으로, 정공 수송 물질로는 양극이나 정공 주입층으로부터 정공을 수송받아 발광층으로 옮겨줄 수 있는 물질로 정공에 대한 이동성이 큰 물질이 적합하다. 상기 정공 수송 물질로 상기 화학식 1로 표시되는 화합물을 사용하거나, 또는 아릴아민 계열의 유기물, 전도성 고분자, 및 공액 부분과 비공액 부분이 함께 있는 블록 공중합체 등을 사용할 수 있으나, 이에 한정되는 것은 아니다.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, and has high mobility for holes. The material is suitable. As the hole transport material, a compound represented by Formula 1 may be used, or an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion may be used, but the present invention is not limited thereto. .
상기 전자억제층(또는 전자저지층)은 상기 정공수송층 상에 형성되어, 바람직하게는 발광층에 접하여 구비되어, 정공이동도를 조절하고, 전자의 과다한 이동을 방지하여 정공-전자간 결합 확률을 높여줌으로써 유기 발광 소자의 효율을 개선하는 역할을 하는 층을 의미한다. 상기 전자억제층은 전자저지물질을 포함하고, 이러한 전자저지물질의 예로 상기 화학식 1로 표시되는 화합물을 사용하거나, 또는 아릴아민 계열의 유기물 등을 사용할 수 있으나, 이에 한정되는 것은 아니다.The electron inhibiting layer (or electron blocking layer) is formed on the hole transport layer and is preferably provided in contact with the light emitting layer to adjust hole mobility and prevent excessive movement of electrons, thereby increasing the probability of hole-electron coupling. It refers to a layer that serves to improve the efficiency of an organic light emitting device by giving it. The electron-suppression layer includes an electron-blocking material, and examples of such an electron-blocking material may include a compound represented by Formula 1 or an arylamine-based organic material, but are not limited thereto.
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 예로 8-히드록시-퀴놀린 알루미늄 착물(Alq 3); 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, 이에 한정되는 것은 아니다. As the light-emitting material, a material capable of emitting light in a visible light 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 for fluorescence or phosphorescence is preferable. Specific examples of 8-hydroxy-quinoline aluminum complex (Alq 3 ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole, and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.
상기 발광층은 상술한 바와 같이 호스트 재료 및 도펀트 재료를 포함할 수 있다. 호스트 재료는 축합 방향족환 유도체 또는 헤테로환 함유 화합물 등을 더 포함할 수 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 한정되는 것은 아니다. As described above, the emission layer may include a host material and a dopant material. The host material may further include 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, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.
도펀트 재료로는 방향족 아민 유도체, 스트릴아민 화합물, 붕소 착체, 플루오란텐 화합물, 금속 착체 등이 있다. 구체적으로 방향족 아민 유도체로는 치환 또는 비치환된 아릴아미노기를 갖는 축합 방향족환 유도체로서, 아릴아미노기를 갖는 피렌, 안트라센, 크리센, 페리플란텐 등이 있으며, 스티릴아민 화합물로는 치환 또는 비치환된 아릴아민에 적어도 1개의 아릴비닐기가 치환되어 있는 화합물로, 아릴기, 실릴기, 알킬기, 사이클로알킬기 및 아릴아미노기로 이루어진 군에서 1 또는 2 이상 선택되는 치환기가 치환 또는 비치환된다. 구체적으로 스티릴아민, 스티릴디아민, 스티릴트리아민, 스티릴테트라아민 등이 있으나, 이에 한정되는 것은 아니다. 또한, 금속 착체로는 이리듐 착체, 백금 착체 등이 있으나, 이에 한정되는 것은 아니다.Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periflanthene and the like having an arylamino group, and the styrylamine compound is substituted or unsubstituted As a compound in which at least one arylvinyl group is substituted on the arylamine, one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, examples of the metal complex include an iridium complex and a platinum complex, but are not limited thereto.
상기 정공저지층(또는 정공억제층)은 발광층 상에 형성되어, 바람직하게는 발광층에 접하여 구비되어, 전자이동도를 조절하고 정공의 과다한 이동을 방지하여 정공-전자간 결합 확률을 높여줌으로써 유기 발광 소자의 효율을 개선하는 역할을 하는 층을 의미한다. 상기 정공저지층은 정공저지물질을 포함하고, 본 발명의 화학식 1로 표시되는 화합물이 사용될 수 있다. 이외에 추가 사용 가능한 정공저지물질의 예로 트리아진을 포함한 아진류유도체; 트리아졸 유도체; 옥사디아졸 유도체; 페난트롤린 유도체; 포스핀옥사이드 유도체 등의 전자흡인기가 도입된 화합물을 사용할 수 있으나, 이에 한정되는 것은 아니다.The hole blocking layer (or hole inhibiting layer) is formed on the emission layer and is preferably provided in contact with the emission layer to control electron mobility and prevent excessive movement of holes, thereby increasing the probability of hole-electron bonding. It refers to a layer that serves to improve the efficiency of the device. The hole blocking layer includes a hole blocking material, and a compound represented by Formula 1 of the present invention may be used. In addition, examples of additionally usable hole-blocking substances include sub-gene derivatives including triazine; Triazole derivatives; Oxadiazole derivatives; Phenanthroline derivatives; A compound into which an electron withdrawing group is introduced, such as a phosphine oxide derivative, may be used, but is not limited thereto.
상기 전자 주입 및 수송층은 전극으로부터 전자를 주입하고, 수취된 전자를 발광층까지 수송하는 전자수송층 및 전자주입층의 역할을 동시에 수행하는 층으로, 상기 발광층 또는 상기 정공저지층 상에 형성된다. 이러한 전자 주입 및 수송물질로는 음극으로부터 전자를 잘 주입 받아 발광층으로 옮겨줄 수 있는 물질로서, 전자에 대한 이동성이 큰 물질이 적합하다. 구체적인 전자 주입 및 수송물질의 예로는 8-히드록시퀴놀린의 Al 착물; Alq 3를 포함한 착물; 유기 라디칼 화합물; 히드록시플라본-금속 착물; 트리아진 유도체 등이 있으나, 이들에만 한정되는 것은 아니다. 또는 플루오레논, 안트라퀴노다이메탄, 다이페노퀴논, 티오피란 다이옥사이드, 옥사졸, 옥사다이아졸, 트리아졸, 이미다졸, 페릴렌테트라카복실산, 프레오레닐리덴 메탄, 안트론 등과 그들의 유도체, 금속 착체 화합물, 또는 질소 함유 5원환 유도체 등과 함께 사용할 수도 있으나, 이에 한정되는 것은 아니다. The electron injection and transport layer is a layer that simultaneously serves as an electron transport layer and an electron injection layer for injecting electrons from an electrode and transporting received electrons to the emission layer, and is formed on the emission layer or the hole blocking layer. As such an electron injection and transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high mobility for electrons is suitable. Examples of specific electron injection and transport materials include Al complex of 8-hydroxyquinoline; Complexes containing Alq 3; Organic radical compounds; Hydroxyflavone-metal complex; Triazine derivatives and the like, but are not limited thereto. Or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and their derivatives, metal complex compounds , Or nitrogen-containing 5-membered cyclic derivatives may be used together, but the present invention is not limited thereto.
상기 전자 주입 및 수송층은 전자 주입층 및 전자 수송층과 같은 별개의 층으로도 형성될 수 있다. 이와 같은 경우, 전자 수송층은 상기 발광층 또는 상기 정공저지층 상에 형성되고, 상기 전자 수송층에 포함되는 전자 수송 물질로는 상술한 전자 주입 및 수송 물질이 사용될 수 있다. 또한, 전자 주입층은 상기 전자 수송층 상에 형성되고, 상기 전자 주입층에 포함되는 전자 주입 물질로는 LiF, NaCl, CsF, Li 2O, BaO, 플루오레논, 안트라퀴노다이메탄, 다이페노퀴논, 티오피란 다이옥사이드, 옥사졸, 옥사다이아졸, 트리아졸, 이미다졸, 페릴렌테트라카복실산, 프레오레닐리덴 메탄, 안트론 등과 그들의 유도체, 금속 착체 화합물 및 질소 함유 5원환 유도체 등이 사용될 수 있다.The electron injection and transport layer may also be formed as separate layers such as an electron injection layer and an electron transport layer. In this case, the electron transport layer is formed on the emission layer or the hole blocking layer, and the electron injection and transport material described above may be used as the electron transport material included in the electron transport layer. In addition, the electron injection layer is formed on the electron transport layer, and electron injection materials included in the electron injection layer include LiF, NaCl, CsF, Li 2 O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, Thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and the like, their derivatives, metal complex compounds, and nitrogen-containing 5-membered ring derivatives.
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 한정되는 것은 아니다.Examples of the metal complex compound 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 thereto.
본 발명에 따른 유기 발광 소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic light emitting device according to the present invention may be a top emission type, a bottom emission type, or a double-sided emission type depending on the material used.
또한, 상기 화학식 1로 표시되는 화합물은 유기 발광 소자 외에도 유기 태양 전지 또는 유기 트랜지스터에 포함될 수 있다.In addition, the compound represented by Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.
상기 화학식 1로 표시되는 화합물 및 이를 포함하는 유기 발광 소자의 제조를 이하 실시예에서 구체적으로 설명한다. 그러나 하기 실시예는 본 발명을 예시하기 위한 것이며, 본 발명의 범위가 이들에 의하여 한정되는 것은 아니다.Preparation of the compound represented by Formula 1 and the organic light emitting device including the same will be described in detail in the following examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.
제조예 A: 중간체 화합물 A의 합성Preparation A: Synthesis of Intermediate Compound A
Figure PCTKR2020014151-appb-img-000044
Figure PCTKR2020014151-appb-img-000044
질소 분위기에서 500 ml 둥근 바닥 플라스크에 화합물 y-1인 2-브로모―4’-클로로바이페닐(23.41 g, 87.66 mmol)을 THF 35 ml에 녹이고, 이를 -78℃로 냉각한 후 tert-부틸리튬(t-BuLi) 11.58 ml(2.5 M in pentane)를 적가한 다음 동일 온도에서 40 분 동안 교반하였다. 제조된 용액에 화합물 x-1인 2-브로모-9H-잔텐-9-온(15.62 g, 79.69 mmol)을 가한 후, 온도를 서서히 상온으로 올려 3 시간 동안 교반하였다. 이후, 디에틸에테르 15 ml와 2N 염산 수용액 25 ml의 혼합 용액에 상기 반응물을 부은 다음 30 분간 교반하여 생성된 고체를 여과하고, 물과 디에틸에테르로 씻은 후 건조하였다. 상기에서 건조된 고체 시료 중 2.5 g을 취하여 50 ml의 아세트산에 녹인 다음 촉매량(10 방울)의 진한 황산을 넣어 3 시간 동안 환류하였다. 이후, 생성된 고체 화합물을 여과하고 아세트산으로 씻어준 후 건조시켜 백색 고체 화합물인 화합물 A-1(18.22 g, 수율: 62%)을 얻었다.In a 500 ml round bottom flask in a nitrogen atmosphere, compound y-1, 2-bromo-4'-chlorobiphenyl (23.41 g, 87.66 mmol) was dissolved in 35 ml of THF, cooled to -78°C, and tert-butyl Lithium (t-BuLi) 11.58 ml (2.5 M in pentane) was added dropwise, followed by stirring at the same temperature for 40 minutes. After adding 2-bromo-9H-xanthene-9-one (15.62 g, 79.69 mmol) as compound x-1 to the prepared solution, the temperature was gradually raised to room temperature and stirred for 3 hours. Thereafter, the reactant was poured into a mixed solution of 15 ml of diethyl ether and 25 ml of 2N hydrochloric acid aqueous solution, and then stirred for 30 minutes to filter the resulting solid, washed with water and diethyl ether, and dried. 2.5 g of the dried solid sample was taken and dissolved in 50 ml of acetic acid, and then a catalytic amount (10 drops) of concentrated sulfuric acid was added and refluxed for 3 hours. Thereafter, the resulting solid compound was filtered, washed with acetic acid, and dried to obtain a white solid compound A-1 (18.22 g, yield: 62%).
다음으로, 질소 분위기에서 화학식 A-1(18.22 g, 49.65 mmol) 및 피나콜다이보론(13.86 g, 54.61 mmol), 아세트산칼륨(14.61 g, 148.94 mmol) 을 섞고, 디옥산(480 ml)에 첨가하고 교반하면서 가열하였다. 환류되는 상태에서 비스(디벤질리딘아세톤)팔라듐(0.38 g, 1.49 mmol)과 트리사이클로헥실포스핀(0.39 g, 2.99 mmol)을 넣고 12시간 동안 가열 및 교반하였다. 반응 종료 후, 상온으로 온도를 낮춘 후 여과하였다. 여과액에 물을 붓고 클로로포름으로 추출하고, 유기층을 무수황산마그네슘으로 건조하였다. 감압 증류 후 에탄올로 재결정하여 중간체 화합물 A(15.49 g, 수율: 68 %)을 얻었다.Next, formula A-1 (18.22 g, 49.65 mmol), pinacol diboron (13.86 g, 54.61 mmol) and potassium acetate (14.61 g, 148.94 mmol) were mixed in a nitrogen atmosphere, and added to dioxane (480 ml). And heated while stirring. In a refluxed state, bis(dibenzylidineacetone)palladium (0.38 g, 1.49 mmol) and tricyclohexylphosphine (0.39 g, 2.99 mmol) were added, followed by heating and stirring for 12 hours. After the reaction was completed, the temperature was lowered to room temperature and then filtered. Water was poured into the filtrate, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, it was recrystallized with ethanol to obtain an intermediate compound A (15.49 g, yield: 68%).
MS[M+H] += 458MS[M+H] + = 458
제조예 B: 중간체 화합물 B의 합성Preparation B: Synthesis of Intermediate Compound B
Figure PCTKR2020014151-appb-img-000045
Figure PCTKR2020014151-appb-img-000045
상기 제조예 A에서 출발물질 y-1 대신 출발물질 y-2를 사용한 것을 제외하고는, 상기 제조예 A와 동일한 방법을 사용하여 중간체 화합물 B를 제조하였다.Intermediate compound B was prepared in the same manner as in Preparation Example A, except that starting material y-2 was used instead of starting material y-1 in Preparation Example A.
MS[M+H] += 458MS[M+H] + = 458
제조예 C: 중간체 화합물 C의 합성Preparation C: Synthesis of Intermediate Compound C
Figure PCTKR2020014151-appb-img-000046
Figure PCTKR2020014151-appb-img-000046
상기 제조예 A에서 출발물질 y-1 대신 출발물질 y-3를 사용한 것을 제외하고는, 상기 제조예 A와 동일한 방법을 사용하여 중간체 화합물 C를 제조하였다.Intermediate compound C was prepared in the same manner as in Preparation Example A, except that starting material y-3 was used instead of starting material y-1 in Preparation Example A.
MS[M+H] += 458MS[M+H] + = 458
제조예 1: 화합물 1의 합성Preparation Example 1: Synthesis of Compound 1
Figure PCTKR2020014151-appb-img-000047
Figure PCTKR2020014151-appb-img-000047
질소 분위기에서 500 ml 둥근 바닥 플라스크에 화합물 A (9.64 g, 21.04 mmol), a-1 (7.69 g, 19.13 mmol)을 테트라하이드로퓨란 240 ml에 완전히 녹인 후 2M 탄산칼륨수용액(120 ml)을 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.66 g, 0.57 mmol)을 넣은 후 3 시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 물 층을 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시키고 테트라하이드로퓨란 310 ml로 재결정하여 화합물 1 (8.63 g, 65%)를 제조하였다.Compound A (9.64 g, 21.04 mmol), a-1 (7.69 g, 19.13 mmol) was completely dissolved in 240 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 ml) was added. , Tetrakis-(triphenylphosphine)palladium (0.66 g, 0.57 mmol) was added, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 310 ml of tetrahydrofuran to prepare compound 1 (8.63 g, 65%).
MS[M+H] += 698MS[M+H] + = 698
제조예 2: 화합물 2의 합성Preparation Example 2: Synthesis of Compound 2
Figure PCTKR2020014151-appb-img-000048
Figure PCTKR2020014151-appb-img-000048
질소 분위기에서 500 ml 둥근 바닥 플라스크에 화합물 A (7.58 g, 16.55 mmol), 및 화합물 a-2(7.19 g, 15.04 mmol)을 테트라하이드로퓨란 240 ml에 완전히 녹인 후 2M 탄산칼륨수용액(120 ml)을 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.52 g, 0.45 mmol)을 넣은 후 4시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 물 층을 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시키고 에틸아세테이트 430 ml로 재결정하여 화합물 2(7.78 g, 67%)를 제조하였다.Compound A (7.58 g, 16.55 mmol) and compound a-2 (7.19 g, 15.04 mmol) were completely dissolved in 240 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 ml) was added. After addition, tetrakis-(triphenylphosphine)palladium (0.52 g, 0.45 mmol) was added, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 430 ml of ethyl acetate to prepare compound 2 (7.78 g, 67%).
MS[M+H] += 774MS[M+H] + = 774
제조예 3: 화합물 3의 합성Preparation Example 3: Synthesis of Compound 3
Figure PCTKR2020014151-appb-img-000049
Figure PCTKR2020014151-appb-img-000049
질소 분위기에서 500 ml 둥근 바닥 플라스크에 화합물 B (8.20 g, 17.91 mmol), 및 화합물 b-1(7.36 g, 16.28 mmol)을 테트라하이드로퓨란 240 ml에 완전히 녹인 후 2M 탄산칼륨수용액(120 ml)을 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.56 g, 0.49 mmol)을 넣은 후 3시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 물 층을 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시키고 테트라하이드로퓨란 310 ml로 재결정하여 화합물 3(7.22 g, 59%)를 제조하였다.Compound B (8.20 g, 17.91 mmol) and compound b-1 (7.36 g, 16.28 mmol) were completely dissolved in 240 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 ml) was added. After addition, tetrakis-(triphenylphosphine)palladium (0.56 g, 0.49 mmol) was added, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 310 ml of tetrahydrofuran to prepare compound 3 (7.22 g, 59%).
MS[M+H] += 748MS[M+H] + = 748
제조예 4: 화합물 4의 합성Preparation Example 4: Synthesis of Compound 4
Figure PCTKR2020014151-appb-img-000050
Figure PCTKR2020014151-appb-img-000050
질소 분위기에서 500 ml 둥근 바닥 플라스크에 화합물 C (7.47 g, 16.31 mmol), 및 화합물 c-1(7.49 g, 14.83 mmol)을 테트라하이드로퓨란 240 ml에 완전히 녹인 후 2M 탄산칼륨수용액(120 ml)을 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.51 g, 0.44 mmol)을 넣은 후 4시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 물 층을 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시키고 테트라하이드로퓨란 270 ml로 재결정하여 화합물 4(8.36 g, 70%)를 제조하였다.Compound C (7.47 g, 16.31 mmol) and compound c-1 (7.49 g, 14.83 mmol) were completely dissolved in 240 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 ml) was added. After addition, tetrakis-(triphenylphosphine)palladium (0.51 g, 0.44 mmol) was added, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 270 ml of tetrahydrofuran to prepare compound 4 (8.36 g, 70%).
MS[M+H] += 805MS[M+H] + = 805
제조예 5: 화합물 5의 합성Preparation Example 5: Synthesis of Compound 5
Figure PCTKR2020014151-appb-img-000051
Figure PCTKR2020014151-appb-img-000051
질소 분위기에서 500 ml 둥근 바닥 플라스크에 화합물 C (7.32 g, 15.97 mmol), 및 화합물 c-2(7.74 g, 14.52 mmol)을 테트라하이드로퓨란 240 mL에 완전히 녹인 후 2M 탄산칼륨수용액(120 ml)을 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.50 g, 0.44 mmol)을 넣은 후 4시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 물 층을 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시키고 에틸아세테이트 310 ml로 재결정하여 화합물 5(9.11 g, 75%)를 제조하였다.Compound C (7.32 g, 15.97 mmol) and compound c-2 (7.74 g, 14.52 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 ml) was added. After addition, tetrakis-(triphenylphosphine)palladium (0.50 g, 0.44 mmol) was added, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 310 ml of ethyl acetate to prepare compound 5 (9.11 g, 75%).
MS[M+H] += 833MS[M+H] + = 833
제조예 6: 화합물 6의 합성Preparation Example 6: Synthesis of Compound 6
Figure PCTKR2020014151-appb-img-000052
Figure PCTKR2020014151-appb-img-000052
질소 분위기에서 500 ml 둥근 바닥 플라스크에 화합물 A (8.16 g, 17.82 mmol), a-3 (7.92g, 16.20 mmol)을 테트라하이드로퓨란 240ml에 완전히 녹인 후 2M 탄산칼륨수용액(120ml)을 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.56 g, 0.49 mmol)을 넣은 후 5 시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 물 층을 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시키고 테트라하이드로퓨란 290 ml로 재결정하여 화합물 6 (8.44 g, 66%)를 제조하였다.Compound A (8.16 g, 17.82 mmol), a-3 (7.92 g, 16.20 mmol) was completely dissolved in 240 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 ml) was added, and tetrahydrofuran was added. After adding kiss-(triphenylphosphine)palladium (0.56 g, 0.49 mmol), the mixture was heated and stirred for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 290 ml of tetrahydrofuran to prepare compound 6 (8.44 g, 66%).
MS[M+H] += 788MS[M+H] + = 788
제조예 7: 화합물 7의 합성Preparation Example 7: Synthesis of Compound 7
Figure PCTKR2020014151-appb-img-000053
Figure PCTKR2020014151-appb-img-000053
질소 분위기에서 500 ml 둥근 바닥 플라스크에 화합물 A (9.43 g, 20.60mmol), a-4 (8.22 g, 18.72 mmol)을 테트라하이드로퓨란 240 ml에 완전히 녹인 후 2M 탄산칼륨수용액(120 ml)을 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.65 g, 0.56 mmol)을 넣은 후 5 시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 물 층을 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시키고 테트라하이드로퓨란 310 ml로 재결정하여 화합물 7 (7.72 g, 56%)를 제조하였다.Compound A (9.43 g, 20.60 mmol) and a-4 (8.22 g, 18.72 mmol) were completely dissolved in 240 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 ml) was added. , Tetrakis-(triphenylphosphine)palladium (0.65 g, 0.56 mmol) was added, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 310 ml of tetrahydrofuran to prepare compound 7 (7.72 g, 56%).
MS[M+H] += 738MS[M+H] + = 738
제조예 8: 화합물 8의 합성Preparation Example 8: Synthesis of Compound 8
Figure PCTKR2020014151-appb-img-000054
Figure PCTKR2020014151-appb-img-000054
질소 분위기에서 500 ml 둥근 바닥 플라스크에 화합물 B (6.55 g, 14.30 mmol), 및 화합물 b-3(6.89 g, 13.01 mmol)을 테트라하이드로퓨란 240 ml에 완전히 녹인 후 2M 탄산칼륨수용액(120 ml)을 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.45 g, 0.39 mmol)을 넣은 후 7 시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 물 층을 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시키고 테트라하이드로퓨란 310 ml로 재결정하여 화합물 8(6.79 g, 63%)를 제조하였다. Compound B (6.55 g, 14.30 mmol) and compound b-3 (6.89 g, 13.01 mmol) were completely dissolved in 240 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then a 2M aqueous potassium carbonate solution (120 ml) was added. After addition, tetrakis-(triphenylphosphine)palladium (0.45 g, 0.39 mmol) was added, followed by heating and stirring for 7 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 310 ml of tetrahydrofuran to prepare compound 8 (6.79 g, 63%).
MS[M+H] += 833MS[M+H] + = 833
제조예 9: 화합물 9의 합성Preparation Example 9: Synthesis of Compound 9
Figure PCTKR2020014151-appb-img-000055
Figure PCTKR2020014151-appb-img-000055
질소 분위기에서 500 ml 둥근 바닥 플라스크에 화합물 C(12.09 g, 26.40 mmol), 및 화합물 c-3(9.12 g, 24.01 mmol)을 테트라하이드로퓨란 240 mL에 완전히 녹인 후 2M 탄산칼륨수용액(120 ml)을 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.83 g, 0.72 mmol)을 넣은 후 5 시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 물 층을 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시키고 에틸아세테이트 380 ml로 재결정하여 화합물 9(11.16 g, 68%)를 제조하였다.Compound C (12.09 g, 26.40 mmol) and compound c-3 (9.12 g, 24.01 mmol) were completely dissolved in 240 mL of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 ml) was added. After addition, tetrakis-(triphenylphosphine)palladium (0.83 g, 0.72 mmol) was added, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 380 ml of ethyl acetate to prepare compound 9 (11.16 g, 68%).
MS[M+H] += 680MS[M+H] + = 680
제조예 10: 화합물 10의 합성Preparation Example 10: Synthesis of Compound 10
Figure PCTKR2020014151-appb-img-000056
Figure PCTKR2020014151-appb-img-000056
질소 분위기에서 500 ml 둥근 바닥 플라스크에 화합물 C(5.91 g, 12.89 mmol), 및 화합물 c-4(7.01 g, 11.72 mmol)을 테트라하이드로퓨란 240 ml에 완전히 녹인 후 2M 탄산칼륨수용액(120 ml)을 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.41 g, 0.35 mmol)을 넣은 후 4시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 물 층을 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시키고 테트라하이드로퓨란 310 ml로 재결정하여 화합물 10(5.72 g, 54%)를 제조하였다.Compound C (5.91 g, 12.89 mmol) and compound c-4 (7.01 g, 11.72 mmol) were completely dissolved in 240 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 ml) was added. After addition, tetrakis-(triphenylphosphine)palladium (0.41 g, 0.35 mmol) was added, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 310 ml of tetrahydrofuran to prepare compound 10 (5.72 g, 54%).
MS[M+H] += 909MS[M+H] + = 909
제조예 11: 화합물 11의 합성Preparation Example 11: Synthesis of Compound 11
Figure PCTKR2020014151-appb-img-000057
Figure PCTKR2020014151-appb-img-000057
질소 분위기에서 500 ml 둥근 바닥 플라스크에 화합물 A(7.99 g, 17.45 mmol), a-4 (8.12 g, 15.86 mmol)을 테트라하이드로퓨란 240ml에 완전히 녹인 후 2M 탄산칼륨수용액(120 ml)을 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.55 g, 0.48 mmol)을 넣은 후 4 시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 물 층을 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시키고 테트라하이드로퓨란 310 ml로 재결정하여 화합물 11 (9.77 g, 71%)를 제조하였다.Compound A (7.99 g, 17.45 mmol), a-4 (8.12 g, 15.86 mmol) was completely dissolved in 240 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 ml) was added, After tetrakis-(triphenylphosphine)palladium (0.55 g, 0.48 mmol) was added, the mixture was heated and stirred for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 310 ml of tetrahydrofuran to prepare compound 11 (9.77 g, 71%).
MS[M+H] += 863MS[M+H] + = 863
제조예 12: 화합물 12의 합성Preparation Example 12: Synthesis of Compound 12
Figure PCTKR2020014151-appb-img-000058
Figure PCTKR2020014151-appb-img-000058
질소 분위기에서 500 ml 둥근 바닥 플라스크에 화합물 B(7.71 g, 16.82 mmol), b-5 (7.77 g, 15.30 mmol)을 테트라하이드로퓨란 240 ml에 완전히 녹인 후 2M 탄산칼륨수용액(120 ml)을 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.53 g, 0.46 mmol)을 넣은 후 4 시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 물 층을 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시키고 테트라하이드로퓨란 250 ml로 재결정하여 화합물 12(6.84 g, 56%)를 제조하였다.Compound B (7.71 g, 16.82 mmol) and b-5 (7.77 g, 15.30 mmol) were completely dissolved in 240 ml of tetrahydrofuran in a 500 ml round bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 ml) was added. , Tetrakis-(triphenylphosphine)palladium (0.53 g, 0.46 mmol) was added, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 250 ml of tetrahydrofuran to prepare compound 12 (6.84 g, 56%).
MS[M+H] += 804MS[M+H] + = 804
제조예 13: 화합물 13의 합성Preparation Example 13: Synthesis of Compound 13
Figure PCTKR2020014151-appb-img-000059
Figure PCTKR2020014151-appb-img-000059
질소 분위기에서 500 ml 둥근 바닥 플라스크에 화합물 B(8.04 g, 17.56 mmol), b-6 (8.11 g, 15.96 mmol)을 테트라하이드로퓨란 240 ml에 완전히 녹인 후 2M 탄산칼륨수용액(120 ml)을 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.55 g, 0.48 mmol)을 넣은 후 4 시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 물 층을 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시키고 테트라하이드로퓨란 280 ml로 재결정하여 화합물 13 (6.29 g, 49%)를 제조하였다.Compound B (8.04 g, 17.56 mmol) and b-6 (8.11 g, 15.96 mmol) were completely dissolved in 240 ml of tetrahydrofuran in a 500 ml round-bottom flask in a nitrogen atmosphere, and then 2M aqueous potassium carbonate solution (120 ml) was added. , Tetrakis-(triphenylphosphine)palladium (0.55 g, 0.48 mmol) was added, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 280 ml of tetrahydrofuran to prepare compound 13 (6.29 g, 49%).
MS[M+H] += 805MS[M+H] + = 805
실시예 1-1: 유기발광소자의 제조Example 1-1: Fabrication of an organic light emitting device
ITO(indium tin oxide)가 1,000Å의 두께로 박막 코팅된 유리 기판을 세제를 녹인 증류수에 넣고 초음파로 세척하였다. 이때, 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, 메탄올의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 수송시켰다. 또한, 산소 플라즈마를 이용하여 상기 기판을 5분간 세정한 후 진공 증착기로 기판을 수송시켰다.A glass substrate coated with a thin film of ITO (indium tin oxide) having a thickness of 1,000Å was put in distilled water dissolved in a detergent and washed with ultrasonic waves. At this time, a product made by Fischer Co. was used as a detergent, and distilled water secondarily filtered with a filter manufactured by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.
이렇게 준비된 양극인 ITO 투명 전극 위에 하기 화합물 HI1 및 하기 화합물 HI2의 화합물을 98:2(몰비)의 비가 되도록 100Å의 두께로 열 진공 증착하여 정공주입층을 형성하였다. 상기 정공주입층 위에 하기 화학식 HT1으로 표시되는 화합물(1150Å)을 진공 증착하여 정공수송층을 형성하였다. 이어서, 상기 정공수송층 위에 막 두께 50Å으로 EB1의 화합물을 진공 증착하여 전자억제층을 형성하였다. 이어서, 상기 전자억제층 위에 막 두께 200Å으로 하기 화학식 BH로 표시되는 화합물 및 하기 화학식 BD로 표시되는 화합물을 25:1의 중량비로 진공증착하여 발광층을 형성하였다. 상기 발광층 위에 막 두께 50Å으로 상기 제조예 1에서 합성한 화합물 1으로 표시되는 화합물을 진공 증착하여 정공저지층을 형성하였다. 이어서, 상기 정공저지층 위에 하기 화학식 ET1으로 표시되는 화합물과 하기 화학식 LiQ로 표시되는 화합물을 1:1의 중량비로 진공증착하여 310Å의 두께로 전자 주입 및 수송층을 형성하였다. 상기 전자 주입 및 수송층 위에 순차적으로 12Å두께로 리튬플로라이드(LiF)와 1,000Å 두께로 알루미늄을 증착하여 음극을 형성하였다. A hole injection layer was formed by thermally vacuum evaporating a compound of the following compound HI1 and the following compound HI2 to a thickness of 100 Å in a ratio of 98:2 (molar ratio) on the prepared ITO transparent electrode, which is an anode. A hole transport layer was formed by vacuum depositing a compound (1150Å) represented by the following formula HT1 on the hole injection layer. Subsequently, an electron suppressing layer was formed by vacuum depositing a compound of EB1 with a film thickness of 50 Å on the hole transport layer. Subsequently, a light emitting layer was formed by vacuum depositing a compound represented by the following formula BH and a compound represented by the following formula BD with a film thickness of 200 Å on the electron suppressing layer at a weight ratio of 25:1. A hole blocking layer was formed by vacuum depositing a compound represented by Compound 1 synthesized in Preparation Example 1 with a film thickness of 50 Å on the emission layer. Subsequently, a compound represented by the following formula ET1 and a compound represented by the following formula LiQ were vacuum-deposited at a weight ratio of 1:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 310Å. Lithium fluoride (LiF) in a thickness of 12 Å and aluminum in a thickness of 1,000 Å were sequentially deposited on the electron injection and transport layer to form a negative electrode.
Figure PCTKR2020014151-appb-img-000060
Figure PCTKR2020014151-appb-img-000060
상기의 과정에서 유기물의 증착속도는 0.4~0.7Å/sec를 유지하였고, 음극의 리튬플로라이드는 0.3Å/sec, 알루미늄은 2Å/sec의 증착 속도를 유지하였으며, 증착시 진공도는 2x10 -7 ~ 5x10 -6 torr를 유지하여, 유기 발광 소자를 제작하였다.In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7Å/sec, the deposition rate of lithium fluoride at the cathode was 0.3Å/sec, and the deposition rate of aluminum was 2Å/sec, and the vacuum degree during deposition was 2x10 -7 ~ Maintaining 5x10 -6 torr, an organic light emitting device was manufactured.
실시예 1-2 내지 실시예 1-13Examples 1-2 to 1-13
제조예 1의 화합물 대신 하기 표 1에 기재된 화합물을 사용하는 것을 제외하고는, 상기 실시예 1-1과 동일한 방법으로 유기 발광 소자를 제조하였다.An organic light-emitting device was manufactured in the same manner as in Example 1-1, except that the compound shown in Table 1 was used instead of the compound of Preparation Example 1.
비교예 1-1 내지 1-3Comparative Examples 1-1 to 1-3
제조예 1의 화합물 대신 하기 표 1에 기재된 화합물을 사용하는 것을 제외하고는, 상기 실시예 1-1과 동일한 방법으로 유기 발광 소자를 제조하였다. 하기 표 1에서 사용한 HB1, HB2, HB3 의 화합물을 하기와 같다.An organic light-emitting device was manufactured in the same manner as in Example 1-1, except that the compound shown in Table 1 was used instead of the compound of Preparation Example 1. The compounds of HB1, HB2, and HB3 used in Table 1 are as follows.
Figure PCTKR2020014151-appb-img-000061
Figure PCTKR2020014151-appb-img-000061
실험예Experimental example
상기 실시예 및 비교예에서 제조한 유기 발광 소자에 전류를 인가하였을 때, 전압, 효율, 색좌표 및 수명을 측정하고 그 결과를 하기 표 1에 나타내었다. T95은 휘도가 초기 휘도(1600 nit)에서 95%로 감소되는데 소요되는 시간을 의미한다.When a current was applied to the organic light emitting device prepared in the above Examples and Comparative Examples, voltage, efficiency, color coordinates, and lifetime were measured, and the results are shown in Table 1 below. T95 refers to the time it takes for the luminance to decrease from the initial luminance (1600 nit) to 95%.
구분division 화합물
(정공저지층)compound
(Hole retention stratum) 		전압
(V@10mA
/cm 2)Voltage
(V@10mA
/cm 2 ) 		효율
(cd/A@10mA
/cm 2)efficiency
(cd/A@10mA
/cm 2 ) 		색좌표
(x,y)Color coordinates
(x,y) 		T95
(hr)T95
(hr)
실시예 1-1Example 1-1 제조예 1Manufacturing Example 1 4.454.45 6.486.48 (0.146, 0.046)(0.146, 0.046) 250250
실시예 1-2Example 1-2 제조예 2Manufacturing Example 2 4.464.46 6.466.46 (0.144, 0.047)(0.144, 0.047) 255255
실시예 1-3Example 1-3 제조예 3Manufacturing Example 3 4.544.54 6.346.34 (0.146, 0.045)(0.146, 0.045) 235235
실시예 1-4Example 1-4 제조예 4Manufacturing Example 4 4.694.69 6.216.21 (0.144, 0.045)(0.144, 0.045) 225225
실시예 1-5Example 1-5 제조예 5Manufacturing Example 5 4.584.58 6.386.38 (0.146, 0.046)(0.146, 0.046) 235235
실시예 1-6Example 1-6 제조예 6Manufacturing Example 6 4.474.47 6.396.39 (0.146, 0.047)(0.146, 0.047) 250250
실시예 1-7Example 1-7 제조예 7Manufacturing Example 7 4.564.56 6.396.39 (0.146, 0.046)(0.146, 0.046) 245245
실시예 1-8Example 1-8 제조예 8Manufacturing Example 8 4.514.51 6.226.22 (0.146, 0.047)(0.146, 0.047) 230230
실시예 1-9Example 1-9 제조예 9Manufacturing Example 9 4.504.50 6.336.33 (0.144, 0.046)(0.144, 0.046) 235235
실시예 1-10Example 1-10 제조예 10Manufacturing Example 10 4.554.55 6.346.34 (0.146, 0.046)(0.146, 0.046) 245245
실시예 1-11Example 1-11 제조예 11Manufacturing Example 11 4.534.53 6.426.42 (0.147, 0.045)(0.147, 0.045) 250250
실시예 1-12Example 1-12 제조예 12Manufacturing Example 12 4.654.65 6.246.24 (0.146, 0.046)(0.146, 0.046) 215215
실시예 1-13Example 1-13 제조예 13Manufacturing Example 13 4.684.68 6.266.26 (0.147, 0.046)(0.147, 0.046) 220220
비교예 1-1Comparative Example 1-1 HB1HB1 4.944.94 5.815.81 (0.145, 0.046)(0.145, 0.046) 165165
비교예 1-2Comparative Example 1-2 HB2HB2 4.834.83 5.925.92 (0.144, 0.045)(0.144, 0.045) 190190
비교예 1-3Comparative Example 1-3 HB3HB3 5.315.31 5.655.65 (0.143, 0.045)(0.143, 0.045) 8585
상기 표 1에 나타난 바와 같이, 본 발명의 화합물을 정공저지층으로 사용한 유기 발광 소자는, 유기 발광 소자의 효율, 구동 전압 및 안정성 면에서 우수한 특성을 나타내었다.As shown in Table 1, the organic light-emitting device using the compound of the present invention as a hole blocking layer exhibited excellent characteristics in terms of efficiency, driving voltage, and stability of the organic light-emitting device.
실시예 1-1 내지 1-13에서, 본원 발명의 화합물을 사용한 유기 발광 소자는 잔텐과 플루오렌이 스피로 결합된 코어 구조에 하나 이상의 아다만틸기를 포함하는 트리아진계 치환기가 치환되지 않은 HB1, HB2, HB3의 물질을 사용하여 제조된 비교예 1-1, 1-2, 1-3의 유기 발광 소자보다 저전압, 고효율 및 장수명의 특성을 나타내었다.In Examples 1-1 to 1-13, the organic light-emitting device using the compound of the present invention is HB1, HB2 in which the triazine-based substituents containing at least one adamantyl group are not substituted in the core structure in which xanthene and fluorene are spiro bonded. , Compared to the organic light-emitting devices of Comparative Examples 1-1, 1-2, and 1-3 prepared using the material of HB3, it exhibited characteristics of low voltage, high efficiency, and long life.
부호의 설명Explanation of the sign
1: 기판 2: 양극1: substrate 2: anode
3: 정공수송층 4: 발광층3: hole transport layer 4: light emitting layer
5: 전자주입 및 수송층 6: 음극5: electron injection and transport layer 6: cathode
7: 정공주입층 8: 전자억제층7: hole injection layer 8: electron suppression layer
9: 정공저지층9: hole block

Claims (9)

  1. 하기 화학식 1로 표시되는 화합물:Compound represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2020014151-appb-img-000062
    Figure PCTKR2020014151-appb-img-000062
    상기 화학식 1에서,In Formula 1,
    X 1 내지 X 3는 각각 독립적으로, N 또는 CH이고, 단, X 1 내지 X 3 중 하나 이상이 N이고, X 1 to X 3 are each independently N or CH, provided that at least one of X 1 to X 3 is N,
    L 1 내지 L 3는 각각 독립적으로, 단일 결합; 또는 치환 또는 비치환된 C 6-60 아릴렌이고,L 1 to L 3 are each independently a single bond; Or a substituted or unsubstituted C 6-60 arylene,
    Ar 1 및 Ar 2는 각각 독립적으로, 수소; 중수소; 아다만틸; 치환 또는 비치환된 C 6-60 아릴; 치환 또는 비치환된 C 7-60 아릴알킬; 치환 또는 비치환된 C 7-60 아릴알케닐; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C 2-60 헤테로아릴이고, 단, Ar 1 및 Ar 2 중 하나 이상은 아다만틸이고, Ar 1 and Ar 2 are each independently hydrogen; heavy hydrogen; Adamantyl; Substituted or unsubstituted C 6-60 aryl; Substituted or unsubstituted C 7-60 arylalkyl; Substituted or unsubstituted C 7-60 arylalkenyl; Or substituted or unsubstituted C 2-60 heteroaryl including any one or more selected from the group consisting of N, O and S, provided that at least one of Ar 1 and Ar 2 is adamantyl,
    R 1 및 R 2는 수소; 중수소; 또는 치환 또는 비치환된 C 1-60 알킬이고,R 1 and R 2 are hydrogen; heavy hydrogen; Or substituted or unsubstituted C 1-60 alkyl,
    m은 0 내지 8의 정수이고,m is an integer from 0 to 8,
    n은 0 내지 7의 정수이다.n is an integer from 0 to 7.
  2. 제 1항에 있어서, The method of claim 1,
    상기 화학식 1로 표시되는 화합물은, 하기 화학식 1-1 내지 화학식 1-3으로 표시되는,The compound represented by Formula 1 is represented by the following Formulas 1-1 to 1-3,
    화합물:compound:
    [화학식 1-1][Formula 1-1]
    Figure PCTKR2020014151-appb-img-000063
    Figure PCTKR2020014151-appb-img-000063
    [화학식 1-2][Formula 1-2]
    Figure PCTKR2020014151-appb-img-000064
    Figure PCTKR2020014151-appb-img-000064
    [화학식 1-3][Formula 1-3]
    Figure PCTKR2020014151-appb-img-000065
    Figure PCTKR2020014151-appb-img-000065
    상기 화학식 1-1 내지 1-3에서, In Formulas 1-1 to 1-3,
    X 1, X 2, X 3, L 1, L 2, L 3, Ar 1, Ar 2, R 1, R 2, m 및 n은 청구항 1에서 정의한 바와 같다.X 1 , X 2 , X 3 , L 1 , L 2 , L 3 , Ar 1 , Ar 2 , R 1 , R 2 , m and n are as defined in claim 1.
  3. 제 1항에 있어서,The method of claim 1,
    L 1 내지 L 3는 각각 독립적으로, 단일 결합; 중수소로 치환 또는 비치환된 페닐렌; 중수소로 치환 또는 비치환된 비페닐릴렌; 중수소로 치환 또는 비치환된 터페닐릴렌; 중수소로 치환 또는 비치환된 플루오레닐렌; 또는 중수소로 치환 또는 비치환된 나프틸렌인,L 1 to L 3 are each independently a single bond; Phenylene unsubstituted or substituted with deuterium; Biphenylylene unsubstituted or substituted with deuterium; Terphenylylene unsubstituted or substituted with deuterium; Fluorenylene unsubstituted or substituted with deuterium; Or naphthylene unsubstituted or substituted with deuterium,
    화합물.compound.
  4. 제 1항에 있어서, The method of claim 1,
    L 1 내지 L 3는 각각 독립적으로, 단일 결합; 페닐렌; 비페닐릴렌 또는 나프틸렌인,L 1 to L 3 are each independently a single bond; Phenylene; Which is biphenylylene or naphthylene,
    화합물.compound.
  5. 제 1항에 있어서, The method of claim 1,
    Ar 1 및 Ar 2는 각각 독립적으로, 중수소; 아다만틸; 또는 하기로 구성되는 군으로부터 선택되는 어느 하나이며, 단, Ar 1 및 Ar 2 중 하나 이상은 아다만틸인, Ar 1 and Ar 2 are each independently deuterium; Adamantyl; Or any one selected from the group consisting of, provided that at least one of Ar 1 and Ar 2 is adamantyl,
    화합물:compound:
    Figure PCTKR2020014151-appb-img-000066
    Figure PCTKR2020014151-appb-img-000066
    상기에서, Above,
    X는 O; S 또는 NR이고,X is O; S or NR,
    R은 치환 또는 비치환된 C 6-12 아릴이고,R is substituted or unsubstituted C 6-12 aryl,
    R' 1 및 R' 2는 각각 독립적으로, 수소; 중수소; 치환 또는 비치환된 C 1-10 알킬; 또는 치환 또는 비치환된 C 6-12 아릴이다.R '1 and R' 2 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 1-10 alkyl; Or substituted or unsubstituted C 6-12 aryl.
  6. 제 1항에 있어서, The method of claim 1,
    R 1 및 R 2는 각각 독립적으로, 수소; 또는 중수소인,R 1 and R 2 are each independently hydrogen; Or deuterium,
    화합물.compound.
  7. 제1항에 있어서,The method of claim 1,
    상기 화학식 1로 표시되는 화합물은 하기로 구성되는 군으로부터 선택되는 어느 하나인,The compound represented by Formula 1 is any one selected from the group consisting of the following,
    화합물:compound:
    Figure PCTKR2020014151-appb-img-000067
    Figure PCTKR2020014151-appb-img-000067
    Figure PCTKR2020014151-appb-img-000068
    Figure PCTKR2020014151-appb-img-000068
    Figure PCTKR2020014151-appb-img-000069
    Figure PCTKR2020014151-appb-img-000069
    Figure PCTKR2020014151-appb-img-000070
    Figure PCTKR2020014151-appb-img-000070
    Figure PCTKR2020014151-appb-img-000071
    Figure PCTKR2020014151-appb-img-000071
    Figure PCTKR2020014151-appb-img-000072
    Figure PCTKR2020014151-appb-img-000072
    Figure PCTKR2020014151-appb-img-000073
    Figure PCTKR2020014151-appb-img-000073
    Figure PCTKR2020014151-appb-img-000074
    Figure PCTKR2020014151-appb-img-000074
    Figure PCTKR2020014151-appb-img-000075
    Figure PCTKR2020014151-appb-img-000075
    Figure PCTKR2020014151-appb-img-000076
    Figure PCTKR2020014151-appb-img-000076
    Figure PCTKR2020014151-appb-img-000077
    Figure PCTKR2020014151-appb-img-000077
    Figure PCTKR2020014151-appb-img-000078
    Figure PCTKR2020014151-appb-img-000078
    Figure PCTKR2020014151-appb-img-000079
    Figure PCTKR2020014151-appb-img-000079
    Figure PCTKR2020014151-appb-img-000080
    Figure PCTKR2020014151-appb-img-000080
    Figure PCTKR2020014151-appb-img-000081
    Figure PCTKR2020014151-appb-img-000081
    Figure PCTKR2020014151-appb-img-000082
    Figure PCTKR2020014151-appb-img-000082
    Figure PCTKR2020014151-appb-img-000083
    Figure PCTKR2020014151-appb-img-000083
    Figure PCTKR2020014151-appb-img-000084
    Figure PCTKR2020014151-appb-img-000084
    Figure PCTKR2020014151-appb-img-000085
    Figure PCTKR2020014151-appb-img-000085
    Figure PCTKR2020014151-appb-img-000086
    Figure PCTKR2020014151-appb-img-000086
    Figure PCTKR2020014151-appb-img-000087
    Figure PCTKR2020014151-appb-img-000087
    Figure PCTKR2020014151-appb-img-000088
    .
    Figure PCTKR2020014151-appb-img-000088
    .
    Figure PCTKR2020014151-appb-img-000089
    Figure PCTKR2020014151-appb-img-000089
    Figure PCTKR2020014151-appb-img-000090
    Figure PCTKR2020014151-appb-img-000090
    Figure PCTKR2020014151-appb-img-000091
    .
    Figure PCTKR2020014151-appb-img-000091
    .
    Figure PCTKR2020014151-appb-img-000092
    Figure PCTKR2020014151-appb-img-000092
    Figure PCTKR2020014151-appb-img-000093
    Figure PCTKR2020014151-appb-img-000093
    Figure PCTKR2020014151-appb-img-000094
    Figure PCTKR2020014151-appb-img-000094
    Figure PCTKR2020014151-appb-img-000095
    Figure PCTKR2020014151-appb-img-000095
    Figure PCTKR2020014151-appb-img-000096
    Figure PCTKR2020014151-appb-img-000096
    ..
  8. 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 제 1항 내지 제 7항 중 어느 하나의 항에 따른 화합물을 포함하는 것인, 유기 발광 소자. 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 of the organic material layers includes the compound according to any one of claims 1 to 7 That is, an organic light-emitting device.
  9. 제 8항에 있어서, The method of claim 8,
    상기 화합물을 포함하는 유기물층은 정공저지층인,The organic material layer containing the compound is a hole blocking layer,
    유기 발광 소자.Organic light emitting device.
PCT/KR2020/014151 2019-10-21 2020-10-16 Novel compound and organic light emitting device comprising same WO2021080254A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202080053544.8A CN114174287B (en) 2019-10-21 2020-10-16 Compound and organic light emitting device comprising the same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2019-0130848 2019-10-21
KR20190130848 2019-10-21
KR10-2020-0131020 2020-10-12
KR1020200131020A KR102397832B1 (en) 2019-10-21 2020-10-12 Novel compound and organic light emitting device comprising the same

Publications (1)

Publication Number Publication Date
WO2021080254A1 true WO2021080254A1 (en) 2021-04-29

Family

ID=75620784

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2020/014151 WO2021080254A1 (en) 2019-10-21 2020-10-16 Novel compound and organic light emitting device comprising same

Country Status (2)

Country Link
CN (1) CN114174287B (en)
WO (1) WO2021080254A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110746429B (en) * 2018-12-10 2022-11-25 广州华睿光电材料有限公司 Adamantane-containing compound, polymer, mixture, composition, and electronic device
CN115477939A (en) * 2022-09-28 2022-12-16 京东方科技集团股份有限公司 Organic electroluminescent composition, organic electroluminescent device, and display device comprising the same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018207750A1 (en) * 2017-05-08 2018-11-15 国立大学法人京都大学 Compound, light emitting material and organic light emitting element
KR20190003389A (en) * 2017-06-30 2019-01-09 주식회사 엘지화학 Novel hetero-cyclic compound and organic light emitting device comprising the same
CN109748909A (en) * 2017-11-02 2019-05-14 江苏三月光电科技有限公司 The compound of a kind of fluorenes of xanthene containing spiral shell and nitrogenous hexa-member heterocycle, preparation method and its application in organic electroluminescence device
KR101987256B1 (en) * 2018-12-14 2019-06-10 주식회사 엘지화학 Condensed compound and organic light emitting device comprising the same
CN110028459A (en) * 2019-05-24 2019-07-19 上海天马有机发光显示技术有限公司 Compound, display panel and display device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018207750A1 (en) * 2017-05-08 2018-11-15 国立大学法人京都大学 Compound, light emitting material and organic light emitting element
KR20190003389A (en) * 2017-06-30 2019-01-09 주식회사 엘지화학 Novel hetero-cyclic compound and organic light emitting device comprising the same
CN109748909A (en) * 2017-11-02 2019-05-14 江苏三月光电科技有限公司 The compound of a kind of fluorenes of xanthene containing spiral shell and nitrogenous hexa-member heterocycle, preparation method and its application in organic electroluminescence device
KR101987256B1 (en) * 2018-12-14 2019-06-10 주식회사 엘지화학 Condensed compound and organic light emitting device comprising the same
CN110028459A (en) * 2019-05-24 2019-07-19 上海天马有机发光显示技术有限公司 Compound, display panel and display device

Also Published As

Publication number Publication date
CN114174287A (en) 2022-03-11
CN114174287B (en) 2024-04-16

Similar Documents

Publication Publication Date Title
WO2020262861A1 (en) Novel compound and organic light emitting device comprising same
WO2021125648A1 (en) Novel compound, and organic light-emitting element using same
WO2015152651A1 (en) Heterocyclic compound and organic light-emitting element comprising same
WO2020149596A1 (en) Novel compound and organic light emitting diode using same
WO2022102992A1 (en) Novel compound and organic light-emitting device using same
WO2021080254A1 (en) Novel compound and organic light emitting device comprising same
WO2021080253A1 (en) Novel compound and organic light emitting device comprising same
WO2021066351A1 (en) Novel compound and organic light-emitting device using same
WO2015178740A2 (en) Heterocyclic compound and organic light emitting device comprising same
WO2020185038A1 (en) Novel compound and organic light emitting device using same
WO2022235101A1 (en) Organic light emitting device
WO2022031013A1 (en) Novel compound and organic light-emitting device comprising same
WO2022031016A1 (en) Novel compound and organic light-emitting device using same
WO2022059923A1 (en) Novel compound and organic light-emitting device comprising same
WO2022031028A1 (en) Novel compound and organic light emitting device using same
WO2022031020A1 (en) Novel compound and organic light emitting device comprising same
WO2021149954A1 (en) Organic light emitting device
WO2021040467A1 (en) Novel heterocyclic compound and organic light-emitting device using same
WO2021066350A1 (en) Novel compound and organic light emitting device using same
WO2020246835A1 (en) Novel compound and organic light-emitting device using same
WO2020185054A9 (en) Novel compound and organic light emitting device using same
WO2023121209A1 (en) Novel compound and organic light-emitting device using same
WO2024117767A1 (en) Novel compound and organic light emitting device comprising same
WO2023055177A1 (en) Novel compound and organic light-emitting device comprising same
WO2024043698A1 (en) Novel compound and organic light-emitting device comprising same

Legal Events

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

Ref document number: 20878656

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20878656

Country of ref document: EP

Kind code of ref document: A1