WO2022250386A1 - Organic light-emitting device - Google Patents

Organic light-emitting device Download PDF

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WO2022250386A1
WO2022250386A1 PCT/KR2022/007243 KR2022007243W WO2022250386A1 WO 2022250386 A1 WO2022250386 A1 WO 2022250386A1 KR 2022007243 W KR2022007243 W KR 2022007243W WO 2022250386 A1 WO2022250386 A1 WO 2022250386A1
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formula
group
comparative example
organic light
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French (fr)
Korean (ko)
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허동욱
홍성길
한미연
이재탁
윤정민
윤희경
박호윤
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주식회사 엘지화학
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Priority to CN202280014856.7A priority Critical patent/CN116965179A/en
Publication of WO2022250386A1 publication Critical patent/WO2022250386A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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
    • 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
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/653—Aromatic compounds comprising a hetero atom comprising only oxygen as heteroatom
    • 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
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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 an organic light emitting device.
  • the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material.
  • An organic light emitting device using an organic light emitting phenomenon has a wide viewing angle, excellent contrast, and a 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, a cathode, and an organic material layer between the anode and the cathode.
  • the organic material layer is often composed of a multi-layered structure composed of different materials, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.
  • 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 when the injected holes and electrons meet, excitons are formed. When it falls back to the ground state, it glows.
  • Patent Document 0001 Korean Patent Publication No. 10-2000-0051826
  • Patent Document 0002 US Patent Publication No. 2007-0196692
  • Patent Document 0003 Korean Patent Publication No. 10-2017-0048159
  • Patent Document 0004 US Patent Registration No. 6821643
  • the present invention relates to an organic light emitting device.
  • the present invention provides the following organic light emitting device.
  • an electron transport layer an electron injection layer, or an electron transport and injection layer
  • the hole blocking layer includes a compound represented by Formula 1 below,
  • the electron transport layer, the electron injection layer, or the electron transport and injection layer comprises a compound represented by Formula 2 or 3 below,
  • X 1 to X 3 are each independently N or CH, but at least one or more of X 1 to X 3 is N;
  • L 1 to L 3 are each independently a direct bond; or a substituted or unsubstituted C 6-60 arylene;
  • Ar 1 and Ar 2 are each independently a substituted or unsubstituted C 6-60 aryl;
  • Ar 3 is a substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O, and S,
  • R 1 to R 4 are each independently hydrogen or deuterium
  • n1 to n4 are integers from 1 to 4;
  • L 4 and L 5 are each independently a direct bond; or a substituted or unsubstituted C 6-60 arylene;
  • Ar 4 and Ar 5 are each independently a substituent represented by Formula 4 below;
  • X 4 to X 8 are each independently N or C (R 5 ), but at least two or more of X 4 to X 8 are N;
  • R 5 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 1-20 Alkyl; Substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S, or two adjacent R 5 of them bond to form a benzene ring.
  • the organic light emitting device by controlling the compounds included in the light emitting layer and the electron transport layer, the organic light emitting device may improve efficiency, low driving voltage, and/or lifespan characteristics.
  • FIG. 1 shows an example of an organic light emitting device composed of a substrate 1, an anode 2, a light emitting layer 3, a hole blocking layer 4, an electron transport and injection layer 5, and a cathode 6.
  • FIG. 2 shows a substrate 1, an anode 2, a hole injection layer 7, a hole transport layer 8, an electron blocking layer 9, a light emitting layer 3, a hole blocking layer 4, and an electron transport and injection layer.
  • substituted or unsubstituted means deuterium; 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; an alkyl sulfoxy group; aryl sulfoxy groups; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; Aralkenyl group; Alkyl aryl group; Alkylamine group; Aralkylamine group; heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing at least one of N, O, and S atoms, or substituted or unsub
  • a substituent in which two or more substituents are connected may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in 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 an aryl group having 6 to 25 carbon atoms or a straight-chain, branched-chain or cyclic chain alkyl group having 1 to 25 carbon atoms in 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 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 a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. but not limited to
  • 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, but is not limited thereto.
  • examples of the halogen group include fluorine, chlorine, bromine or iodine.
  • the alkyl group may be straight-chain or branched-chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the number of carbon atoms of the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 10. 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, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl
  • the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one 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, etc., but is 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 number of carbon atoms of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 6.
  • the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 30. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 20.
  • the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc. as a monocyclic aryl group, but is not limited thereto.
  • the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, 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, etc.
  • it is not limited thereto.
  • the heterocyclic group is a heterocyclic group containing at least one of O, N, Si, and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but preferably has 2 to 60 carbon atoms.
  • the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, and an acridyl group.
  • pyridazine group pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinoline group, indole group , carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia A zolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.
  • an aralkyl group, an aralkenyl group, an alkylaryl group, and an aryl group among arylamine groups are the same as the examples 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 examples of the above-mentioned alkyl group.
  • the description of the heterocyclic group described above may be applied to the heteroaryl of the heteroarylamine.
  • the alkenyl group among the aralkenyl groups is the same as the examples 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 heterocyclic group described above 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 combining two substituents.
  • the heterocyclic group is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that it is formed by combining two substituents.
  • the present invention is a positive electrode; hole transport layer; light emitting layer; an electron transport layer, an electron injection layer, or an electron transport and injection layer; and a cathode, wherein the light emitting layer includes the compound represented by Formula 1, and the electron transport layer, the electron injection layer, or the electron transport and injection layer is selected from among the compound represented by Formula 2 and the compound represented by Formula 3. It provides an organic light-emitting device including any one or more.
  • the organic light emitting device adjusts the compound included in the light emitting layer and the electron transport layer, the electron injection layer, or the electron transport and injection layer to improve efficiency, lower driving voltage and/or lifetime in the organic light emitting device. characteristics can be improved.
  • the cathode material a material having a high work function is generally preferred so that holes can be smoothly injected into the organic 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; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.
  • the cathode material is preferably a material having a small work function so as to easily inject electrons into the organic material layer.
  • Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO 2 /Al, but are not limited thereto.
  • the organic light emitting device may include a hole injection layer between the anode and the hole transport layer, if necessary.
  • the hole injection layer is a layer for injecting holes from the electrode, and the hole injection material has the ability to transport holes and has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and generated in the light emitting layer A compound that prevents migration of excitons to the electron injecting layer or electron injecting material and has excellent thin film formation ability is preferred.
  • the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer.
  • the hole injection material include metal porphyrins, oligothiophenes, arylamine-based organic materials, hexanitrilehexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene-based organic materials. of organic materials, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.
  • the hole transport layer used in the present invention is a layer that receives holes from an anode or a hole injection layer formed on the anode and transports the holes to the light emitting layer, and can transport holes from the anode or the hole injection layer to the light emitting layer as a hole transport material.
  • a material having high hole mobility is suitable. Specific examples include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated parts.
  • the organic light emitting device may include an electron blocking layer between the hole transport layer and the light emitting layer, if necessary.
  • the electron blocking layer is formed on the hole transport layer, and is preferably provided in contact with the light emitting layer to control hole mobility and prevent excessive movement of electrons to increase hole-electron coupling probability, thereby increasing the efficiency of the organic light emitting device.
  • the electron suppression layer includes an electron suppression material, and an example of such an electron suppression material may be an arylamine-based organic material, but is not limited thereto.
  • the light emitting material included in the light emitting layer is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable.
  • Specific examples include 8-hydroxy-quinoline aluminum complex (Alq 3 ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; Polyfluorene, rubrene, etc., but are not limited thereto.
  • the light emitting layer may include a host material and a dopant material.
  • the host material includes a condensed aromatic ring derivative or a compound containing a hetero ring.
  • condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc.
  • heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type furan compounds, pyrimidine derivatives, etc., but are not limited thereto.
  • Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like.
  • aromatic amine derivatives are condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, periplanthene, etc.
  • styrylamine compounds include substituted or unsubstituted arylamine is substituted with at least one arylvinyl group, wherein one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group are substituted or unsubstituted.
  • substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group are substituted or unsubstituted.
  • metal complexes include, but are not limited to, iridium complexes and platinum complexes.
  • the organic light emitting device includes a hole blocking layer between the light emitting layer, an electron transport layer, an electron injection layer, or an electron transport and injection layer, as necessary.
  • the hole blocking layer is in contact with the light emitting layer.
  • the hole blocking layer serves to improve the efficiency of the organic light emitting device by suppressing the transfer of holes injected from the anode to the cathode without recombination in the light emitting layer.
  • the compound represented by Formula 1 is used as a material constituting the hole blocking layer.
  • L 1 and L 2 are each independently a direct bond or phenylene;
  • L 3 is a direct key, phenylene, biphenyldiyl, or terphenyldiyl.
  • Ar 1 and Ar 2 are each independently phenyl, biphenylyl, or naphthyl.
  • Ar 3 is any one of substituents represented by Formulas 1-1 to 1-7 below:
  • R 6 and R 7 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 1-10 Alkyl; or a substituted or unsubstituted C 6-60 aryl; Z is each independently NR 9 , O, or S; R 8 and R 9 are each independently a substituted or unsubstituted C 6-60 aryl.
  • R 6 and R 7 are each independently hydrogen, deuterium, methyl, or substituted or unsubstituted phenyl; R 8 and R 9 are phenyl.
  • Ar 3 is any one selected from the group consisting of:
  • the present invention provides a method for preparing the compound represented by Formula 1, as shown in Reaction Scheme 1 below.
  • X 1 to X 3 , L 1 to L 3 , and Ar 1 to Ar 3 are as defined above, and Z is halogen, preferably bromo or chloro.
  • the manufacturing method may be more specific in Preparation Examples to be described later.
  • electron transport layer electron injection layer, or electron transport and injection layer
  • the organic light emitting device may include an electron transport layer, an electron injection layer, or an electron transport and injection layer between the light emitting layer and the cathode.
  • the electron transport layer is a layer that receives electrons from the cathode or an electron injection layer formed on the cathode, transports electrons to the light emitting layer, and suppresses the transfer of holes in the light emitting layer.
  • an electron transport material electrons are well injected from the cathode.
  • the present invention may include at least one of the compound represented by Chemical Formula 2 and the compound represented by Chemical Formula 3.
  • the electron injection layer is a layer for injecting electrons from an electrode, has an ability to transport electrons, has an excellent electron injection effect from a cathode, a light emitting layer or a light emitting material, and has a hole of excitons generated in the light emitting layer.
  • the present invention may include at least one of the compound represented by Chemical Formula 2 and the compound represented by Chemical Formula 3.
  • the electron transport and injection layer is a layer that simultaneously transports and injects electrons, and may include the compound represented by Chemical Formula 2 or 3.
  • Formula 2 is represented by Formula 2-1 below;
  • Formula 3 is represented by Formula 3-1 below.
  • L 4 , L 5 , Ar 4 and Ar 5 are as defined above.
  • L 4 and L 5 are each independently a direct bond, phenylene, or biphenyldiyl.
  • Ar 4 and Ar 5 are each independently any one selected from the group consisting of:
  • R 5 is as defined above.
  • each R 5 is independently hydrogen, deuterium, methyl, tert-butyl, phenyl, biphenylyl, terphenylyl, naphthyl, pyridinyl, furanyl, or thiophenyl, or two adjacent ones thereof R 5 is bonded to form a benzene ring;
  • the phenyl, biphenylyl, terphenylyl, naphthyl, pyridinyl, furanyl, or thiophenyl are each independently unsubstituted or substituted with deuterium, methyl, or tert-butyl.
  • Ar 4 and Ar 5 are each independently any one selected from the group consisting of:
  • the present invention provides a method for producing a compound represented by Formula 2 or 3, as shown in Schemes 2 to 5 below.
  • L 4 , L 5 , Ar 4 , Ar 5 , R 1 to R 4 , and n1 to n4 are as defined above, and Z is halogen, preferably bromo or chloro.
  • the electron transport layer may further include a metal complex compound.
  • the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato) aluminum, tris(2-methyl-8-hydroxyquinolinato) aluminum, tris(8-hydroxyquinolinato) gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( There are o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium. Not limited to this.
  • the electron injection layer may further include a metal complex compound.
  • the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato) aluminum, tris(2-methyl-8-hydroxyquinolinato) aluminum, tris(8-hydroxyquinolinato) gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( There are o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium. Not limited to this.
  • FIG. 1 shows an example of an organic light emitting device composed of a substrate 1, an anode 2, a light emitting layer 3, a hole blocking layer 4, an electron transport and injection layer 5 and a cathode 6 .
  • FIG. 2 shows a substrate 1, an anode 2, a hole injection layer 7, a hole transport layer 8, an electron blocking layer 9, a light emitting layer 3, a hole blocking layer 4, electron transport and
  • An example of an organic light emitting device composed of an injection layer 5 and a cathode 6 is shown.
  • the organic light emitting device according to the present invention can be manufactured by sequentially stacking the above-described components. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, depositing a metal or a metal oxide having conductivity or an alloy thereof on the substrate to form an anode And, after forming each of the above-mentioned layers thereon, it can be manufactured by depositing a material that can be used as a cathode thereon.
  • PVD physical vapor deposition
  • an organic light emitting device may be manufactured by sequentially depositing a cathode material on a substrate and an anode material in the reverse order of the above configuration (WO 2003/012890).
  • the light emitting layer may be formed by a solution coating method as well as a vacuum deposition method of a host and a dopant.
  • the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.
  • the organic light emitting device according to the present invention may be a bottom emission device, a top emission device, or a double-sided light emitting device, and in particular, may be a bottom emission device requiring relatively high light emitting efficiency.
  • B1-A (20 g, 43.1 mmol) and B1-B (10.3 g, 43.1 mmol) were added to 400 ml of tetrahydrofuran, stirred and refluxed. Thereafter, potassium carbonate (17.9 g, 129.2 mmol) was dissolved in 18 ml of water, and after stirring sufficiently, tetrakistriphenyl-phosphinopalladium (1.5 g, 1.3 mmol) was added. After reacting for 3 hours, cooling to room temperature, separating the organic layer and the water layer, and distilling the organic layer.
  • Compound B2 was prepared in the same manner as in Preparation Example 1-1, except for using each starting material as in the reaction scheme.
  • Compound B3 was prepared in the same manner as in Preparation Example 1-1, except for using each starting material as in the above reaction scheme.
  • Compound B4 was prepared in the same manner as in Preparation Example 1-1, except for using each starting material as in the above reaction scheme.
  • Compound B5 was prepared in the same manner as in Preparation Example 1-1, except for using each starting material as in the above reaction scheme.
  • Compound B6 was prepared in the same manner as in Preparation Example 1-1, except for using each starting material as in the above reaction scheme.
  • Compound B7 was prepared in the same manner as in Preparation Example 1-1, except for using each starting material as in the above reaction scheme.
  • B8-A (20 g, 43.1 mmol) and B8-B (15.4 g, 43.1 mmol) were added to 400 ml of xylene, stirred and refluxed. Thereafter, sodium tert-butoxide (12.4 g, 129.2 mmol) was added, and after stirring sufficiently, bis(tri tert-butylphosphine)palladium (0.7 g, 1.3 mmol) was added. After reacting for 1 hour, cooled to room temperature, the organic layer was filtered to remove salts, and the filtered organic layer was distilled.
  • E1-A (20 g, 64.1 mmol) and E1-B (55.8 g, 128.2 mmol) were added to tetrahydrofuran (400 ml), stirred and refluxed. Thereafter, potassium carbonate (26.6 g, 192.3 mmol) was dissolved in water (27 ml), and after stirring sufficiently, tetrakistriphenyl-phosphinopalladium (2.2 g, 1.9 mmol) was added. After reacting for 1 hour, cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled.
  • Compound E2 was prepared in the same manner as in Preparation Example 2-1, except for using each starting material as in the above reaction scheme.
  • Compound E4 was prepared in the same manner as in Preparation Example 2-1, except for using each starting material as in the above reaction scheme.
  • Compound E5 was prepared in the same manner as in Preparation Example 2-1, except for using each starting material as in the above reaction scheme.
  • E8-A (20 g, 47.6 mmol) and E8-B (28 g, 47.6 mmol) were added to 1,4-Dioxane (400 ml), stirred and refluxed. Thereafter, potassium triphosphate (30.3 g, 142.9 mmol) was dissolved in water (30 ml), added, stirred sufficiently, dibenzylideneacetone palladium (0.8 g, 1.4 mmol) and tricyclohexylphosphine (0.8 g, 2.9 g). mmol) was added. After reacting for 5 hours, the resulting solid was filtered after cooling to room temperature.
  • Compound E9 was prepared in the same manner as in Preparation Examples 2-8, except for using each starting material as in the above reaction scheme.
  • Compound E10 was prepared in the same manner as in Preparation Examples 2-8, except for using each starting material as in the reaction scheme.
  • Compound E12 was prepared in the same manner as in Preparation Example 2-1, except for using each starting material as in the reaction scheme.
  • Compound E15 was prepared in the same manner as in Preparation Example 2-1, except for using each starting material as in the above reaction scheme.
  • Compound E16 was prepared in the same manner as in Preparation Examples 2-8, except for using each starting material as in the reaction scheme.
  • Compound E17 was prepared in the same manner as in Preparation Examples 2-8, except for using each starting material as in the above reaction scheme.
  • Compound E18 was prepared in the same manner as in Preparation Examples 2-8, except for using each starting material as in the above reaction scheme.
  • Compound E19 was prepared in the same manner as in Preparation Example 2-1, except for using each starting material as in the reaction scheme.
  • Compound E20 was prepared in the same manner as in Preparation Example 2-1, except for using each starting material as in the reaction scheme.
  • a glass substrate coated with indium tin oxide (ITO) to a thickness of 1,000 ⁇ was put in distilled water in which detergent was dissolved and washed with ultrasonic waves.
  • ITO indium tin oxide
  • a Fischer Co. product was used as the detergent
  • distilled water filtered through a second filter of a Millipore Co. product was used as the distilled water.
  • ultrasonic cleaning was performed twice with distilled water for 10 minutes.
  • ultrasonic cleaning was performed with solvents such as isopropyl alcohol, acetone, and methanol, dried, and transported to a plasma cleaner.
  • solvents such as isopropyl alcohol, acetone, and methanol
  • a hole injection layer was formed by thermally vacuum depositing the following compound HI-A to a thickness of 600 ⁇ on the prepared ITO transparent electrode.
  • a hole transport layer was formed by sequentially vacuum depositing hexanitrile hexaazatriphenylene (HAT, 50 ⁇ ) and the compound HT-A (600 ⁇ ) of the following chemical formula on the hole injection layer.
  • the following compounds BH and BD were vacuum deposited at a weight ratio of 25:1 to a film thickness of 200 ⁇ on the hole transport layer to form a light emitting layer.
  • the compound B1 was thermally vacuum deposited on the light emitting layer to a thickness of 50 ⁇ to form a hole blocking layer.
  • the compound E1 and the following compound [LiQ] (Lithiumquinolate) were vacuum deposited in a weight ratio of 1:1 to form an electron transport and injection layer with a thickness of 300 ⁇ .
  • a negative electrode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 10 ⁇ and aluminum to a thickness of 1,000 ⁇ on the electron transport and injection layer.
  • the deposition rate of the organic material was maintained at 0.4 ⁇ 0.9 ⁇ /sec
  • the deposition rate of lithium fluoride on the anode was 0.3 ⁇ /sec
  • the deposition rate of aluminum was 2 ⁇ /sec
  • the vacuum level during deposition was 1 ⁇ 10 Maintaining -7 to 5 ⁇ 10 -8 torr, an organic light emitting device was fabricated.
  • An organic light emitting device was manufactured in the same manner as in Example 1, except that the compounds of Table 1 were used instead of Compound B1 or Compound E1.
  • the compounds of ET-1 to ET-19 used in Table 1 are as follows.
  • the compound represented by Chemical Formula 1 of the present invention may be used in an organic material layer corresponding to a hole blocking layer of an organic light emitting device.
  • the compound represented by Chemical Formula 2 or Chemical Formula 3 of the present invention may be used in an organic material layer capable of simultaneously transporting and injecting electrons in an organic light emitting device.
  • the organic light emitting device including the compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 or 3 of the present invention is represented by Chemical Formula 2 , or 3, it was confirmed that the organic light emitting diode does not contain a heterocyclic compound, showing significantly better characteristics in terms of efficiency and lifespan.
  • substrate 2 anode
  • hole injection layer 8 hole transport layer

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Abstract

The present invention provides an organic light-emitting device.

Description

유기 발광 소자organic light emitting device
관련 출원(들)과의 상호 인용Cross-citation with related application(s)
본 출원은 2021년 5월 25일자 한국 특허 출원 제10-2021-0067128호에 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. 10-2021-0067128 dated May 25, 2021, and all contents disclosed in the literature of the Korean patent applications are included as part of this specification.
본 발명은 유기 발광 소자에 관한 것이다.The present invention relates to an organic light emitting device.
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 emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon has a wide viewing angle, excellent contrast, and a 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 유기물층을 포함하는 구조를 가진다. 상기 유기물층은 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, a cathode, and an organic material layer between the anode and the cathode. In order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often composed of a multi-layered structure composed of different materials, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. In the structure of this 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 when the injected holes and electrons meet, excitons are formed. When it falls back to the ground state, it glows.
상기와 같은 유기 발광 소자에 사용되는 유기물에 대하여 새로운 재료의 개발이 지속적으로 요구되고 있다.The development of new materials for organic materials used in the organic light emitting device as described above is continuously required.
선행기술문헌Prior art literature
특허문헌Patent literature
(특허문헌 0001) 한국특허 공개번호 제10-2000-0051826호(Patent Document 0001) Korean Patent Publication No. 10-2000-0051826
(특허문헌 0002) 미국특허 공개번호 제2007-0196692호(Patent Document 0002) US Patent Publication No. 2007-0196692
(특허문헌 0003) 한국특허 공개번호 제10-2017-0048159호(Patent Document 0003) Korean Patent Publication No. 10-2017-0048159
(특허문헌 0004) 미국특허 등록번호 제6821643호(Patent Document 0004) US Patent Registration No. 6821643
본 발명은 유기 발광 소자에 관한 것이다. The present invention relates to an organic light emitting device.
본 발명은 하기의 유기 발광 소자를 제공한다.The present invention provides the following organic light emitting device.
양극;anode;
발광층;light emitting layer;
정공차단층;hole blocking layer;
전자수송층, 전자주입층, 또는 전자수송 및 주입층; 및an electron transport layer, an electron injection layer, or an electron transport and injection layer; and
음극을 포함하고,contains a cathode,
상기 정공차단층은 하기 화학식 1로 표시되는 화합물을 포함하고,The hole blocking layer includes a compound represented by Formula 1 below,
상기 전자수송층, 전자주입층, 또는 전자수송 및 주입층은 하기 화학식 2 또는 3으로 표시되는 화합물을 포함하는,The electron transport layer, the electron injection layer, or the electron transport and injection layer comprises a compound represented by Formula 2 or 3 below,
유기 발광 소자:Organic Light-Emitting Elements:
[화학식 1][Formula 1]
Figure PCTKR2022007243-appb-img-000001
Figure PCTKR2022007243-appb-img-000001
상기 화학식 1에서,In Formula 1,
X1 내지 X3는 각각 독립적으로, N 또는 CH이되, X1 내지 X3 중 적어도 하나 이상은 N이고,X 1 to X 3 are each independently N or CH, but at least one or more of X 1 to X 3 is N;
L1 내지 L3는 각각 독립적으로, 직접 결합; 또는 치환 또는 비치환된 C6-60 아릴렌이고,L 1 to L 3 are each independently a direct bond; or a substituted or unsubstituted C 6-60 arylene;
Ar1 및 Ar2는 각각 독립적으로, 치환 또는 비치환된 C6-60 아릴이고,Ar 1 and Ar 2 are each independently a substituted or unsubstituted C 6-60 aryl;
Ar3는 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O, 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴이고,Ar 3 is a substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O, and S,
[화학식 2][Formula 2]
Figure PCTKR2022007243-appb-img-000002
Figure PCTKR2022007243-appb-img-000002
[화학식 3][Formula 3]
Figure PCTKR2022007243-appb-img-000003
Figure PCTKR2022007243-appb-img-000003
상기 화학식 2, 또는 화학식 3에서,In Formula 2 or Formula 3,
R1 내지 R4는 각각 독립적으로, 수소, 또는 중수소이고, R 1 to R 4 are each independently hydrogen or deuterium;
n1 내지 n4는 1 내지 4의 정수이고,n1 to n4 are integers from 1 to 4;
L4 및 L5는 각각 독립적으로, 직접 결합; 또는 치환 또는 비치환된 C6-60 아릴렌이고,L 4 and L 5 are each independently a direct bond; or a substituted or unsubstituted C 6-60 arylene;
Ar4 및 Ar5는 각각 독립적으로, 하기 화학식 4로 표시되는 치환기이고,Ar 4 and Ar 5 are each independently a substituent represented by Formula 4 below;
[화학식 4][Formula 4]
Figure PCTKR2022007243-appb-img-000004
Figure PCTKR2022007243-appb-img-000004
상기 화학식 4에서,In Formula 4,
X4 내지 X8은 각각 독립적으로, N 또는 C(R5)이되, X4 내지 X8 중 적어도 둘 이상은 N이고,X 4 to X 8 are each independently N or C (R 5 ), but at least two or more of X 4 to X 8 are N;
R5는 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 C1-20 알킬; 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴이거나, 이들 중 인접한 2개의 R5가 결합하여 벤젠 고리를 형성한다.R 5 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 1-20 Alkyl; Substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S, or two adjacent R 5 of them bond to form a benzene ring.
상술한 유기 발광 소자는 발광층과 전자수송층에 포함되는 화합물을 조절하여, 유기 발광 소자에서 효율의 향상, 낮은 구동전압 및/또는 수명 특성을 향상시킬 수 있다.In the organic light emitting device described above, by controlling the compounds included in the light emitting layer and the electron transport layer, the organic light emitting device may improve efficiency, low driving voltage, and/or lifespan characteristics.
도 1은 기판(1), 양극(2), 발광층(3), 정공차단층(4), 전자수송 및 주입층(5) 및 음극(6)으로 이루어진 유기 발광 소자의 예를 도시한 것이다.1 shows an example of an organic light emitting device composed of a substrate 1, an anode 2, a light emitting layer 3, a hole blocking layer 4, an electron transport and injection layer 5, and a cathode 6.
도 2는 기판(1), 양극(2), 정공주입층(7), 정공수송층(8), 전자억제층(9), 발광층(3), 정공차단층(4), 전자수송 및 주입층(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 8, an electron blocking layer 9, a light emitting layer 3, a hole blocking layer 4, and an electron transport and injection layer. (5) and an example of an organic light emitting element composed of a cathode (6) is shown.
이하, 본 발명의 이해를 돕기 위하여 보다 상세히 설명한다.Hereinafter, in order to aid understanding of the present invention, it will be described in more detail.
본 명세서에서,
Figure PCTKR2022007243-appb-img-000005
또는
Figure PCTKR2022007243-appb-img-000006
는 다른 치환기에 연결되는 결합을 의미한다. In this specification,
Figure PCTKR2022007243-appb-img-000005
or
Figure PCTKR2022007243-appb-img-000006
means a bond connected to another substituent.
본 명세서에서 "치환 또는 비치환된" 이라는 용어는 중수소; 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 this specification, the term "substituted or unsubstituted" means deuterium; 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; an alkyl sulfoxy group; aryl sulfoxy groups; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; Aralkenyl group; Alkyl aryl group; Alkylamine group; Aralkylamine group; heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing at least one of N, O, and S atoms, or substituted or unsubstituted with two or more substituents linked to each other among the substituents exemplified above. . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in 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 PCTKR2022007243-appb-img-000007
Figure PCTKR2022007243-appb-img-000007
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 an aryl group having 6 to 25 carbon atoms or a straight-chain, branched-chain or cyclic chain alkyl group having 1 to 25 carbon atoms in the ester group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.
Figure PCTKR2022007243-appb-img-000008
Figure PCTKR2022007243-appb-img-000008
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 is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.
Figure PCTKR2022007243-appb-img-000009
Figure PCTKR2022007243-appb-img-000009
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 a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. but not limited to
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, but is not limited thereto.
본 명세서에 있어서, 할로겐기의 예로는 불소, 염소, 브롬 또는 요오드가 있다.In this 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 straight-chain or branched-chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the number of carbon atoms of the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 10. 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, cyclohexylmethyl, 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, etc., but is 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 linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one 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, etc., but is 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 number of carbon atoms of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 6. 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 preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 30. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 20. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc. as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, 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 PCTKR2022007243-appb-img-000010
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 PCTKR2022007243-appb-img-000010
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), 이소옥사졸릴기, 티아디아졸릴기, 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 heterogeneous elements, and the number of carbon atoms is not particularly limited, but preferably has 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, and an acridyl group. , pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinoline group, indole group , carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia A zolyl group, a phenothiazinyl group, and a dibenzofuranyl group, 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, an aralkyl group, an aralkenyl group, an alkylaryl group, and an aryl group among arylamine groups are the same as the examples 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 examples of the above-mentioned alkyl group. In the present specification, the description of the heterocyclic group described above may be applied to the heteroaryl of the heteroarylamine. In the present specification, the alkenyl group among the aralkenyl groups is the same as the examples 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 heterocyclic group described above 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 combining two substituents. In the present specification, the heterocyclic group is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that it is formed by combining two substituents.
본 발명은 양극; 정공수송층; 발광층; 전자수송층, 전자주입층, 또는 전자수송 및 주입층; 및 음극을 포함하고, 상기 발광층은 상기 화학식 1로 표시되는 화합물을 포함하고, 상기 전자수송층, 전자주입층, 또는 전자수송 및 주입층은 상기 화학식 2로 표시되는 화합물 및 화학식 3으로 표시되는 화합물 중 어느 하나 이상을 포함하는, 유기 발광 소자를 제공한다.The present invention is a positive electrode; hole transport layer; light emitting layer; an electron transport layer, an electron injection layer, or an electron transport and injection layer; and a cathode, wherein the light emitting layer includes the compound represented by Formula 1, and the electron transport layer, the electron injection layer, or the electron transport and injection layer is selected from among the compound represented by Formula 2 and the compound represented by Formula 3. It provides an organic light-emitting device including any one or more.
본 발명에 따른 유기 발광 소자는 발광층에 포함되는 화합물과 전자수송층, 전자주입층, 또는 전자수송 및 주입층에 포함되는 화합물을 조절하여, 유기 발광 소자에서 효율의 향상, 낮은 구동전압 및/또는 수명 특성을 향상시킬 수 있다.The organic light emitting device according to the present invention adjusts the compound included in the light emitting layer and the electron transport layer, the electron injection layer, or the electron transport and injection layer to improve efficiency, lower driving voltage and/or lifetime in the organic light emitting device. characteristics can be improved.
이하 각 구성 별로 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail for each configuration.
양극 및 음극anode and cathode
상기 양극 물질로는 통상 유기물 층으로 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 SnO2:Sb와 같은 금속과 산화물의 조합; 폴리(3-메틸티오펜), 폴리[3,4-(에틸렌-1,2-디옥시)티오펜](PEDOT), 폴리피롤 및 폴리아닐린과 같은 전도성 고분자 등이 있으나, 이들에만 한정되는 것은 아니다. As the anode material, a material having a high work function is generally preferred so that holes can be smoothly injected into the organic 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; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.
상기 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 LiO2/Al과 같은 다층 구조 물질 등이 있으나, 이들에만 한정되는 것은 아니다.The cathode material is preferably a material having a small work function so as to easily inject electrons into the organic material layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO 2 /Al, but are not limited thereto.
정공주입층hole injection layer
본 발명에 따른 유기 발광 소자는 필요에 따라 양극과 정공수송층 사이에 정공주입층을 포함할 수 있다. The organic light emitting device according to the present invention may include a hole injection layer between the anode and the hole transport layer, if necessary.
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. The hole injection layer is a layer for injecting holes from the electrode, and the hole injection material has the ability to transport holes and has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and generated in the light emitting layer A compound that prevents migration of excitons to the electron injecting layer or electron injecting material and has excellent thin film formation ability is preferred.
정공 주입 물질의 HOMO(highest occupied molecular orbital)가 양극 물질의 일함수와 주변 유기물 층의 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 한정되는 것은 아니다. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include metal porphyrins, oligothiophenes, arylamine-based organic materials, hexanitrilehexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene-based organic materials. of organic materials, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.
정공수송층hole transport layer
본 발명에서 사용되는 정공수송층은 양극 또는 양극 상에 형성된 정공주입층으로부터 정공을 수취하여 발광층까지 정공을 수송하는 층으로, 정공 수송 물질로 양극이나 정공 주입층으로부터 정공을 수송받아 발광층으로 옮겨줄 수 있는 물질로 정공에 대한 이동성이 큰 물질이 적합하다. 구체적인 예로는 아릴아민 계열의 유기물, 전도성 고분자, 및 공액 부분과 비공액 부분이 함께 있는 블록 공중합체 등이 있으나, 이들에만 한정되는 것은 아니다.The hole transport layer used in the present invention is a layer that receives holes from an anode or a hole injection layer formed on the anode and transports the holes to the light emitting layer, and can transport holes from the anode or the hole injection layer to the light emitting layer as a hole transport material. A material having high hole mobility is suitable. Specific examples include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated parts.
전자억제층electron suppression layer
본 발명에 따른 유기 발광 소자는 필요에 따라 정공수송층과 발광층 사이에 전자억제층을 포함할 수 있다. 상기 전자억제층은 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 전자억제물질을 포함하고, 이러한 전자억제물질의 예로 아릴아민 계열의 유기물 등을 사용할 수 있으나, 이에 한정되는 것은 아니다.The organic light emitting device according to the present invention may include an electron blocking layer between the hole transport layer and the light emitting layer, if necessary. The electron blocking layer is formed on the hole transport layer, and is preferably provided in contact with the light emitting layer to control hole mobility and prevent excessive movement of electrons to increase hole-electron coupling probability, thereby increasing the efficiency of the organic light emitting device. means a layer that serves to improve The electron suppression layer includes an electron suppression material, and an example of such an electron suppression material may be an arylamine-based organic material, but is not limited thereto.
발광층light emitting layer
상기 발광층에 포함되는 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(Alq3); 카르바졸 계열 화합물; 이량체화 스티릴(dimerized styryl) 화합물; BAlq; 10-히드록시벤조 퀴놀린-금속 화합물; 벤족사졸, 벤즈티아졸 및 벤즈이미다졸 계열의 화합물; 폴리(p-페닐렌비닐렌)(PPV) 계열의 고분자; 스피로(spiro) 화합물; 폴리플루오렌, 루브렌 등이 있으나, 이들에만 한정되는 것은 아니다. The light emitting material included in the light emitting layer is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq 3 ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; Polyfluorene, rubrene, etc., but are not limited thereto.
상기 발광층은 호스트 재료 및 도펀트 재료를 포함할 수 있다. 호스트 재료는 축합 방향족환 유도체 또는 헤테로환 함유 화합물 등이 있다. 구체적으로 축합 방향족환 유도체로는 안트라센 유도체, 피렌 유도체, 나프탈렌 유도체, 펜타센 유도체, 페난트렌 화합물, 플루오란텐 화합물 등이 있고, 헤테로환 함유 화합물로는 카바졸 유도체, 디벤조퓨란 유도체, 래더형 퓨란 화합물, 피리미딘 유도체 등이 있으나, 이에 한정되지 않는다. The light emitting layer may include a host material and a dopant material. The host material includes a condensed aromatic ring derivative or a compound containing a hetero ring. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type furan compounds, pyrimidine derivatives, etc., 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 한정되지 않는다. 또한, 금속 착체로는 이리듐 착체, 백금 착체 등이 있으나, 이에 한정되지 않는다.Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, aromatic amine derivatives are condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, periplanthene, etc. having an arylamino group, and styrylamine compounds include substituted or unsubstituted arylamine is substituted with at least one arylvinyl group, wherein one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc., but is not limited thereto. In addition, metal complexes include, but are not limited to, iridium complexes and platinum complexes.
정공차단층hole blocking layer
본 발명에 따른 유기 발광 소자는, 필요에 따라 상기 발광층과 전자수송층, 전자주입층, 또는 전자수송 및 주입층 사이에 정공차단층을 포함한다. 바람직하게는, 상기 정공차단층은 상기 발광층에 접한다. The organic light emitting device according to the present invention includes a hole blocking layer between the light emitting layer, an electron transport layer, an electron injection layer, or an electron transport and injection layer, as necessary. Preferably, the hole blocking layer is in contact with the light emitting layer.
상기 정공차단층은, 양극에서 주입된 정공이 발광층에서 재결합하지 않고 음극 쪽으로 전달되는 것을 억제하여 유기 발광 소자의 효율을 향상시키는 역할을 한다. 본 발명에서는 상기 정공차단층을 구성하는 물질로서 상기 화학식 1로 표시되는 화합물을 사용한다.The hole blocking layer serves to improve the efficiency of the organic light emitting device by suppressing the transfer of holes injected from the anode to the cathode without recombination in the light emitting layer. In the present invention, the compound represented by Formula 1 is used as a material constituting the hole blocking layer.
바람직하게는, L1 및 L2는 각각 독립적으로, 직접 결합, 또는 페닐렌이고; L3는 직접 결합, 페닐렌, 비페닐디일, 또는 터페닐디일이다.Preferably, L 1 and L 2 are each independently a direct bond or phenylene; L 3 is a direct key, phenylene, biphenyldiyl, or terphenyldiyl.
바람직하게는, Ar1 및 Ar2는 각각 독립적으로, 페닐, 비페닐릴, 또는 나프틸이다.Preferably, Ar 1 and Ar 2 are each independently phenyl, biphenylyl, or naphthyl.
바람직하게는, Ar3는 하기 화학식 1-1 내지 화학식 1-7로 표시되는 치환기 중 어느 하나이다:Preferably, Ar 3 is any one of substituents represented by Formulas 1-1 to 1-7 below:
[화학식 1-1][Formula 1-1]
Figure PCTKR2022007243-appb-img-000011
Figure PCTKR2022007243-appb-img-000011
[화학식 1-2][Formula 1-2]
Figure PCTKR2022007243-appb-img-000012
Figure PCTKR2022007243-appb-img-000012
[화학식 1-3][Formula 1-3]
Figure PCTKR2022007243-appb-img-000013
Figure PCTKR2022007243-appb-img-000013
[화학식 1-4][Formula 1-4]
Figure PCTKR2022007243-appb-img-000014
Figure PCTKR2022007243-appb-img-000014
[화학식 1-5][Formula 1-5]
Figure PCTKR2022007243-appb-img-000015
Figure PCTKR2022007243-appb-img-000015
[화학식 1-6][Formula 1-6]
Figure PCTKR2022007243-appb-img-000016
Figure PCTKR2022007243-appb-img-000016
[화학식 1-7][Formula 1-7]
Figure PCTKR2022007243-appb-img-000017
Figure PCTKR2022007243-appb-img-000017
상기 화학식 1-1 내지 화학식 1-7에서,In Formula 1-1 to Formula 1-7,
R6 및 R7은 각각 독립적으로, 수소; 중수소; 치환 또는 비치환된 C1-10 알킬; 또는 치환 또는 비치환된 C6-60 아릴이고; Z는 각각 독립적으로, NR9, O, 또는 S이고; R8 및 R9는 각각 독립적으로, 치환 또는 비치환된 C6-60 아릴이다.R 6 and R 7 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 1-10 Alkyl; or a substituted or unsubstituted C 6-60 aryl; Z is each independently NR 9 , O, or S; R 8 and R 9 are each independently a substituted or unsubstituted C 6-60 aryl.
바람직하게는, R6 및 R7은 각각 독립적으로, 수소, 중수소, 메틸, 또는 치환 또는 비치환된 페닐이고; R8 및 R9는 페닐이다.Preferably, R 6 and R 7 are each independently hydrogen, deuterium, methyl, or substituted or unsubstituted phenyl; R 8 and R 9 are phenyl.
바람직하게는, Ar3는 하기로 구성되는 군으로부터 선택되는 어느 하나이다:Preferably, Ar 3 is any one selected from the group consisting of:
Figure PCTKR2022007243-appb-img-000018
Figure PCTKR2022007243-appb-img-000018
상기 화학식 1로 표시되는 화합물의 대표적인 예는 하기와 같다:Representative examples of the compound represented by Formula 1 are as follows:
Figure PCTKR2022007243-appb-img-000019
Figure PCTKR2022007243-appb-img-000019
Figure PCTKR2022007243-appb-img-000020
Figure PCTKR2022007243-appb-img-000020
Figure PCTKR2022007243-appb-img-000021
Figure PCTKR2022007243-appb-img-000021
Figure PCTKR2022007243-appb-img-000022
Figure PCTKR2022007243-appb-img-000022
Figure PCTKR2022007243-appb-img-000023
Figure PCTKR2022007243-appb-img-000023
Figure PCTKR2022007243-appb-img-000024
Figure PCTKR2022007243-appb-img-000024
Figure PCTKR2022007243-appb-img-000025
Figure PCTKR2022007243-appb-img-000025
Figure PCTKR2022007243-appb-img-000026
Figure PCTKR2022007243-appb-img-000026
Figure PCTKR2022007243-appb-img-000027
Figure PCTKR2022007243-appb-img-000027
Figure PCTKR2022007243-appb-img-000028
Figure PCTKR2022007243-appb-img-000028
Figure PCTKR2022007243-appb-img-000029
Figure PCTKR2022007243-appb-img-000029
Figure PCTKR2022007243-appb-img-000030
Figure PCTKR2022007243-appb-img-000030
Figure PCTKR2022007243-appb-img-000031
Figure PCTKR2022007243-appb-img-000031
Figure PCTKR2022007243-appb-img-000032
Figure PCTKR2022007243-appb-img-000032
Figure PCTKR2022007243-appb-img-000033
Figure PCTKR2022007243-appb-img-000033
Figure PCTKR2022007243-appb-img-000034
Figure PCTKR2022007243-appb-img-000034
Figure PCTKR2022007243-appb-img-000035
Figure PCTKR2022007243-appb-img-000035
Figure PCTKR2022007243-appb-img-000036
Figure PCTKR2022007243-appb-img-000036
Figure PCTKR2022007243-appb-img-000037
Figure PCTKR2022007243-appb-img-000037
Figure PCTKR2022007243-appb-img-000038
Figure PCTKR2022007243-appb-img-000038
또한, 본 발명은 하기 반응식 1과 같은, 상기 화학식 1로 표시되는 화합물의 제조 방법을 제공한다.In addition, the present invention provides a method for preparing the compound represented by Formula 1, as shown in Reaction Scheme 1 below.
[반응식 1][Scheme 1]
Figure PCTKR2022007243-appb-img-000039
Figure PCTKR2022007243-appb-img-000039
상기 반응식 1에서, X1 내지 X3, L1 내지 L3, 및 Ar1 내지 Ar3는 앞서 정의한 바와 같으며, Z는 할로겐이고, 바람직하게는 브로모, 또는 클로로이다.In Scheme 1, X 1 to X 3 , L 1 to L 3 , and Ar 1 to Ar 3 are as defined above, and Z is halogen, preferably bromo or chloro.
상기 제조 방법은 후술할 제조예에서 보다 구체화될 수 있다.The manufacturing method may be more specific in Preparation Examples to be described later.
전자수송층, 전자주입층, 또는 전자수송 및 주입층electron transport layer, electron injection layer, or electron transport and injection layer
본 발명에 따른 유기 발광 소자는, 상기 발광층과 음극 사이에 전자 수송층, 전자주입층, 또는 전자수송 및 주입층을 포함할 수 있다.The organic light emitting device according to the present invention may include an electron transport layer, an electron injection layer, or an electron transport and injection layer between the light emitting layer and the cathode.
상기 전자수송층은, 음극 또는 음극 상에 형성된 전자주입층으로부터 전자를 수취하여 발광층까지 전자를 수송하고, 또한 발광층에서 정공이 전달되는 것을 억제하는 층으로, 전자 수송 물질로는 음극으로부터 전자를 잘 주입 받아 발광층으로 옮겨줄 수 있는 물질로서, 본 발명에는 상기 화학식 2로 표시되는 화합물 및 화학식 3으로 표시되는 화합물 중 어느 하나 이상을 포함할 수 있다.The electron transport layer is a layer that receives electrons from the cathode or an electron injection layer formed on the cathode, transports electrons to the light emitting layer, and suppresses the transfer of holes in the light emitting layer. As an electron transport material, electrons are well injected from the cathode. As a material capable of receiving and transferring to the light emitting layer, the present invention may include at least one of the compound represented by Chemical Formula 2 and the compound represented by Chemical Formula 3.
상기 전자주입층은, 전극으로부터 전자를 주입하는 층으로, 전자를 수송하는 능력을 갖고, 음극으로부터의 전자 주입 효과, 발광층 또는 발광 재료에 대하여 우수한 전자주입 효과를 가지며, 발광층에서 생성된 여기자의 정공주입층에의 이동을 방지하고, 또한, 박막형성능력이 우수한 화합물로서, 본 발명에는 상기 화학식 2로 표시되는 화합물 및 화학식 3으로 표시되는 화합물 중 어느 하나 이상을 포함할 수 있다.The electron injection layer is a layer for injecting electrons from an electrode, has an ability to transport electrons, has an excellent electron injection effect from a cathode, a light emitting layer or a light emitting material, and has a hole of excitons generated in the light emitting layer. As a compound that prevents migration to the injection layer and has excellent thin film formation ability, the present invention may include at least one of the compound represented by Chemical Formula 2 and the compound represented by Chemical Formula 3.
상기 전자수송 및 주입층은, 전자 수송과 주입을 동시에 하는 층으로, 상기 화학식 2 또는 3으로 표시되는 화합물을 포함할 수 있다.The electron transport and injection layer is a layer that simultaneously transports and injects electrons, and may include the compound represented by Chemical Formula 2 or 3.
바람직하게는, 상기 화학식 2는 하기 화학식 2-1로 표시되고; 상기 화학식 3은 하기 화학식 3-1로 표시된다.Preferably, Formula 2 is represented by Formula 2-1 below; Formula 3 is represented by Formula 3-1 below.
[화학식 2-1][Formula 2-1]
Figure PCTKR2022007243-appb-img-000040
Figure PCTKR2022007243-appb-img-000040
[화학식 3-1][Formula 3-1]
Figure PCTKR2022007243-appb-img-000041
Figure PCTKR2022007243-appb-img-000041
상기 화학식 2-1, 또는 화학식 3-1에서, L4, L5, Ar4 및 Ar5는 앞서 정의한 바와 같다.In Formula 2-1 or Formula 3-1, L 4 , L 5 , Ar 4 and Ar 5 are as defined above.
바람직하게는, L4 및 L5는 각각 독립적으로 직접 결합, 페닐렌, 또는 비페닐디일이다.Preferably, L 4 and L 5 are each independently a direct bond, phenylene, or biphenyldiyl.
바람직하게는, Ar4 및 Ar5는 각각 독립적으로, 하기로 구성되는 군으로부터 선택되는 어느 하나이다:Preferably, Ar 4 and Ar 5 are each independently any one selected from the group consisting of:
Figure PCTKR2022007243-appb-img-000042
Figure PCTKR2022007243-appb-img-000042
상기 군에서, R5는 앞서 정의한 바와 같다.In this group, R 5 is as defined above.
바람직하게는, R5는 각각 독립적으로, 수소, 중수소, 메틸, tert-부틸, 페닐, 비페닐릴, 터페닐릴, 나프틸, 피리디닐, 퓨라닐, 또는 티오페닐이거나, 이들 중 인접한 2개의 R5가 결합하여 벤젠 고리를 형성하고; 상기 페닐, 비페닐릴, 터페닐릴, 나프틸, 피리디닐, 퓨라닐, 또는 티오페닐은 각각 독립적으로 비치환되거나, 중수소, 메틸, 또는 tert-부틸로 치환된다.Preferably, each R 5 is independently hydrogen, deuterium, methyl, tert-butyl, phenyl, biphenylyl, terphenylyl, naphthyl, pyridinyl, furanyl, or thiophenyl, or two adjacent ones thereof R 5 is bonded to form a benzene ring; The phenyl, biphenylyl, terphenylyl, naphthyl, pyridinyl, furanyl, or thiophenyl are each independently unsubstituted or substituted with deuterium, methyl, or tert-butyl.
바람직하게는, Ar4 및 Ar5는 각각 독립적으로, 하기로 구성되는 군으로부터 선택되는 어느 하나이다:Preferably, Ar 4 and Ar 5 are each independently any one selected from the group consisting of:
Figure PCTKR2022007243-appb-img-000043
Figure PCTKR2022007243-appb-img-000043
Figure PCTKR2022007243-appb-img-000044
Figure PCTKR2022007243-appb-img-000044
상기 화학식 2 또는 3으로 표시되는 화합물의 대표적인 예는 하기와 같다:Representative examples of the compound represented by Formula 2 or 3 are as follows:
Figure PCTKR2022007243-appb-img-000045
Figure PCTKR2022007243-appb-img-000045
Figure PCTKR2022007243-appb-img-000046
Figure PCTKR2022007243-appb-img-000046
Figure PCTKR2022007243-appb-img-000047
Figure PCTKR2022007243-appb-img-000047
Figure PCTKR2022007243-appb-img-000048
Figure PCTKR2022007243-appb-img-000048
Figure PCTKR2022007243-appb-img-000049
Figure PCTKR2022007243-appb-img-000049
또한, 본 발명은 하기 반응식 2 내지 5와 같은, 상기 화학식 2 또는 3으로 표시되는 화합물의 제조 방법을 제공한다.In addition, the present invention provides a method for producing a compound represented by Formula 2 or 3, as shown in Schemes 2 to 5 below.
[반응식 2][Scheme 2]
Figure PCTKR2022007243-appb-img-000050
[반응식 3]
Figure PCTKR2022007243-appb-img-000050
[Scheme 3]
Figure PCTKR2022007243-appb-img-000051
[반응식 4]
Figure PCTKR2022007243-appb-img-000051
[Scheme 4]
Figure PCTKR2022007243-appb-img-000052
[반응식 5]
Figure PCTKR2022007243-appb-img-000052
[Scheme 5]
Figure PCTKR2022007243-appb-img-000053
상기 반응식 2 내지 5에서, L은 각각 독립적으로, L4, 또는 L5이고; Ar은 각각 독립적으로, Ar4, 또는 Ar5이고; R은 각각 독립적으로 R1 내지 R4 중 어느 하나이고; n은 각각 독립적으로 n1 내지 n4 중 어느 하나이다. 또한, L4, L5, Ar4, Ar5, R1 내지 R4, 및 n1 내지 n4는 앞서 정의한 바와 같으며, Z는 할로겐이고, 바람직하게는 브로모, 또는 클로로이다.
Figure PCTKR2022007243-appb-img-000053
In Schemes 2 to 5, L is each independently L 4 or L 5 ; Ar is each independently Ar 4 or Ar 5 ; R is each independently any one of R 1 to R 4 ; n is each independently any one of n1 to n4. In addition, L 4 , L 5 , Ar 4 , Ar 5 , R 1 to R 4 , and n1 to n4 are as defined above, and Z is halogen, preferably bromo or chloro.
또한, 상기 전자수송층은 금속 착체 화합물을 추가로 포함할 수 있다. 상기 금속 착체 화합물로서는 8-하이드록시퀴놀리나토 리튬, 비스(8-하이드록시퀴놀리나토)아연, 비스(8-하이드록시퀴놀리나토)구리, 비스(8-하이드록시퀴놀리나토)망간, 트리스(8-하이드록시퀴놀리나토)알루미늄, 트리스(2-메틸-8-하이드록시퀴놀리나토)알루미늄, 트리스(8-하이드록시퀴놀리나토)갈륨, 비스(10-하이드록시벤조[h]퀴놀리나토)베릴륨, 비스(10-하이드록시벤조[h]퀴놀리나토)아연, 비스(2-메틸-8-퀴놀리나토)클로로갈륨, 비스(2-메틸-8-퀴놀리나토)(o-크레졸라토)갈륨, 비스(2-메틸-8-퀴놀리나토)(1-나프톨라토)알루미늄, 비스(2-메틸-8-퀴놀리나토)(2-나프톨라토)갈륨 등이 있으나, 이에 한정되지 않는다.In addition, the electron transport layer may further include a metal complex compound. Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato) aluminum, tris(2-methyl-8-hydroxyquinolinato) aluminum, tris(8-hydroxyquinolinato) gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( There are o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium. Not limited to this.
또한, 상기 전자주입층은 금속 착제 화합물을 추가로 포함할 수 있다. 상기 금속 착체 화합물로서는 8-하이드록시퀴놀리나토 리튬, 비스(8-하이드록시퀴놀리나토)아연, 비스(8-하이드록시퀴놀리나토)구리, 비스(8-하이드록시퀴놀리나토)망간, 트리스(8-하이드록시퀴놀리나토)알루미늄, 트리스(2-메틸-8-하이드록시퀴놀리나토)알루미늄, 트리스(8-하이드록시퀴놀리나토)갈륨, 비스(10-하이드록시벤조[h]퀴놀리나토)베릴륨, 비스(10-하이드록시벤조[h]퀴놀리나토)아연, 비스(2-메틸-8-퀴놀리나토)클로로갈륨, 비스(2-메틸-8-퀴놀리나토)(o-크레졸라토)갈륨, 비스(2-메틸-8-퀴놀리나토)(1-나프톨라토)알루미늄, 비스(2-메틸-8-퀴놀리나토)(2-나프톨라토)갈륨 등이 있으나, 이에 한정되지 않는다.In addition, the electron injection layer may further include a metal complex compound. Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato) aluminum, tris(2-methyl-8-hydroxyquinolinato) aluminum, tris(8-hydroxyquinolinato) gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( There are o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium. Not limited to this.
유기 발광 소자organic light emitting device
본 발명에 따른 유기 발광 소자의 구조를 도 1에 예시하였다. 도 1은, 기판(1), 양극(2), 발광층(3), 정공차단층(4), 전자수송 및 주입층(5) 및 음극(6)으로 이루어진 유기 발광 소자의 예를 도시한 것이다.The structure of the organic light emitting device according to the present invention is illustrated in FIG. 1 . 1 shows an example of an organic light emitting device composed of a substrate 1, an anode 2, a light emitting layer 3, a hole blocking layer 4, an electron transport and injection layer 5 and a cathode 6 .
또한, 도 2는 기판(1), 양극(2), 정공주입층(7), 정공수송층(8), 전자억제층(9), 발광층(3), 정공차단층(4), 전자수송 및 주입층(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 8, an electron blocking layer 9, a light emitting layer 3, a hole blocking layer 4, electron transport and An example of an organic light emitting device composed of an injection layer 5 and a cathode 6 is shown.
본 발명에 따른 유기 발광 소자는 상술한 구성을 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 상술한 각 층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시켜 제조할 수 있다. 이와 같은 방법 외에도, 기판 상에 음극 물질부터 상술한 구성의 역순으로 양극 물질까지 차례로 증착시켜 유기 발광 소자를 만들 수 있다(WO 2003/012890). 또한, 발광층은 호스트 및 도펀트를 진공 증착법 뿐만 아니라 용액 도포법에 의하여 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.The organic light emitting device according to the present invention can be manufactured by sequentially stacking the above-described components. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, depositing a metal or a metal oxide having conductivity or an alloy thereof on the substrate to form an anode And, after forming each of the above-mentioned layers thereon, it can be manufactured 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 on a substrate and an anode material in the reverse order of the above configuration (WO 2003/012890). In addition, the light emitting layer may be formed by a solution coating method as well as a vacuum deposition method of a host and a dopant. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.
한편, 본 발명에 따른 유기 발광 소자는 배면 발광(bottom emission) 소자, 전면 발광(top emission) 소자, 또는 양면 발광 소자일 수 있으며, 특히 상대적으로 높은 발광 효율이 요구되는 배면 발광 소자일 수 있다.Meanwhile, the organic light emitting device according to the present invention may be a bottom emission device, a top emission device, or a double-sided light emitting device, and in particular, may be a bottom emission device requiring relatively high light emitting efficiency.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 이에 의해 본 발명의 내용이 한정되는 것은 아니다.Hereinafter, a preferred embodiment is presented to aid understanding of the present invention. However, the following examples are only provided to more easily understand the present invention, and the content of the present invention is not limited thereby.
[제조예][Production Example]
제조예 1-1: 화합물 B1의 제조Preparation Example 1-1: Preparation of Compound B1
Figure PCTKR2022007243-appb-img-000054
Figure PCTKR2022007243-appb-img-000054
질소 분위기에서 B1-A(20 g, 43.1 mmol)와 B1-B(10.3 g, 43.1 mmol)를 테트라하이드로 퓨란 400 ml에 넣고 교반 및 환류하였다. 이 후 포타슘카보네이트(17.9 g, 129.2 mmol)를 물18 ml에 녹여 투입하고 충분히 교반한 후 테트라키스트리페닐-포스피노팔라듐(1.5 g, 1.3 mmol)을 투입하였다. 3시간 반응 후 상온으로 식인 후 유기층과 물층을 분리 후 유기층을 증류하였다. 이를 다시클로로포름 20배 498 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트재결정을 통해 흰색의 고체 화합물 B1(12.9 g, 52%)을 제조하였다.In a nitrogen atmosphere, B1-A (20 g, 43.1 mmol) and B1-B (10.3 g, 43.1 mmol) were added to 400 ml of tetrahydrofuran, stirred and refluxed. Thereafter, potassium carbonate (17.9 g, 129.2 mmol) was dissolved in 18 ml of water, and after stirring sufficiently, tetrakistriphenyl-phosphinopalladium (1.5 g, 1.3 mmol) was added. After reacting for 3 hours, cooling to room temperature, separating the organic layer and the water layer, and distilling the organic layer. This was put into 498 mL of 20 times chloroform again to dissolve, washed twice with water, separated the organic layer, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethyl acetate to obtain compound B1 (12.9 g, 52%) as a white solid.
MS: [M+H]+ = 578MS: [M+H] + = 578
제조예 1-2: 화합물 B2의 제조Preparation Example 1-2: Preparation of Compound B2
Figure PCTKR2022007243-appb-img-000055
Figure PCTKR2022007243-appb-img-000055
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 1-1의 제조 방법과 동일한 방법으로 상기 화합물 B2를 제조하였다.Compound B2 was prepared in the same manner as in Preparation Example 1-1, except for using each starting material as in the reaction scheme.
MS: [M+H]+ = 625MS: [M+H] + = 625
제조예 1-3: 화합물 B3의 제조Preparation Example 1-3: Preparation of Compound B3
Figure PCTKR2022007243-appb-img-000056
Figure PCTKR2022007243-appb-img-000056
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 1-1의 제조 방법과 동일한 방법으로 상기 화합물 B3를 제조하였다.Compound B3 was prepared in the same manner as in Preparation Example 1-1, except for using each starting material as in the above reaction scheme.
MS: [M+H]+ = 617MS: [M+H] + = 617
제조예 1-4: 화합물 B4의 제조Preparation Example 1-4: Preparation of Compound B4
Figure PCTKR2022007243-appb-img-000057
Figure PCTKR2022007243-appb-img-000057
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 1-1의 제조 방법과 동일한 방법으로 상기 화합물 B4를 제조하였다.Compound B4 was prepared in the same manner as in Preparation Example 1-1, except for using each starting material as in the above reaction scheme.
MS: [M+H]+ = 654MS: [M+H] + = 654
제조예 1-5: 화합물 B5의 제조Preparation Example 1-5: Preparation of Compound B5
Figure PCTKR2022007243-appb-img-000058
Figure PCTKR2022007243-appb-img-000058
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 1-1의 제조 방법과 동일한 방법으로 상기 화합물 B5를 제조하였다.Compound B5 was prepared in the same manner as in Preparation Example 1-1, except for using each starting material as in the above reaction scheme.
MS: [M+H]+ = 653MS: [M+H] + = 653
제조예 1-6: 화합물 B6의 제조Preparation Example 1-6: Preparation of Compound B6
Figure PCTKR2022007243-appb-img-000059
Figure PCTKR2022007243-appb-img-000059
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 1-1의 제조 방법과 동일한 방법으로 상기 화합물 B6를 제조하였다.Compound B6 was prepared in the same manner as in Preparation Example 1-1, except for using each starting material as in the above reaction scheme.
MS: [M+H]+ = 653MS: [M+H] + = 653
제조예 1-7: 화합물 B7의 제조Preparation Example 1-7: Preparation of Compound B7
Figure PCTKR2022007243-appb-img-000060
Figure PCTKR2022007243-appb-img-000060
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 1-1의 제조 방법과 동일한 방법으로 상기 화합물 B7을 제조하였다.Compound B7 was prepared in the same manner as in Preparation Example 1-1, except for using each starting material as in the above reaction scheme.
MS: [M+H]+ = 624MS: [M+H] + = 624
제조예 1-8: 화합물 B8의 제조Preparation Example 1-8: Preparation of Compound B8
Figure PCTKR2022007243-appb-img-000061
Figure PCTKR2022007243-appb-img-000061
질소 분위기에서 B8-A(20 g, 43.1 mmol)와 B8-B(15.4 g, 43.1 mmol)를 자일렌 400ml에 넣고 교반 및 환류하였다. 이 후 나트륨 터셔리-부톡사이드 (12.4 g, 129.2 mmol)를투입하고 충분히 교반한 후 비스(트리 터셔리-부틸포스핀)팔라듐(0.7 g, 1.3 mmol)을 투입하였다. 1시간 반응 후 상온으로 식인 후 유기층을 필터처리하여 염을 제거 한 후 걸러진 유기층을 증류하였다. 이를 다시 클로로포름 10 배 320 mL에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하여, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트를 이용하여 실리카 컬럼을 통해 정제하여 노랑의 고체 화합물 B8(18.2 g, 57%)을 제조하였다.In a nitrogen atmosphere, B8-A (20 g, 43.1 mmol) and B8-B (15.4 g, 43.1 mmol) were added to 400 ml of xylene, stirred and refluxed. Thereafter, sodium tert-butoxide (12.4 g, 129.2 mmol) was added, and after stirring sufficiently, bis(tri tert-butylphosphine)palladium (0.7 g, 1.3 mmol) was added. After reacting for 1 hour, cooled to room temperature, the organic layer was filtered to remove salts, and the filtered organic layer was distilled. This was put into 320 mL of 10 times chloroform again to dissolve, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to obtain a yellow solid compound B8 (18.2 g, 57%).
MS: [M+H]+ = 742MS: [M+H] + = 742
제조예 2-1: 화합물 E1의 제조Preparation Example 2-1: Preparation of Compound E1
Figure PCTKR2022007243-appb-img-000062
Figure PCTKR2022007243-appb-img-000062
질소 분위기에서 E1-A(20 g, 64.1 mmol)와 E1-B(55.8 g, 128.2 mmol)를 테트라하이드로퓨란(400 ml)에 넣고 교반 및 환류하였다. 이후, 포타슘카보네이트(26.6 g, 192.3 mmol)를 물(27 ml)에 녹여 투입하고 충분히 교반한 후 테트라키스트리페닐-포스피노팔라듐(2.2 g, 1.9 mmol)을 투입하였다. 1시간 반응 후 상온으로 식힌 후 유기층과 물층을 분리하고 유기층을 증류하였다. 이를 다시 클로로포름(20배, 986 mL)에 투입하여 녹이고, 물로 2회 세척후에 유기층을 분리하고, 무수황산마그네슘을 넣어 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트 재결정을 통해 흰색의 고체 화합물 E1(32.5 g, 66%)을 제조하였다.In a nitrogen atmosphere, E1-A (20 g, 64.1 mmol) and E1-B (55.8 g, 128.2 mmol) were added to tetrahydrofuran (400 ml), stirred and refluxed. Thereafter, potassium carbonate (26.6 g, 192.3 mmol) was dissolved in water (27 ml), and after stirring sufficiently, tetrakistriphenyl-phosphinopalladium (2.2 g, 1.9 mmol) was added. After reacting for 1 hour, cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was put into chloroform (20 times, 986 mL) again to dissolve it, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to obtain compound E1 (32.5 g, 66%) as a white solid.
MS: [M+H]+ = 769MS: [M+H] + = 769
제조예 2-2: 화합물 E2의 제조Preparation Example 2-2: Preparation of Compound E2
Figure PCTKR2022007243-appb-img-000063
Figure PCTKR2022007243-appb-img-000063
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 2-1의 제조 방법과 동일한 방법으로 상기 화합물 E2를 제조하였다.Compound E2 was prepared in the same manner as in Preparation Example 2-1, except for using each starting material as in the above reaction scheme.
MS: [M+H]+ = 767MS: [M+H] + = 767
제조예 2-3: 화합물 E3의 제조Preparation Example 2-3: Preparation of Compound E3
Figure PCTKR2022007243-appb-img-000064
Figure PCTKR2022007243-appb-img-000064
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 2-1의 제조 방법과 동일한 방법으로 상기 화합물 E3를 제조하였다.Compound E3 was prepared in the same manner as in Preparation Example 2-1, except for using each starting material as in the above reaction scheme.
MS: [M+H]+ = 715MS: [M+H] + = 715
제조예 2-4: 화합물 E4의 제조Preparation Example 2-4: Preparation of Compound E4
Figure PCTKR2022007243-appb-img-000065
Figure PCTKR2022007243-appb-img-000065
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 2-1의 제조 방법과 동일한 방법으로 상기 화합물 E4를 제조하였다.Compound E4 was prepared in the same manner as in Preparation Example 2-1, except for using each starting material as in the above reaction scheme.
MS: [M+H]+ = 615MS: [M+H] + = 615
제조예 2-5: 화합물 E5의 제조Preparation Example 2-5: Preparation of Compound E5
Figure PCTKR2022007243-appb-img-000066
Figure PCTKR2022007243-appb-img-000066
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 2-1의 제조 방법과 동일한 방법으로 상기 화합물 E5를 제조하였다.Compound E5 was prepared in the same manner as in Preparation Example 2-1, except for using each starting material as in the above reaction scheme.
MS: [M+H]+ = 619MS: [M+H] + = 619
제조예 2-6: 화합물 E6의 제조Preparation Example 2-6: Preparation of Compound E6
Figure PCTKR2022007243-appb-img-000067
Figure PCTKR2022007243-appb-img-000067
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 2-1의 제조 방법과 동일한 방법으로 상기 화합물 E6를 제조하였다.Compound E6 was prepared in the same manner as in Preparation Example 2-1, except for using each starting material as in the above reaction scheme.
MS: [M+H]+ = 715MS: [M+H] + = 715
제조예 2-7: 화합물 E7의 제조Preparation Example 2-7: Preparation of Compound E7
Figure PCTKR2022007243-appb-img-000068
Figure PCTKR2022007243-appb-img-000068
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 2-1의 제조 방법과 동일한 방법으로 상기 화합물 E7을 제조하였다.Compound E7 was prepared in the same manner as in Preparation Example 2-1, except for using each starting material as in the above reaction scheme.
MS: [M+H]+ = 919MS: [M+H] + = 919
제조예 2-8: 화합물 E8의 제조Preparation Example 2-8: Preparation of Compound E8
Figure PCTKR2022007243-appb-img-000069
Figure PCTKR2022007243-appb-img-000069
질소 분위기에서 E8-A(20 g, 47.6 mmol)와 E8-B(28 g, 47.6 mmol)를 1,4-Dioxane(400 ml)에 넣고 교반 및 환류하였다. 이후, 제3인산칼륨(30.3 g, 142.9 mmol)을 물(30 ml)에 녹여 투입하고 충분히 교반한 후 디벤질리덴아세톤팔라듐(0.8 g, 1.4 mmol) 및 트리시클로헥실포스핀(0.8 g, 2.9 mmol)을 투입하였다. 5시간 반응 후 상온으로 식힌 후 생성된 고체를 여과하였다. 고체를 클로로포름(30 배, 1207 mL)에 투입하여 녹이고, 물로 2회 세척 후에 유기층을 분리하고, 무수황산마그네슘을 넣고 교반한 후 여과하여 여액을 감압 증류하였다. 농축한 화합물을 클로로포름과 에틸아세테이트재결정을 통해 흰색의 고체 화합물 E8(6 g, 15%)을 제조하였다.In a nitrogen atmosphere, E8-A (20 g, 47.6 mmol) and E8-B (28 g, 47.6 mmol) were added to 1,4-Dioxane (400 ml), stirred and refluxed. Thereafter, potassium triphosphate (30.3 g, 142.9 mmol) was dissolved in water (30 ml), added, stirred sufficiently, dibenzylideneacetone palladium (0.8 g, 1.4 mmol) and tricyclohexylphosphine (0.8 g, 2.9 g). mmol) was added. After reacting for 5 hours, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (30 times, 1207 mL), washed twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to obtain a white solid compound E8 (6 g, 15%).
MS: [M+H]+ = 845MS: [M+H] + = 845
제조예 2-9: 화합물 E9의 제조Preparation Example 2-9: Preparation of Compound E9
Figure PCTKR2022007243-appb-img-000070
Figure PCTKR2022007243-appb-img-000070
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 2-8의 제조 방법과 동일한 방법으로 상기 화합물 E9을 제조하였다.Compound E9 was prepared in the same manner as in Preparation Examples 2-8, except for using each starting material as in the above reaction scheme.
MS: [M+H]+ = 769MS: [M+H] + = 769
제조예 2-10: 화합물 E10의 제조Preparation Example 2-10: Preparation of Compound E10
Figure PCTKR2022007243-appb-img-000071
Figure PCTKR2022007243-appb-img-000071
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 2-8의 제조 방법과 동일한 방법으로 상기 화합물 E10을 제조하였다.Compound E10 was prepared in the same manner as in Preparation Examples 2-8, except for using each starting material as in the reaction scheme.
MS: [M+H]+ = 843MS: [M+H] + = 843
제조예 2-11: 화합물 E11의 제조Preparation Example 2-11: Preparation of compound E11
Figure PCTKR2022007243-appb-img-000072
Figure PCTKR2022007243-appb-img-000072
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 2-1의 제조 방법과 동일한 방법으로 상기 화합물 E11을 제조하였다.Compound E11 was prepared in the same manner as in Preparation Example 2-1, except for using each starting material as in the above reaction scheme.
MS: [M+H]+ = 769MS: [M+H] + = 769
제조예 2-12: 화합물 E12의 제조Preparation Example 2-12: Preparation of compound E12
Figure PCTKR2022007243-appb-img-000073
Figure PCTKR2022007243-appb-img-000073
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 2-1의 제조 방법과 동일한 방법으로 상기 화합물 E12를 제조하였다.Compound E12 was prepared in the same manner as in Preparation Example 2-1, except for using each starting material as in the reaction scheme.
MS: [M+H]+ = 715MS: [M+H] + = 715
제조예 2-13: 화합물 E13의 제조Preparation Example 2-13: Preparation of Compound E13
Figure PCTKR2022007243-appb-img-000074
Figure PCTKR2022007243-appb-img-000074
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 2-1의 제조 방법과 동일한 방법으로 상기 화합물 E13을 제조하였다.Compound E13 was prepared in the same manner as in Preparation Example 2-1, except for using each starting material as in the above reaction scheme.
MS: [M+H]+ = 795MS: [M+H] + = 795
제조예 2-14: 화합물 E14의 제조Preparation Example 2-14: Preparation of Compound E14
Figure PCTKR2022007243-appb-img-000075
Figure PCTKR2022007243-appb-img-000075
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 2-1의 제조 방법과 동일한 방법으로 상기 화합물 E14을 제조하였다.Compound E14 was prepared in the same manner as in Preparation Example 2-1, except for using each starting material as in the above reaction scheme.
MS: [M+H]+ = 869MS: [M+H] + = 869
제조예 2-15: 화합물 E15의 제조Preparation Example 2-15: Preparation of compound E15
Figure PCTKR2022007243-appb-img-000076
Figure PCTKR2022007243-appb-img-000076
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 2-1의 제조 방법과 동일한 방법으로 상기 화합물 E15을 제조하였다.Compound E15 was prepared in the same manner as in Preparation Example 2-1, except for using each starting material as in the above reaction scheme.
MS: [M+H]+ = 919MS: [M+H] + = 919
제조예 2-16: 화합물 E16의 제조Preparation Example 2-16: Preparation of compound E16
Figure PCTKR2022007243-appb-img-000077
Figure PCTKR2022007243-appb-img-000077
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 2-8의 제조 방법과 동일한 방법으로 상기 화합물 E16을 제조하였다.Compound E16 was prepared in the same manner as in Preparation Examples 2-8, except for using each starting material as in the reaction scheme.
MS: [M+H]+ = 768MS: [M+H] + = 768
제조예 2-17: 화합물 E17의 제조Preparation Example 2-17: Preparation of Compound E17
Figure PCTKR2022007243-appb-img-000078
Figure PCTKR2022007243-appb-img-000078
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 2-8의 제조 방법과 동일한 방법으로 상기 화합물 E17을 제조하였다.Compound E17 was prepared in the same manner as in Preparation Examples 2-8, except for using each starting material as in the above reaction scheme.
MS: [M+H]+ = 845MS: [M+H] + = 845
제조예 2-18: 화합물 E18의 제조Preparation Example 2-18: Preparation of Compound E18
Figure PCTKR2022007243-appb-img-000079
Figure PCTKR2022007243-appb-img-000079
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 2-8의 제조 방법과 동일한 방법으로 상기 화합물 E18을 제조하였다.Compound E18 was prepared in the same manner as in Preparation Examples 2-8, except for using each starting material as in the above reaction scheme.
MS: [M+H]+ = 775MS: [M+H] + = 775
제조예 2-19: 화합물 E19의 제조Preparation Example 2-19: Preparation of compound E19
Figure PCTKR2022007243-appb-img-000080
Figure PCTKR2022007243-appb-img-000080
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 2-1의 제조 방법과 동일한 방법으로 상기 화합물 E19을 제조하였다.Compound E19 was prepared in the same manner as in Preparation Example 2-1, except for using each starting material as in the reaction scheme.
MS: [M+H]+ = 921MS: [M+H] + = 921
제조예 2-20: 화합물 E20의 제조Preparation Example 2-20: Preparation of Compound E20
Figure PCTKR2022007243-appb-img-000081
Figure PCTKR2022007243-appb-img-000081
각 출발 물질을 상기 반응식과 같이 하는 것을 제외하고는, 상기 제조예 2-1의 제조 방법과 동일한 방법으로 상기 화합물 E20를 제조하였다.Compound E20 was prepared in the same manner as in Preparation Example 2-1, except for using each starting material as in the reaction scheme.
MS: [M+H]+ = 919MS: [M+H] + = 919
[실시예][Example]
실시예 1Example 1
ITO(indium tin oxide)가 1,000Å의 두께로 박막 코팅된 유리 기판을 세제를 녹인 증류수에 넣고 초음파로 세척하였다. 이 때, 세제로는 피셔사(Fischer Co.) 제품을 사용하였으며, 증류수로는 밀러포어사(Millipore Co.) 제품의 필터(Filter)로 2차로 걸러진 증류수를 사용하였다. ITO를 30분간 세척한 후 증류수로 2회 반복하여 초음파 세척을 10분간 진행하였다. 증류수 세척이 끝난 후, 이소프로필알콜, 아세톤, 메탄올의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 수송시켰다. 또한, 산소 플라즈마를 이용하여 상기 기판을 5분간 세정한 후 진공 증착기로 기판을 수송시켰다.A glass substrate coated with indium tin oxide (ITO) to a thickness of 1,000 Å was put in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a Fischer Co. product was used as the detergent, and distilled water filtered through a second filter of a Millipore Co. product was used as the distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was performed twice with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with solvents such as isopropyl alcohol, acetone, and methanol, dried, and transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transferred to a vacuum deposition machine.
이렇게 준비된 ITO 투명 전극 위에 하기 화합물 HI-A를 600Å의 두께로 열 진공증착하여 정공주입층을 형성하였다. 상기 정공주입층 위에 하기 화학식의 헥사니트릴 헥사아자트리페닐렌(hexaazatriphenylene; HAT, 50Å) 및 하기 화합물 HT-A(600Å)를 순차적으로 진공증착하여 정공수송층을 형성하였다.A hole injection layer was formed by thermally vacuum depositing the following compound HI-A to a thickness of 600 Å on the prepared ITO transparent electrode. A hole transport layer was formed by sequentially vacuum depositing hexanitrile hexaazatriphenylene (HAT, 50 Å) and the compound HT-A (600 Å) of the following chemical formula on the hole injection layer.
이어서, 상기 정공수송층 위에 막 두께 200Å으로 하기 화합물 BH와 BD를 25:1의 중량비로 진공증착하여 발광층을 형성하였다.Subsequently, the following compounds BH and BD were vacuum deposited at a weight ratio of 25:1 to a film thickness of 200 Å on the hole transport layer to form a light emitting layer.
상기 발광층 위에 상기 화합물 B1을 50Å의 두께로 열진공증착하여 정공차단층을 형성하였다. 상기 정공차단층 위에 상기 화합물 E1과 하기 화합물 [LiQ](Lithiumquinolate)를 1:1 중량비로 진공증착하여 300Å의 두께로 전자수송 및 주입층을 형성하였다. 상기 전자수송 및 주입층 위에 순차적으로 10Å 두께로 리튬 플루오라이드(LiF)와 1,000Å 두께로 알루미늄을 증착하여 음극을 형성하였다.The compound B1 was thermally vacuum deposited on the light emitting layer to a thickness of 50 Å to form a hole blocking layer. On the hole blocking layer, the compound E1 and the following compound [LiQ] (Lithiumquinolate) were vacuum deposited in a weight ratio of 1:1 to form an electron transport and injection layer with a thickness of 300 Å. A negative electrode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 10 Å and aluminum to a thickness of 1,000 Å on the electron transport and injection layer.
Figure PCTKR2022007243-appb-img-000082
Figure PCTKR2022007243-appb-img-000082
상기의 과정에서 유기물의 증착속도는 0.4 ~ 0.9 Å/sec를 유지하였고, 음극의 리튬 플루오라이드는 0.3 Å/sec, 알루미늄은 2 Å/sec의 증착 속도를 유지하였으며, 증착 시 진공도는 1 × 10-7 ~ 5 × 10-8 torr를 유지하여, 유기 발광 소자를 제작하였다.In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.9 Å/sec, the deposition rate of lithium fluoride on the anode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec, and the vacuum level during deposition was 1 × 10 Maintaining -7 to 5 × 10 -8 torr, an organic light emitting device was fabricated.
실시예 2 내지 160Examples 2 to 160
화합물 B1 또는 화합물 E1 대신 하기 표 1의 화합물을 사용한 것을 제외하고는 실험예 1과 동일한 방법으로 유기 발광 소자를 제조하였다.Instead of Compound B1 or Compound E1 An organic light emitting diode was manufactured in the same manner as in Experimental Example 1, except for using the compounds of Table 1 below.
비교예 1 내지 191Comparative Examples 1 to 191
화합물 B1 또는 화합물 E1 대신 하기 표 1의 화합물을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 유기 발광 소자를 제조하였다. 하기 표 1에서 사용한 ET-1 내지 ET-19의 화합물은 하기와 같다.An organic light emitting device was manufactured in the same manner as in Example 1, except that the compounds of Table 1 were used instead of Compound B1 or Compound E1. The compounds of ET-1 to ET-19 used in Table 1 are as follows.
Figure PCTKR2022007243-appb-img-000083
Figure PCTKR2022007243-appb-img-000083
상기 실시예 및 비교예에서 제조한 유기 발광 소자에 대하여, 10 mA/cm2의 전류밀도에서 구동 전압, 발광 효율 및 색좌표를 측정하였고, 20 mA/cm2의 전류밀도에서 초기 휘도 대비 90%가 되는 시간(T90)을 측정하였다. 그 결과를 하기 표 1에 나타내었다.With respect to the organic light emitting device prepared in the above Examples and Comparative Examples, driving voltage, luminous efficiency and color coordinates were measured at a current density of 10 mA/cm 2 , and 90% of the initial luminance at a current density of 20 mA/cm 2 The time to become (T 90 ) was measured. The results are shown in Table 1 below.
화합물
(정공차단층)compound
(hole blocking layer) 		화합물
(전자수송 및 주입층)compound
(electron transport and injection layer) 		전압
(V@10mA/cm2)Voltage
(V@10mA/cm 2 ) 		효율
(cd/A@10mA/cm2)efficiency
(cd/A@10mA/cm 2 ) 		색좌표
(x,y)color coordinates
(x,y) 		T90
(hr@20mA/cm2)T -90
(hr@20mA/cm 2 )
실시예 1Example 1 B1B1 E1E1 3.403.40 4.754.75 (0.133, 0.130)(0.133, 0.130) 150150
실시예 2Example 2 B1B1 E2E2 3.543.54 4.704.70 (0.133, 0.131)(0.133, 0.131) 138138
실시예 3Example 3 B1B1 E3E3 3.573.57 4.614.61 (0.133, 0.134)(0.133, 0.134) 134134
실시예 4Example 4 B1B1 E4E4 3.683.68 4.244.24 (0.133, 0.131)(0.133, 0.131) 123123
실시예 5Example 5 B1B1 E5E5 3.753.75 4.204.20 (0.135, 0.130)(0.135, 0.130) 126126
실시예 6Example 6 B1B1 E6E6 3.683.68 4.184.18 (0.133, 0.133)(0.133, 0.133) 120120
실시예 7Example 7 B1B1 E7E7 3.573.57 4.664.66 (0.133, 0.132)(0.133, 0.132) 135135
실시예 8Example 8 B1B1 E8E8 3.433.43 4.804.80 (0.133, 0.130)(0.133, 0.130) 146146
실시예 9Example 9 B1B1 E9E9 3.473.47 4.664.66 (0.133, 0.131)(0.133, 0.131) 156156
실시예 10Example 10 B1B1 E10E10 3.473.47 4.804.80 (0.133, 0.134)(0.133, 0.134) 141141
실시예 11Example 11 B1B1 E11E11 3.433.43 4.704.70 (0.133, 0.131)(0.133, 0.131) 156156
실시예 12Example 12 B1B1 E12E12 3.503.50 4.814.81 (0.135, 0.130)(0.135, 0.130) 135135
실시예 13Example 13 B1B1 E13E13 3.543.54 4.714.71 (0.133, 0.133)(0.133, 0.133) 130130
실시예 14Example 14 B1B1 E14E14 3.473.47 4.614.61 (0.133, 0.132)(0.133, 0.132) 165165
실시예 15Example 15 B1B1 E15E15 3.503.50 4.624.62 (0.133, 0.130)(0.133, 0.130) 135135
실시예 16Example 16 B1B1 E16E16 3.473.47 4.664.66 (0.133, 0.130)(0.133, 0.130) 153153
실시예 17Example 17 B1B1 E17E17 3.453.45 4.704.70 (0.133, 0.131)(0.133, 0.131) 152152
실시예 18Example 18 B1B1 E18E18 3.503.50 4.474.47 (0.133, 0.134)(0.133, 0.134) 141141
실시예 19Example 19 B1B1 E19E19 3.473.47 4.664.66 (0.133, 0.131)(0.133, 0.131) 154154
실시예 20Example 20 B1B1 E20E20 3.503.50 4.614.61 (0.135, 0.130)(0.135, 0.130) 152152
실시예 21Example 21 B2B2 E1E1 3.303.30 4.904.90 (0.133, 0.133)(0.133, 0.133) 117117
실시예 22Example 22 B2B2 E2E2 3.433.43 4.854.85 (0.133, 0.132)(0.133, 0.132) 108108
실시예 23Example 23 B2B2 E3E3 3.463.46 4.764.76 (0.133, 0.130)(0.133, 0.130) 104104
실시예 24Example 24 B2B2 E4E4 3.573.57 4.384.38 (0.133, 0.131)(0.133, 0.131) 9696
실시예 25Example 25 B2B2 E5E5 3.643.64 4.334.33 (0.133, 0.134)(0.133, 0.134) 9898
실시예 26Example 26 B2B2 E6E6 3.573.57 4.314.31 (0.133, 0.131)(0.133, 0.131) 9494
실시예 27Example 27 B2B2 E7E7 3.463.46 4.804.80 (0.135, 0.130)(0.135, 0.130) 105105
실시예 28Example 28 B2B2 E8E8 3.333.33 4.954.95 (0.133, 0.133)(0.133, 0.133) 113113
실시예 29Example 29 B2B2 E9E9 3.363.36 4.804.80 (0.133, 0.132)(0.133, 0.132) 122122
실시예 30Example 30 B2B2 E10E10 3.363.36 4.954.95 (0.133, 0.130)(0.133, 0.130) 110110
실시예 31Example 31 B2B2 E11E11 3.333.33 4.854.85 (0.133, 0.130)(0.133, 0.130) 122122
실시예 32Example 32 B2B2 E12E12 3.403.40 4.964.96 (0.133, 0.131)(0.133, 0.131) 105105
실시예 33Example 33 B2B2 E13E13 3.433.43 4.864.86 (0.133, 0.134)(0.133, 0.134) 101101
실시예 34Example 34 B2B2 E14E14 3.363.36 4.764.76 (0.133, 0.131)(0.133, 0.131) 129129
실시예 35Example 35 B2B2 E15E15 3.403.40 4.764.76 (0.135, 0.130)(0.135, 0.130) 105105
실시예 36Example 36 B2B2 E16E16 3.363.36 4.804.80 (0.133, 0.133)(0.133, 0.133) 119119
실시예 37Example 37 B2B2 E17E17 3.353.35 4.854.85 (0.133, 0.132)(0.133, 0.132) 118118
실시예 38Example 38 B2B2 E18E18 3.403.40 4.614.61 (0.133, 0.130)(0.133, 0.130) 110110
실시예 39Example 39 B2B2 E19E19 3.363.36 4.814.81 (0.133, 0.131)(0.133, 0.131) 120120
실시예 40Example 40 B2B2 E20E20 3.403.40 4.764.76 (0.133, 0.134)(0.133, 0.134) 119119
실시예 41Example 41 B3B3 E1E1 3.373.37 4.824.82 (0.133, 0.131)(0.133, 0.131) 141141
실시예 42Example 42 B3B3 E2E2 3.503.50 4.774.77 (0.135, 0.130)(0.135, 0.130) 130130
실시예 43Example 43 B3B3 E3E3 3.543.54 4.674.67 (0.133, 0.133)(0.133, 0.133) 126126
실시예 44Example 44 B3B3 E4E4 3.643.64 4.304.30 (0.133, 0.132)(0.133, 0.132) 116116
실시예 45Example 45 B3B3 E5E5 3.713.71 4.264.26 (0.133, 0.130)(0.133, 0.130) 118118
실시예 46Example 46 B3B3 E6E6 3.643.64 4.244.24 (0.133, 0.130)(0.133, 0.130) 113113
실시예 47Example 47 B3B3 E7E7 3.543.54 4.724.72 (0.133, 0.131)(0.133, 0.131) 127127
실시예 48Example 48 B3B3 E8E8 3.403.40 4.864.86 (0.133, 0.134)(0.133, 0.134) 137137
실시예 49Example 49 B3B3 E9E9 3.433.43 4.724.72 (0.133, 0.131)(0.133, 0.131) 147147
실시예 50Example 50 B3B3 E10E10 3.433.43 4.864.86 (0.135, 0.130)(0.135, 0.130) 133133
실시예 51Example 51 B3B3 E11E11 3.403.40 4.774.77 (0.133, 0.133)(0.133, 0.133) 147147
실시예 52Example 52 B3B3 E12E12 3.473.47 4.874.87 (0.133, 0.132)(0.133, 0.132) 127127
실시예 53Example 53 B3B3 E13E13 3.503.50 4.784.78 (0.133, 0.130)(0.133, 0.130) 122122
실시예 54Example 54 B3B3 E14E14 3.433.43 4.674.67 (0.133, 0.131)(0.133, 0.131) 156156
실시예 55Example 55 B3B3 E15E15 3.473.47 4.684.68 (0.133, 0.134)(0.133, 0.134) 127127
실시예 56Example 56 B3B3 E16E16 3.433.43 4.724.72 (0.133, 0.131)(0.133, 0.131) 144144
실시예 57Example 57 B3B3 E17E17 3.423.42 4.774.77 (0.135, 0.130)(0.135, 0.130) 143143
실시예 58Example 58 B3B3 E18E18 3.473.47 4.534.53 (0.133, 0.133)(0.133, 0.133) 133133
실시예 59Example 59 B3B3 E19E19 3.433.43 4.724.72 (0.133, 0.132)(0.133, 0.132) 145145
실시예 60Example 60 B3B3 E20E20 3.473.47 4.684.68 (0.133, 0.130)(0.133, 0.130) 143143
실시예 61Example 61 B4B4 E1E1 3.473.47 4.614.61 (0.133, 0.130)(0.133, 0.130) 174174
실시예 62Example 62 B4B4 E2E2 3.613.61 4.564.56 (0.133, 0.131)(0.133, 0.131) 160160
실시예 63Example 63 B4B4 E3E3 3.643.64 4.474.47 (0.133, 0.134)(0.133, 0.134) 155155
실시예 64Example 64 B4B4 E4E4 3.753.75 4.114.11 (0.133, 0.131)(0.133, 0.131) 143143
실시예 65Example 65 B4B4 E5E5 3.833.83 4.074.07 (0.135, 0.130)(0.135, 0.130) 146146
실시예 66Example 66 B4B4 E6E6 3.753.75 4.054.05 (0.133, 0.133)(0.133, 0.133) 139139
실시예 67Example 67 B4B4 E7E7 3.643.64 4.524.52 (0.133, 0.132)(0.133, 0.132) 157157
실시예 68Example 68 B4B4 E8E8 3.503.50 4.654.65 (0.133, 0.130)(0.133, 0.130) 169169
실시예 69Example 69 B4B4 E9E9 3.543.54 4.524.52 (0.133, 0.131)(0.133, 0.131) 181181
실시예 70Example 70 B4B4 E10E10 3.543.54 4.654.65 (0.133, 0.134)(0.133, 0.134) 164164
실시예 71Example 71 B4B4 E11E11 3.503.50 4.564.56 (0.133, 0.131)(0.133, 0.131) 181181
실시예 72Example 72 B4B4 E12E12 3.573.57 4.664.66 (0.135, 0.130)(0.135, 0.130) 157157
실시예 73Example 73 B4B4 E13E13 3.613.61 4.574.57 (0.133, 0.133)(0.133, 0.133) 150150
실시예 74Example 74 B4B4 E14E14 3.543.54 4.474.47 (0.133, 0.132)(0.133, 0.132) 192192
실시예 75Example 75 B4B4 E15E15 3.573.57 4.484.48 (0.133, 0.130)(0.133, 0.130) 156156
실시예 76Example 76 B4B4 E16E16 3.543.54 4.524.52 (0.133, 0.130)(0.133, 0.130) 177177
실시예 77Example 77 B4B4 E17E17 3.523.52 4.564.56 (0.133, 0.131)(0.133, 0.131) 176176
실시예 78Example 78 B4B4 E18E18 3.573.57 4.334.33 (0.133, 0.134)(0.133, 0.134) 164164
실시예 79Example 79 B4B4 E19E19 3.543.54 4.524.52 (0.133, 0.131)(0.133, 0.131) 178178
실시예 80Example 80 B4B4 E20E20 3.573.57 4.474.47 (0.135, 0.130)(0.135, 0.130) 177177
실시예 81Example 81 B5B5 E1E1 3.393.39 4.734.73 (0.133, 0.133)(0.133, 0.133) 147147
실시예 82Example 82 B5B5 E2E2 3.523.52 4.684.68 (0.133, 0.132)(0.133, 0.132) 135135
실시예 83Example 83 B5B5 E3E3 3.563.56 4.594.59 (0.133, 0.130)(0.133, 0.130) 131131
실시예 84Example 84 B5B5 E4E4 3.663.66 4.224.22 (0.133, 0.131)(0.133, 0.131) 121121
실시예 85Example 85 B5B5 E5E5 3.743.74 4.184.18 (0.133, 0.134)(0.133, 0.134) 123123
실시예 86Example 86 B5B5 E6E6 3.663.66 4.164.16 (0.133, 0.131)(0.133, 0.131) 118118
실시예 87Example 87 B5B5 E7E7 3.563.56 4.634.63 (0.135, 0.130)(0.135, 0.130) 133133
실시예 88Example 88 B5B5 E8E8 3.423.42 4.774.77 (0.133, 0.133)(0.133, 0.133) 143143
실시예 89Example 89 B5B5 E9E9 3.453.45 4.634.63 (0.133, 0.132)(0.133, 0.132) 153153
실시예 90Example 90 B5B5 E10E10 3.453.45 4.774.77 (0.133, 0.130)(0.133, 0.130) 138138
실시예 91Example 91 B5B5 E11E11 3.423.42 4.684.68 (0.133, 0.130)(0.133, 0.130) 153153
실시예 92Example 92 B5B5 E12E12 3.493.49 4.784.78 (0.133, 0.131)(0.133, 0.131) 132132
실시예 93Example 93 B5B5 E13E13 3.523.52 4.694.69 (0.133, 0.134)(0.133, 0.134) 127127
실시예 94Example 94 B5B5 E14E14 3.453.45 4.594.59 (0.133, 0.131)(0.133, 0.131) 162162
실시예 95Example 95 B5B5 E15E15 3.493.49 4.594.59 (0.135, 0.130)(0.135, 0.130) 132132
실시예 96Example 96 B5B5 E16E16 3.453.45 4.634.63 (0.133, 0.133)(0.133, 0.133) 150150
실시예 97Example 97 B5B5 E17E17 3.443.44 4.684.68 (0.133, 0.132)(0.133, 0.132) 148148
실시예 98Example 98 B5B5 E18E18 3.493.49 4.444.44 (0.133, 0.130)(0.133, 0.130) 138138
실시예 99Example 99 B5B5 E19E19 3.453.45 4.644.64 (0.133, 0.131)(0.133, 0.131) 151151
실시예 100Example 100 B5B5 E20E20 3.493.49 4.594.59 (0.133, 0.134)(0.133, 0.134) 149149
실시예 101Example 101 B6B6 E1E1 3.333.33 4.824.82 (0.133, 0.131)(0.133, 0.131) 135135
실시예 102Example 102 B6B6 E2E2 3.473.47 4.774.77 (0.135, 0.130)(0.135, 0.130) 124124
실시예 103Example 103 B6B6 E3E3 3.503.50 4.674.67 (0.133, 0.133)(0.133, 0.133) 120120
실시예 104Example 104 B6B6 E4E4 3.603.60 4.304.30 (0.133, 0.132)(0.133, 0.132) 111111
실시예 105Example 105 B6B6 E5E5 3.683.68 4.264.26 (0.133, 0.130)(0.133, 0.130) 113113
실시예 106Example 106 B6B6 E6E6 3.603.60 4.244.24 (0.133, 0.130)(0.133, 0.130) 108108
실시예 107Example 107 B6B6 E7E7 3.503.50 4.724.72 (0.133, 0.131)(0.133, 0.131) 122122
실시예 108Example 108 B6B6 E8E8 3.373.37 4.864.86 (0.133, 0.134)(0.133, 0.134) 131131
실시예 109Example 109 B6B6 E9E9 3.403.40 4.724.72 (0.133, 0.131)(0.133, 0.131) 140140
실시예 110Example 110 B6B6 E10E10 3.403.40 4.864.86 (0.135, 0.130)(0.135, 0.130) 127127
실시예 111Example 111 B6B6 E11E11 3.373.37 4.774.77 (0.133, 0.133)(0.133, 0.133) 140140
실시예 112Example 112 B6B6 E12E12 3.433.43 4.874.87 (0.133, 0.132)(0.133, 0.132) 122122
실시예 113Example 113 B6B6 E13E13 3.473.47 4.784.78 (0.133, 0.130)(0.133, 0.130) 117117
실시예 114Example 114 B6B6 E14E14 3.403.40 4.674.67 (0.133, 0.131)(0.133, 0.131) 149149
실시예 115Example 115 B6B6 E15E15 3.433.43 4.684.68 (0.133, 0.134)(0.133, 0.134) 121121
실시예 116Example 116 B6B6 E16E16 3.403.40 4.724.72 (0.133, 0.131)(0.133, 0.131) 138138
실시예 117Example 117 B6B6 E17E17 3.383.38 4.774.77 (0.135, 0.130)(0.135, 0.130) 136136
실시예 118Example 118 B6B6 E18E18 3.433.43 4.534.53 (0.133, 0.133)(0.133, 0.133) 127127
실시예 119Example 119 B6B6 E19E19 3.403.40 4.724.72 (0.133, 0.132)(0.133, 0.132) 138138
실시예 120Example 120 B6B6 E20E20 3.433.43 4.684.68 (0.133, 0.130)(0.133, 0.130) 137137
실시예 121Example 121 B7B7 E1E1 3.333.33 4.864.86 (0.133, 0.130)(0.133, 0.130) 129129
실시예 122Example 122 B7B7 E2E2 3.473.47 4.824.82 (0.133, 0.131)(0.133, 0.131) 119119
실시예 123Example 123 B7B7 E3E3 3.503.50 4.724.72 (0.133, 0.134)(0.133, 0.134) 115115
실시예 124Example 124 B7B7 E4E4 3.603.60 4.344.34 (0.133, 0.131)(0.133, 0.131) 106106
실시예 125Example 125 B7B7 E5E5 3.683.68 4.304.30 (0.135, 0.130)(0.135, 0.130) 108108
실시예 126Example 126 B7B7 E6E6 3.603.60 4.284.28 (0.133, 0.133)(0.133, 0.133) 103103
실시예 127Example 127 B7B7 E7E7 3.503.50 4.774.77 (0.133, 0.132)(0.133, 0.132) 116116
실시예 128Example 128 B7B7 E8E8 3.373.37 4.914.91 (0.133, 0.130)(0.133, 0.130) 125125
실시예 129Example 129 B7B7 E9E9 3.403.40 4.774.77 (0.133, 0.131)(0.133, 0.131) 134134
실시예 130Example 130 B7B7 E10E10 3.403.40 4.914.91 (0.133, 0.134)(0.133, 0.134) 121121
실시예 131Example 131 B7B7 E11E11 3.373.37 4.824.82 (0.133, 0.131)(0.133, 0.131) 134134
실시예 132Example 132 B7B7 E12E12 3.433.43 4.924.92 (0.135, 0.130)(0.135, 0.130) 116116
실시예 133Example 133 B7B7 E13E13 3.473.47 4.824.82 (0.133, 0.133)(0.133, 0.133) 111111
실시예 134Example 134 B7B7 E14E14 3.403.40 4.724.72 (0.133, 0.132)(0.133, 0.132) 142142
실시예 135Example 135 B7B7 E15E15 3.433.43 4.734.73 (0.133, 0.130)(0.133, 0.130) 116116
실시예 136Example 136 B7B7 E16E16 3.403.40 4.774.77 (0.133, 0.130)(0.133, 0.130) 131131
실시예 137Example 137 B7B7 E17E17 3.383.38 4.824.82 (0.133, 0.131)(0.133, 0.131) 130130
실시예 138Example 138 B7B7 E18E18 3.433.43 4.574.57 (0.133, 0.134)(0.133, 0.134) 121121
실시예 139Example 139 B7B7 E19E19 3.403.40 4.774.77 (0.133, 0.131)(0.133, 0.131) 132132
실시예 140Example 140 B7B7 E20E20 3.433.43 4.724.72 (0.135, 0.130)(0.135, 0.130) 131131
실시예 141Example 141 B8B8 E1E1 3.503.50 4.604.60 (0.133, 0.133)(0.133, 0.133) 173173
실시예 142Example 142 B8B8 E2E2 3.643.64 4.554.55 (0.133, 0.132)(0.133, 0.132) 159159
실시예 143Example 143 B8B8 E3E3 3.683.68 4.464.46 (0.133, 0.130)(0.133, 0.130) 154154
실시예 144Example 144 B8B8 E4E4 3.793.79 4.104.10 (0.133, 0.131)(0.133, 0.131) 142142
실시예 145Example 145 B8B8 E5E5 3.863.86 4.064.06 (0.133, 0.134)(0.133, 0.134) 144144
실시예 146Example 146 B8B8 E6E6 3.793.79 4.054.05 (0.133, 0.131)(0.133, 0.131) 138138
실시예 147Example 147 B8B8 E7E7 3.683.68 4.514.51 (0.135, 0.130)(0.135, 0.130) 156156
실시예 148Example 148 B8B8 E8E8 3.543.54 4.644.64 (0.133, 0.133)(0.133, 0.133) 167167
실시예 149Example 149 B8B8 E9E9 3.573.57 4.514.51 (0.133, 0.132)(0.133, 0.132) 179179
실시예 150Example 150 B8B8 E10E10 3.573.57 4.644.64 (0.133, 0.130)(0.133, 0.130) 162162
실시예 151Example 151 B8B8 E11E11 3.543.54 4.554.55 (0.133, 0.130)(0.133, 0.130) 179179
실시예 152Example 152 B8B8 E12E12 3.613.61 4.654.65 (0.133, 0.131)(0.133, 0.131) 155155
실시예 153Example 153 B8B8 E13E13 3.643.64 4.564.56 (0.133, 0.134)(0.133, 0.134) 149149
실시예 154Example 154 B8B8 E14E14 3.573.57 4.464.46 (0.133, 0.131)(0.133, 0.131) 190190
실시예 155Example 155 B8B8 E15E15 3.613.61 4.474.47 (0.135, 0.130)(0.135, 0.130) 155155
실시예 156Example 156 B8B8 E16E16 3.573.57 4.514.51 (0.133, 0.133)(0.133, 0.133) 176176
실시예 157Example 157 B8B8 E17E17 3.553.55 4.554.55 (0.133, 0.132)(0.133, 0.132) 174174
실시예 158Example 158 B8B8 E18E18 3.613.61 4.324.32 (0.133, 0.130)(0.133, 0.130) 162162
실시예 159Example 159 B8B8 E19E19 3.573.57 4.514.51 (0.133, 0.131)(0.133, 0.131) 177177
실시예 160Example 160 B8B8 E20E20 3.613.61 4.474.47 (0.133, 0.134)(0.133, 0.134) 175175
비교예 1Comparative Example 1 E1E1 3.573.57 4.044.04 (0.133, 0.131)(0.133, 0.131) 7575
비교예 2Comparative Example 2 E2E2 3.713.71 4.004.00 (0.135, 0.130)(0.135, 0.130) 6969
비교예 3Comparative Example 3 E3E3 3.753.75 3.923.92 (0.133, 0.133)(0.133, 0.133) 6767
비교예 4Comparative Example 4 E4E4 3.863.86 3.603.60 (0.133, 0.132)(0.133, 0.132) 6262
비교예 5Comparative Example 5 E5E5 3.943.94 3.573.57 (0.133, 0.130)(0.133, 0.130) 6363
비교예 6Comparative Example 6 E6E6 3.863.86 3.553.55 (0.133, 0.130)(0.133, 0.130) 6060
비교예 7Comparative Example 7 E7E7 3.753.75 3.963.96 (0.133, 0.131)(0.133, 0.131) 6868
비교예 8Comparative Example 8 E8E8 3.613.61 4.084.08 (0.133, 0.134)(0.133, 0.134) 7373
비교예 9Comparative Example 9 E9E9 3.643.64 3.963.96 (0.133, 0.131)(0.133, 0.131) 7878
비교예 10Comparative Example 10 E10E10 3.643.64 4.084.08 (0.135, 0.130)(0.135, 0.130) 7171
비교예 11Comparative Example 11 E11E11 3.613.61 4.004.00 (0.133, 0.133)(0.133, 0.133) 7878
비교예 12Comparative Example 12 E12E12 3.683.68 4.094.09 (0.133, 0.132)(0.133, 0.132) 6868
비교예 13Comparative Example 13 E13E13 3.713.71 4.004.00 (0.133, 0.130)(0.133, 0.130) 6565
비교예 14Comparative Example 14 E14E14 3.643.64 3.923.92 (0.133, 0.131)(0.133, 0.131) 8383
비교예 15Comparative Example 15 E15E15 3.683.68 3.923.92 (0.133, 0.134)(0.133, 0.134) 6767
비교예 16Comparative Example 16 E16E16 3.643.64 3.963.96 (0.133, 0.131)(0.133, 0.131) 7676
비교예 17Comparative Example 17 E17E17 3.623.62 4.004.00 (0.135, 0.130)(0.135, 0.130) 7676
비교예 18Comparative Example 18 E18E18 3.683.68 3.803.80 (0.133, 0.133)(0.133, 0.133) 7171
비교예 19Comparative Example 19 E19E19 3.643.64 3.963.96 (0.133, 0.132)(0.133, 0.132) 7777
비교예 20Comparative Example 20 E20E20 3.683.68 3.923.92 (0.133, 0.130)(0.133, 0.130) 7676
비교예 21Comparative Example 21 ET-1ET-1 4.414.41 1.511.51 (0.133, 0.130)(0.133, 0.130) 1616
비교예 22Comparative Example 22 ET-2ET-2 4.324.32 1.501.50 (0.133, 0.131)(0.133, 0.131) 1616
비교예 23Comparative Example 23 ET-3ET-3 4.004.00 1.711.71 (0.133, 0.134)(0.133, 0.134) 2020
비교예 24Comparative Example 24 ET-4ET-4 4.044.04 1.691.69 (0.133, 0.131)(0.133, 0.131) 1919
비교예 25Comparative Example 25 ET-5ET-5 3.963.96 2.052.05 (0.135, 0.130)(0.135, 0.130) 4646
비교예 26Comparative Example 26 ET-6ET-6 4.124.12 1.661.66 (0.133, 0.133)(0.133, 0.133) 2929
비교예 27Comparative Example 27 ET-7ET-7 4.164.16 1.641.64 (0.133, 0.132)(0.133, 0.132) 2929
비교예 28Comparative Example 28 ET-8ET-8 3.963.96 2.142.14 (0.133, 0.130)(0.133, 0.130) 4848
비교예 29Comparative Example 29 ET-9ET-9 4.244.24 1.631.63 (0.133, 0.131)(0.133, 0.131) 2828
비교예 30Comparative Example 30 ET-10ET-10 4.374.37 1.581.58 (0.133, 0.134)(0.133, 0.134) 5050
비교예 31Comparative Example 31 ET-11ET-11 4.634.63 1.561.56 (0.133, 0.131)(0.133, 0.131) 4141
비교예 32Comparative Example 32 ET-12ET-12 4.634.63 1.241.24 (0.135, 0.130)(0.135, 0.130) 1212
비교예 33Comparative Example 33 ET-13ET-13 4.184.18 3.023.02 (0.133, 0.133)(0.133, 0.133) 4848
비교예 34Comparative Example 34 ET-14ET-14 4.134.13 3.053.05 (0.133, 0.132)(0.133, 0.132) 4444
비교예 35Comparative Example 35 ET-15ET-15 4.384.38 2.962.96 (0.133, 0.130)(0.133, 0.130) 4949
비교예 36Comparative Example 36 ET-16ET-16 4.434.43 2.902.90 (0.133, 0.130)(0.133, 0.130) 5050
비교예 37Comparative Example 37 ET-17ET-17 4.474.47 2.812.81 (0.133, 0.131)(0.133, 0.131) 5151
비교예 38Comparative Example 38 ET-18ET-18 4.344.34 2.842.84 (0.133, 0.134)(0.133, 0.134) 5151
비교예 39Comparative Example 39 ET-19ET-19 4.364.36 1.651.65 (0.133, 0.131)(0.133, 0.131) 3838
비교예 40Comparative Example 40 B1B1 ET-1ET-1 4.204.20 1.681.68 (0.135, 0.130)(0.135, 0.130) 3333
비교예 41Comparative Example 41 B1B1 ET-2ET-2 4.124.12 1.671.67 (0.133, 0.133)(0.133, 0.133) 3131
비교예 42Comparative Example 42 B1B1 ET-3ET-3 3.813.81 1.901.90 (0.133, 0.132)(0.133, 0.132) 3939
비교예 43Comparative Example 43 B1B1 ET-4ET-4 3.853.85 1.881.88 (0.133, 0.130)(0.133, 0.130) 3838
비교예 44Comparative Example 44 B1B1 ET-5ET-5 3.773.77 2.282.28 (0.133, 0.131)(0.133, 0.131) 9292
비교예 45Comparative Example 45 B1B1 ET-6ET-6 3.923.92 1.841.84 (0.133, 0.134)(0.133, 0.134) 5959
비교예 46Comparative Example 46 B1B1 ET-7ET-7 3.963.96 1.821.82 (0.133, 0.131)(0.133, 0.131) 5757
비교예 47Comparative Example 47 B1B1 ET-8ET-8 3.773.77 2.382.38 (0.135, 0.130)(0.135, 0.130) 9696
비교예 48Comparative Example 48 B1B1 ET-9ET-9 4.044.04 1.811.81 (0.133, 0.133)(0.133, 0.133) 5656
비교예 49Comparative Example 49 B1B1 ET-10ET-10 4.164.16 1.751.75 (0.133, 0.132)(0.133, 0.132) 100100
비교예 50Comparative Example 50 B1B1 ET-11ET-11 4.414.41 1.731.73 (0.133, 0.130)(0.133, 0.130) 8383
비교예 51Comparative Example 51 B1B1 ET-12ET-12 4.414.41 1.371.37 (0.133, 0.130)(0.133, 0.130) 2424
비교예 52Comparative Example 52 B1B1 ET-13ET-13 3.983.98 3.363.36 (0.133, 0.131)(0.133, 0.131) 9797
비교예 53Comparative Example 53 B1B1 ET-14ET-14 3.943.94 3.393.39 (0.133, 0.134)(0.133, 0.134) 8787
비교예 54Comparative Example 54 B1B1 ET-15ET-15 4.174.17 3.293.29 (0.133, 0.131)(0.133, 0.131) 9898
비교예 55Comparative Example 55 B1B1 ET-16ET-16 4.224.22 3.223.22 (0.135, 0.130)(0.135, 0.130) 9999
비교예 56Comparative Example 56 B1B1 ET-17ET-17 4.264.26 3.133.13 (0.133, 0.133)(0.133, 0.133) 102102
비교예 57Comparative Example 57 B1B1 ET-18ET-18 4.134.13 3.163.16 (0.133, 0.132)(0.133, 0.132) 101101
비교예 58Comparative Example 58 B1B1 ET-19ET-19 4.154.15 1.831.83 (0.133, 0.130)(0.133, 0.130) 7575
비교예 59Comparative Example 59 B2B2 ET-1ET-1 4.084.08 1.731.73 (0.133, 0.131)(0.133, 0.131) 2525
비교예 60Comparative Example 60 B2B2 ET-2ET-2 3.993.99 1.731.73 (0.133, 0.134)(0.133, 0.134) 2424
비교예 61Comparative Example 61 B2B2 ET-3ET-3 3.693.69 1.961.96 (0.133, 0.131)(0.133, 0.131) 3030
비교예 62Comparative Example 62 B2B2 ET-4ET-4 3.733.73 1.941.94 (0.135, 0.130)(0.135, 0.130) 3030
비교예 63Comparative Example 63 B2B2 ET-5ET-5 3.663.66 2.352.35 (0.133, 0.133)(0.133, 0.133) 7171
비교예 64Comparative Example 64 B2B2 ET-6ET-6 3.803.80 1.901.90 (0.133, 0.132)(0.133, 0.132) 4646
비교예 65Comparative Example 65 B2B2 ET-7ET-7 3.843.84 1.881.88 (0.133, 0.130)(0.133, 0.130) 4545
비교예 66Comparative Example 66 B2B2 ET-8ET-8 3.663.66 2.452.45 (0.133, 0.130)(0.133, 0.130) 7575
비교예 67Comparative Example 67 B2B2 ET-9ET-9 3.923.92 1.861.86 (0.133, 0.131)(0.133, 0.131) 4444
비교예 68Comparative Example 68 B2B2 ET-10ET-10 4.034.03 1.811.81 (0.133, 0.134)(0.133, 0.134) 7878
비교예 69Comparative Example 69 B2B2 ET-11ET-11 4.274.27 1.791.79 (0.133, 0.131)(0.133, 0.131) 6464
비교예 70Comparative Example 70 B2B2 ET-12ET-12 4.284.28 1.421.42 (0.135, 0.130)(0.135, 0.130) 1919
비교예 71Comparative Example 71 B2B2 ET-13ET-13 3.863.86 3.473.47 (0.133, 0.133)(0.133, 0.133) 7575
비교예 72Comparative Example 72 B2B2 ET-14ET-14 3.823.82 3.503.50 (0.133, 0.132)(0.133, 0.132) 6868
비교예 73Comparative Example 73 B2B2 ET-15ET-15 4.054.05 3.403.40 (0.133, 0.130)(0.133, 0.130) 7777
비교예 74Comparative Example 74 B2B2 ET-16ET-16 4.094.09 3.333.33 (0.133, 0.131)(0.133, 0.131) 7777
비교예 75Comparative Example 75 B2B2 ET-17ET-17 4.134.13 3.233.23 (0.133, 0.134)(0.133, 0.134) 8080
비교예 76Comparative Example 76 B2B2 ET-18ET-18 4.014.01 3.263.26 (0.133, 0.131)(0.133, 0.131) 7979
비교예 77Comparative Example 77 B2B2 ET-19ET-19 4.024.02 1.891.89 (0.135, 0.130)(0.135, 0.130) 5959
비교예 78Comparative Example 78 B3B3 ET-1ET-1 4.164.16 1.701.70 (0.133, 0.133)(0.133, 0.133) 3131
비교예 79Comparative Example 79 B3B3 ET-2ET-2 4.084.08 1.701.70 (0.133, 0.132)(0.133, 0.132) 2929
비교예 80Comparative Example 80 B3B3 ET-3ET-3 3.773.77 1.931.93 (0.133, 0.130)(0.133, 0.130) 3737
비교예 81Comparative Example 81 B3B3 ET-4ET-4 3.813.81 1.911.91 (0.133, 0.130)(0.133, 0.130) 3636
비교예 82Comparative Example 82 B3B3 ET-5ET-5 3.733.73 2.312.31 (0.133, 0.131)(0.133, 0.131) 8686
비교예 83Comparative Example 83 B3B3 ET-6ET-6 3.883.88 1.871.87 (0.133, 0.134)(0.133, 0.134) 5555
비교예 84Comparative Example 84 B3B3 ET-7ET-7 3.923.92 1.851.85 (0.133, 0.131)(0.133, 0.131) 5454
비교예 85Comparative Example 85 B3B3 ET-8ET-8 3.743.74 2.412.41 (0.135, 0.130)(0.135, 0.130) 9090
비교예 86Comparative Example 86 B3B3 ET-9ET-9 4.004.00 1.831.83 (0.133, 0.133)(0.133, 0.133) 5353
비교예 87Comparative Example 87 B3B3 ET-10ET-10 4.124.12 1.781.78 (0.133, 0.132)(0.133, 0.132) 9494
비교예 88Comparative Example 88 B3B3 ET-11ET-11 4.364.36 1.761.76 (0.133, 0.130)(0.133, 0.130) 7878
비교예 89Comparative Example 89 B3B3 ET-12ET-12 4.374.37 1.391.39 (0.133, 0.131)(0.133, 0.131) 2323
비교예 90Comparative Example 90 B3B3 ET-13ET-13 3.943.94 3.403.40 (0.133, 0.134)(0.133, 0.134) 9191
비교예 91Comparative Example 91 B3B3 ET-14ET-14 3.903.90 3.443.44 (0.133, 0.131)(0.133, 0.131) 8282
비교예 92Comparative Example 92 B3B3 ET-15ET-15 4.134.13 3.343.34 (0.135, 0.130)(0.135, 0.130) 9393
비교예 93Comparative Example 93 B3B3 ET-16ET-16 4.174.17 3.273.27 (0.133, 0.133)(0.133, 0.133) 9494
비교예 94Comparative Example 94 B3B3 ET-17ET-17 4.214.21 3.173.17 (0.133, 0.132)(0.133, 0.132) 9696
비교예 95Comparative Example 95 B3B3 ET-18ET-18 4.094.09 3.203.20 (0.133, 0.130)(0.133, 0.130) 9595
비교예 96Comparative Example 96 B3B3 ET-19ET-19 4.114.11 1.851.85 (0.133, 0.130)(0.133, 0.130) 7171
비교예 97Comparative Example 97 B4B4 ET-1ET-1 4.294.29 1.631.63 (0.133, 0.131)(0.133, 0.131) 3838
비교예 98Comparative Example 98 B4B4 ET-2ET-2 4.204.20 1.621.62 (0.133, 0.134)(0.133, 0.134) 3636
비교예 99Comparative Example 99 B4B4 ET-3ET-3 3.883.88 1.841.84 (0.133, 0.131)(0.133, 0.131) 4545
비교예 100Comparative Example 100 B4B4 ET-4ET-4 3.923.92 1.821.82 (0.135, 0.130)(0.135, 0.130) 4444
비교예 101Comparative Example 101 B4B4 ET-5ET-5 3.853.85 2.212.21 (0.133, 0.133)(0.133, 0.133) 106106
비교예 102Comparative Example 102 B4B4 ET-6ET-6 4.004.00 1.791.79 (0.133, 0.132)(0.133, 0.132) 6868
비교예 103Comparative Example 103 B4B4 ET-7ET-7 4.044.04 1.771.77 (0.133, 0.130)(0.133, 0.130) 6767
비교예 104Comparative Example 104 B4B4 ET-8ET-8 3.853.85 2.302.30 (0.133, 0.131)(0.133, 0.131) 111111
비교예 105Comparative Example 105 B4B4 ET-9ET-9 4.124.12 1.751.75 (0.133, 0.134)(0.133, 0.134) 6565
비교예 106Comparative Example 106 B4B4 ET-10ET-10 4.244.24 1.701.70 (0.133, 0.131)(0.133, 0.131) 116116
비교예 107Comparative Example 107 B4B4 ET-11ET-11 4.504.50 1.681.68 (0.135, 0.130)(0.135, 0.130) 9696
비교예 108Comparative Example 108 B4B4 ET-12ET-12 4.504.50 1.331.33 (0.133, 0.133)(0.133, 0.133) 2828
비교예 109Comparative Example 109 B4B4 ET-13ET-13 4.064.06 3.263.26 (0.133, 0.132)(0.133, 0.132) 112112
비교예 110Comparative Example 110 B4B4 ET-14ET-14 4.024.02 3.293.29 (0.133, 0.130)(0.133, 0.130) 101101
비교예 111Comparative Example 111 B4B4 ET-15ET-15 4.264.26 3.193.19 (0.133, 0.130)(0.133, 0.130) 114114
비교예 112Comparative Example 112 B4B4 ET-16ET-16 4.304.30 3.133.13 (0.133, 0.131)(0.133, 0.131) 115115
비교예 113Comparative Example 113 B4B4 ET-17ET-17 4.344.34 3.033.03 (0.133, 0.134)(0.133, 0.134) 119119
비교예 114Comparative Example 114 B4B4 ET-18ET-18 4.224.22 3.063.06 (0.133, 0.131)(0.133, 0.131) 117117
비교예 115Comparative Example 115 B4B4 ET-19ET-19 4.234.23 1.771.77 (0.135, 0.130)(0.135, 0.130) 8787
비교예 116Comparative Example 116 B5B5 ET-1ET-1 4.194.19 1.671.67 (0.133, 0.133)(0.133, 0.133) 3232
비교예 117Comparative Example 117 B5B5 ET-2ET-2 4.104.10 1.661.66 (0.133, 0.132)(0.133, 0.132) 3131
비교예 118Comparative Example 118 B5B5 ET-3ET-3 3.793.79 1.891.89 (0.133, 0.130)(0.133, 0.130) 3838
비교예 119Comparative Example 119 B5B5 ET-4ET-4 3.833.83 1.871.87 (0.133, 0.131)(0.133, 0.131) 3737
비교예 120Comparative Example 120 B5B5 ET-5ET-5 3.753.75 2.272.27 (0.133, 0.134)(0.133, 0.134) 9090
비교예 121Comparative Example 121 B5B5 ET-6ET-6 3.913.91 1.831.83 (0.133, 0.131)(0.133, 0.131) 5757
비교예 122Comparative Example 122 B5B5 ET-7ET-7 3.953.95 1.821.82 (0.135, 0.130)(0.135, 0.130) 5656
비교예 123Comparative Example 123 B5B5 ET-8ET-8 3.763.76 2.362.36 (0.133, 0.133)(0.133, 0.133) 9494
비교예 124Comparative Example 124 B5B5 ET-9ET-9 4.024.02 1.801.80 (0.133, 0.132)(0.133, 0.132) 5555
비교예 125Comparative Example 125 B5B5 ET-10ET-10 4.144.14 1.741.74 (0.133, 0.130)(0.133, 0.130) 9898
비교예 126Comparative Example 126 B5B5 ET-11ET-11 4.394.39 1.721.72 (0.133, 0.130)(0.133, 0.130) 8181
비교예 127Comparative Example 127 B5B5 ET-12ET-12 4.394.39 1.371.37 (0.133, 0.131)(0.133, 0.131) 2424
비교예 128Comparative Example 128 B5B5 ET-13ET-13 3.963.96 3.343.34 (0.133, 0.134)(0.133, 0.134) 9595
비교예 129Comparative Example 129 B5B5 ET-14ET-14 3.923.92 3.373.37 (0.133, 0.131)(0.133, 0.131) 8585
비교예 130Comparative Example 130 B5B5 ET-15ET-15 4.164.16 3.273.27 (0.135, 0.130)(0.135, 0.130) 9696
비교예 131Comparative Example 131 B5B5 ET-16ET-16 4.204.20 3.213.21 (0.133, 0.133)(0.133, 0.133) 9797
비교예 132Comparative Example 132 B5B5 ET-17ET-17 4.244.24 3.113.11 (0.133, 0.132)(0.133, 0.132) 100100
비교예 133Comparative Example 133 B5B5 ET-18ET-18 4.124.12 3.143.14 (0.133, 0.130)(0.133, 0.130) 9999
비교예 134Comparative Example 134 B5B5 ET-19ET-19 4.134.13 1.821.82 (0.133, 0.131)(0.133, 0.131) 7474
비교예 135Comparative Example 135 B6B6 ET-1ET-1 4.124.12 1.701.70 (0.133, 0.134)(0.133, 0.134) 2929
비교예 136Comparative Example 136 B6B6 ET-2ET-2 4.044.04 1.701.70 (0.133, 0.131)(0.133, 0.131) 2828
비교예 137Comparative Example 137 B6B6 ET-3ET-3 3.733.73 1.931.93 (0.135, 0.130)(0.135, 0.130) 3535
비교예 138Comparative Example 138 B6B6 ET-4ET-4 3.773.77 1.911.91 (0.133, 0.133)(0.133, 0.133) 3434
비교예 139Comparative Example 139 B6B6 ET-5ET-5 3.693.69 2.312.31 (0.133, 0.132)(0.133, 0.132) 8282
비교예 140Comparative Example 140 B6B6 ET-6ET-6 3.843.84 1.871.87 (0.133, 0.130)(0.133, 0.130) 5353
비교예 141Comparative Example 141 B6B6 ET-7ET-7 3.883.88 1.851.85 (0.133, 0.130)(0.133, 0.130) 5252
비교예 142Comparative Example 142 B6B6 ET-8ET-8 3.703.70 2.412.41 (0.133, 0.131)(0.133, 0.131) 8686
비교예 143Comparative Example 143 B6B6 ET-9ET-9 3.963.96 1.831.83 (0.133, 0.134)(0.133, 0.134) 5151
비교예 144Comparative Example 144 B6B6 ET-10ET-10 4.074.07 1.781.78 (0.133, 0.131)(0.133, 0.131) 9090
비교예 145Comparative Example 145 B6B6 ET-11ET-11 4.324.32 1.761.76 (0.135, 0.130)(0.135, 0.130) 7474
비교예 146Comparative Example 146 B6B6 ET-12ET-12 4.324.32 1.391.39 (0.133, 0.133)(0.133, 0.133) 2222
비교예 147Comparative Example 147 B6B6 ET-13ET-13 3.903.90 3.403.40 (0.133, 0.132)(0.133, 0.132) 8787
비교예 148Comparative Example 148 B6B6 ET-14ET-14 3.863.86 3.443.44 (0.133, 0.130)(0.133, 0.130) 7878
비교예 149Comparative Example 149 B6B6 ET-15ET-15 4.094.09 3.343.34 (0.133, 0.131)(0.133, 0.131) 8989
비교예 150Comparative Example 150 B6B6 ET-16ET-16 4.134.13 3.273.27 (0.133, 0.134)(0.133, 0.134) 8989
비교예 151Comparative Example 151 B6B6 ET-17ET-17 4.174.17 3.173.17 (0.133, 0.131)(0.133, 0.131) 9292
비교예 152Comparative Example 152 B6B6 ET-18ET-18 4.054.05 3.203.20 (0.135, 0.130)(0.135, 0.130) 9191
비교예 153Comparative Example 153 B6B6 ET-19ET-19 4.074.07 1.851.85 (0.133, 0.133)(0.133, 0.133) 6868
비교예 154Comparative Example 154 B7B7 ET-1ET-1 4.124.12 1.721.72 (0.133, 0.132)(0.133, 0.132) 2828
비교예 155Comparative Example 155 B7B7 ET-2ET-2 4.044.04 1.711.71 (0.133, 0.130)(0.133, 0.130) 2727
비교예 156Comparative Example 156 B7B7 ET-3ET-3 3.733.73 1.951.95 (0.133, 0.130)(0.133, 0.130) 3434
비교예 157Comparative Example 157 B7B7 ET-4ET-4 3.773.77 1.931.93 (0.133, 0.131)(0.133, 0.131) 3333
비교예 158Comparative Example 158 B7B7 ET-5ET-5 3.693.69 2.332.33 (0.133, 0.134)(0.133, 0.134) 7979
비교예 159Comparative Example 159 B7B7 ET-6ET-6 3.843.84 1.891.89 (0.133, 0.131)(0.133, 0.131) 5050
비교예 160Comparative Example 160 B7B7 ET-7ET-7 3.883.88 1.871.87 (0.135, 0.130)(0.135, 0.130) 4949
비교예 161Comparative Example 161 B7B7 ET-8ET-8 3.703.70 2.432.43 (0.133, 0.133)(0.133, 0.133) 8383
비교예 162Comparative Example 162 B7B7 ET-9ET-9 3.963.96 1.851.85 (0.133, 0.132)(0.133, 0.132) 4848
비교예 163Comparative Example 163 B7B7 ET-10ET-10 4.074.07 1.791.79 (0.133, 0.130)(0.133, 0.130) 8686
비교예 164Comparative Example 164 B7B7 ET-11ET-11 4.324.32 1.771.77 (0.133, 0.131)(0.133, 0.131) 7171
비교예 165Comparative Example 165 B7B7 ET-12ET-12 4.324.32 1.411.41 (0.133, 0.134)(0.133, 0.134) 2121
비교예 166Comparative Example 166 B7B7 ET-13ET-13 3.903.90 3.443.44 (0.133, 0.131)(0.133, 0.131) 8383
비교예 167Comparative Example 167 B7B7 ET-14ET-14 3.863.86 3.473.47 (0.135, 0.130)(0.135, 0.130) 7575
비교예 168Comparative Example 168 B7B7 ET-15ET-15 4.094.09 3.373.37 (0.133, 0.133)(0.133, 0.133) 8585
비교예 169Comparative Example 169 B7B7 ET-16ET-16 4.134.13 3.303.30 (0.133, 0.132)(0.133, 0.132) 8585
비교예 170Comparative Example 170 B7B7 ET-17ET-17 4.174.17 3.203.20 (0.133, 0.130)(0.133, 0.130) 8888
비교예 171Comparative Example 171 B7B7 ET-18ET-18 4.054.05 3.233.23 (0.133, 0.130)(0.133, 0.130) 8787
비교예 172Comparative Example 172 B7B7 ET-19ET-19 4.074.07 1.871.87 (0.133, 0.131)(0.133, 0.131) 6565
비교예 173Comparative Example 173 B8B8 ET-1ET-1 4.334.33 1.631.63 (0.133, 0.134)(0.133, 0.134) 3838
비교예 174Comparative Example 174 B8B8 ET-2ET-2 4.244.24 1.621.62 (0.133, 0.131)(0.133, 0.131) 3636
비교예 175Comparative Example 175 B8B8 ET-3ET-3 3.923.92 1.841.84 (0.135, 0.130)(0.135, 0.130) 4545
비교예 176Comparative Example 176 B8B8 ET-4ET-4 3.963.96 1.821.82 (0.133, 0.133)(0.133, 0.133) 4444
비교예 177Comparative Example 177 B8B8 ET-5ET-5 3.883.88 2.212.21 (0.133, 0.132)(0.133, 0.132) 105105
비교예 178Comparative Example 178 B8B8 ET-6ET-6 4.044.04 1.781.78 (0.133, 0.130)(0.133, 0.130) 6767
비교예 179Comparative Example 179 B8B8 ET-7ET-7 4.084.08 1.771.77 (0.133, 0.131)(0.133, 0.131) 6666
비교예 180Comparative Example 180 B8B8 ET-8ET-8 3.893.89 2.302.30 (0.133, 0.134)(0.133, 0.134) 110110
비교예 181Comparative Example 181 B8B8 ET-9ET-9 4.164.16 1.751.75 (0.133, 0.131)(0.133, 0.131) 6565
비교예 182Comparative Example 182 B8B8 ET-10ET-10 4.284.28 1.691.69 (0.135, 0.130)(0.135, 0.130) 115115
비교예 183Comparative Example 183 B8B8 ET-11ET-11 4.544.54 1.681.68 (0.133, 0.133)(0.133, 0.133) 9595
비교예 184Comparative Example 184 B8B8 ET-12ET-12 4.544.54 1.331.33 (0.133, 0.132)(0.133, 0.132) 2828
비교예 185Comparative Example 185 B8B8 ET-13ET-13 4.104.10 3.253.25 (0.133, 0.130)(0.133, 0.130) 111111
비교예 186Comparative Example 186 B8B8 ET-14ET-14 4.064.06 3.283.28 (0.133, 0.130)(0.133, 0.130) 100100
비교예 187Comparative Example 187 B8B8 ET-15ET-15 4.304.30 3.183.18 (0.133, 0.131)(0.133, 0.131) 113113
비교예 188Comparative Example 188 B8B8 ET-16ET-16 4.344.34 3.123.12 (0.133, 0.134)(0.133, 0.134) 114114
비교예 189Comparative Example 189 B8B8 ET-17ET-17 4.394.39 3.033.03 (0.133, 0.131)(0.133, 0.131) 118118
비교예 190Comparative Example 190 B8B8 ET-18ET-18 4.264.26 3.063.06 (0.135, 0.130)(0.135, 0.130) 116116
비교예 191Comparative Example 191 B8B8 ET-19ET-19 4.274.27 1.771.77 (0.133, 0.133)(0.133, 0.133) 8686
상기 표 1에 기재된 바와 같이, 본 발명의 화학식 1로 표시되는 화합물은 유기 발광 소자의 정공차단층에 해당하는 유기물층에 사용될 수 있다.As described in Table 1, the compound represented by Chemical Formula 1 of the present invention may be used in an organic material layer corresponding to a hole blocking layer of an organic light emitting device.
상기 표 1에 기재된 바와 같이, 본 발명의 화학식 2, 또는 화학식 3으로 표시되는 화합물은 유기 발광 소자의 전자 수송 및 전자 주입을 동시에 할 수 있는 유기물층에 사용될 수 있다.As described in Table 1 above, the compound represented by Chemical Formula 2 or Chemical Formula 3 of the present invention may be used in an organic material layer capable of simultaneously transporting and injecting electrons in an organic light emitting device.
상기 표 1의 실험예 1 내지 160과 비교실험예 1 내지 20을 비교하면, 본 발명의 화학식 1로 표시되는 화합물, 및 화학식 2 또는 3으로 표시되는 헤테로고리 화합물을 포함하는 유기 발광 소자는 화학식 1의 화합물을 포함하지 않는 유기 발광 소자보다 효율, 수명 면에서 현저히 우수한 특성을 보임을 확인할 수 있었다.Comparing Experimental Examples 1 to 160 and Comparative Experimental Examples 1 to 20 in Table 1, the organic light emitting device including the compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 or 3 of the present invention is represented by Formula 1 It was confirmed that the organic light emitting device not containing the compound of showed significantly superior characteristics in terms of efficiency and lifespan.
상기 표 1의 실험예 1 내지 160과 비교실험예 21 내지 191을 비교하면, 본 발명의 화학식 1로 표시되는 화합물, 및 화학식 2 또는 3으로 표시되는 헤테로고리 화합물을 포함하는 유기 발광 소자는 화학식 2, 또는 3으로 표시되는 헤테로고리 화합물을 포함하지 않는 유기 발광 소자보다 효율, 수명 면에서 현저히 우수한 특성을 보임을 확인할 수 있었다.Comparing Experimental Examples 1 to 160 and Comparative Experimental Examples 21 to 191 in Table 1, the organic light emitting device including the compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 or 3 of the present invention is represented by Chemical Formula 2 , or 3, it was confirmed that the organic light emitting diode does not contain a heterocyclic compound, showing significantly better characteristics in terms of efficiency and lifespan.
[부호의 설명][Description of code]
1: 기판 2: 양극1: substrate 2: anode
3: 발광층 4: 정공차단층3: light emitting layer 4: hole blocking layer
5: 전자수송 및 주입층 6: 음극5: electron transport and injection layer 6: cathode
7: 정공주입층 8: 정공수송층7: hole injection layer 8: hole transport layer
9: 전자억제층 9: electron suppression layer

Claims (13)

  1. 양극;anode;
    발광층;light emitting layer;
    정공차단층;hole blocking layer;
    전자수송층, 전자주입층, 또는 전자수송 및 주입층; 및an electron transport layer, an electron injection layer, or an electron transport and injection layer; and
    음극을 포함하고,contains a cathode,
    상기 정공차단층은 하기 화학식 1로 표시되는 화합물을 포함하고,The hole blocking layer includes a compound represented by Formula 1 below,
    상기 전자수송층, 전자주입층, 또는 전자수송 및 주입층은 하기 화학식 2 또는 3으로 표시되는 화합물을 포함하는,The electron transport layer, the electron injection layer, or the electron transport and injection layer comprises a compound represented by Formula 2 or 3 below,
    유기 발광 소자:Organic Light-Emitting Elements:
    [화학식 1][Formula 1]
    Figure PCTKR2022007243-appb-img-000084
    Figure PCTKR2022007243-appb-img-000084
    상기 화학식 1에서,In Formula 1,
    X1 내지 X3는 각각 독립적으로, N 또는 CH이되, X1 내지 X3 중 적어도 하나 이상은 N이고,X 1 to X 3 are each independently N or CH, but at least one or more of X 1 to X 3 is N;
    L1 내지 L3는 각각 독립적으로, 직접 결합; 또는 치환 또는 비치환된 C6-60 아릴렌이고,L 1 to L 3 are each independently a direct bond; or a substituted or unsubstituted C 6-60 arylene;
    Ar1 및 Ar2는 각각 독립적으로, 치환 또는 비치환된 C6-60 아릴이고,Ar 1 and Ar 2 are each independently a substituted or unsubstituted C 6-60 aryl;
    Ar3는 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O, 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴이고,Ar 3 is a substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O, and S,
    [화학식 2][Formula 2]
    Figure PCTKR2022007243-appb-img-000085
    Figure PCTKR2022007243-appb-img-000085
    [화학식 3][Formula 3]
    Figure PCTKR2022007243-appb-img-000086
    Figure PCTKR2022007243-appb-img-000086
    상기 화학식 2, 또는 화학식 3에서,In Formula 2 or Formula 3,
    R1 내지 R4는 각각 독립적으로, 수소, 또는 중수소이고, R 1 to R 4 are each independently hydrogen or deuterium;
    n1 내지 n4는 1 내지 4의 정수이고,n1 to n4 are integers from 1 to 4;
    L4 및 L5는 각각 독립적으로, 직접 결합; 또는 치환 또는 비치환된 C6-60 아릴렌이고,L 4 and L 5 are each independently a direct bond; or a substituted or unsubstituted C 6-60 arylene;
    Ar4 및 Ar5는 각각 독립적으로, 하기 화학식 4로 표시되는 치환기이고,Ar 4 and Ar 5 are each independently a substituent represented by Formula 4 below;
    [화학식 4][Formula 4]
    Figure PCTKR2022007243-appb-img-000087
    Figure PCTKR2022007243-appb-img-000087
    상기 화학식 4에서,In Formula 4,
    X4 내지 X8은 각각 독립적으로, N 또는 C(R5)이되, X4 내지 X8 중 적어도 둘 이상은 N이고,X 4 to X 8 are each independently N or C (R 5 ), but at least two or more of X 4 to X 8 are N;
    R5는 각각 독립적으로 수소; 중수소; 치환 또는 비치환된 C1-20 알킬; 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상의 헤테로원자를 포함하는 C2-60 헤테로아릴이거나, 이들 중 인접한 2개의 R5가 결합하여 벤젠 고리를 형성한다.R 5 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 1-20 Alkyl; Substituted or unsubstituted C 6-60 aryl; Or a C 2-60 heteroaryl containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S, or two adjacent R 5 of them bond to form a benzene ring.
  2. 제1항에 있어서,According to claim 1,
    L1 및 L2는 각각 독립적으로, 직접 결합, 또는 페닐렌이고,L 1 and L 2 are each independently a direct bond or phenylene;
    L3는 직접 결합, 페닐렌, 비페닐디일, 또는 터페닐디일인,L 3 is a direct key, phenylene, biphenyldiyl, or terphenyldiyl;
    유기 발광 소자.organic light emitting device.
  3. 제1항에 있어서,According to claim 1,
    Ar1 및 Ar2는 각각 독립적으로, 페닐, 비페닐릴, 또는 나프틸인,Ar 1 and Ar 2 are each independently phenyl, biphenylyl, or naphthyl;
    유기 발광 소자.organic light emitting device.
  4. 제1항에 있어서,According to claim 1,
    Ar3는 하기 화학식 1-1 내지 화학식 1-7로 표시되는 치환기 중 어느 하나인,Ar 3 is any one of the substituents represented by Formulas 1-1 to 1-7 below;
    유기 발광 소자:Organic Light-Emitting Elements:
    [화학식 1-1][Formula 1-1]
    Figure PCTKR2022007243-appb-img-000088
    Figure PCTKR2022007243-appb-img-000088
    [화학식 1-2][Formula 1-2]
    Figure PCTKR2022007243-appb-img-000089
    Figure PCTKR2022007243-appb-img-000089
    [화학식 1-3][Formula 1-3]
    Figure PCTKR2022007243-appb-img-000090
    Figure PCTKR2022007243-appb-img-000090
    [화학식 1-4][Formula 1-4]
    Figure PCTKR2022007243-appb-img-000091
    Figure PCTKR2022007243-appb-img-000091
    [화학식 1-5][Formula 1-5]
    Figure PCTKR2022007243-appb-img-000092
    Figure PCTKR2022007243-appb-img-000092
    [화학식 1-6][Formula 1-6]
    Figure PCTKR2022007243-appb-img-000093
    Figure PCTKR2022007243-appb-img-000093
    [화학식 1-7][Formula 1-7]
    Figure PCTKR2022007243-appb-img-000094
    Figure PCTKR2022007243-appb-img-000094
    상기 화학식 1-1 내지 화학식 1-7에서,In Formula 1-1 to Formula 1-7,
    R6 및 R7은 각각 독립적으로, 수소; 중수소; 치환 또는 비치환된 C1-10 알킬; 또는 치환 또는 비치환된 C6-60 아릴이고,R 6 and R 7 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 1-10 Alkyl; or a substituted or unsubstituted C 6-60 aryl;
    Z는 각각 독립적으로, NR9, O, 또는 S이고,Z is each independently NR 9 , O, or S;
    R8 및 R9는 각각 독립적으로, 치환 또는 비치환된 C6-60 아릴인,R 8 and R 9 are each independently a substituted or unsubstituted C 6-60 aryl;
    유기 발광 소자.organic light emitting device.
  5. 제4항에 있어서,According to claim 4,
    R6 및 R7은 각각 독립적으로, 수소, 중수소, 메틸, 또는 치환 또는 비치환된 페닐이고,R 6 and R 7 are each independently hydrogen, deuterium, methyl, or substituted or unsubstituted phenyl;
    R8 및 R9는 페닐인,R 8 and R 9 are phenyl;
    유기 발광 소자.organic light emitting device.
  6. 제1항에 있어서,According to claim 1,
    Ar3는 하기로 구성되는 군으로부터 선택되는 어느 하나인,Ar 3 is any one selected from the group consisting of
    유기 발광 소자:Organic Light-Emitting Elements:
    Figure PCTKR2022007243-appb-img-000095
    Figure PCTKR2022007243-appb-img-000095
  7. 제1항에 있어서,According to claim 1,
    상기 화학식 1로 표시되는 화합물은 하기 화합물로 구성되는 군으로부터 선택되는 어느 하나인,The compound represented by Formula 1 is any one selected from the group consisting of the following compounds,
    유기 발광 소자:Organic Light-Emitting Elements:
    Figure PCTKR2022007243-appb-img-000096
    Figure PCTKR2022007243-appb-img-000096
    Figure PCTKR2022007243-appb-img-000097
    Figure PCTKR2022007243-appb-img-000097
    Figure PCTKR2022007243-appb-img-000098
    Figure PCTKR2022007243-appb-img-000098
    Figure PCTKR2022007243-appb-img-000099
    Figure PCTKR2022007243-appb-img-000099
    Figure PCTKR2022007243-appb-img-000100
    Figure PCTKR2022007243-appb-img-000100
    Figure PCTKR2022007243-appb-img-000101
    Figure PCTKR2022007243-appb-img-000101
    Figure PCTKR2022007243-appb-img-000102
    Figure PCTKR2022007243-appb-img-000102
    Figure PCTKR2022007243-appb-img-000103
    Figure PCTKR2022007243-appb-img-000103
    Figure PCTKR2022007243-appb-img-000104
    Figure PCTKR2022007243-appb-img-000104
    Figure PCTKR2022007243-appb-img-000105
    Figure PCTKR2022007243-appb-img-000105
    Figure PCTKR2022007243-appb-img-000106
    Figure PCTKR2022007243-appb-img-000106
    Figure PCTKR2022007243-appb-img-000107
    Figure PCTKR2022007243-appb-img-000107
    Figure PCTKR2022007243-appb-img-000108
    Figure PCTKR2022007243-appb-img-000108
    Figure PCTKR2022007243-appb-img-000109
    Figure PCTKR2022007243-appb-img-000109
    Figure PCTKR2022007243-appb-img-000110
    Figure PCTKR2022007243-appb-img-000110
    Figure PCTKR2022007243-appb-img-000111
    Figure PCTKR2022007243-appb-img-000111
    Figure PCTKR2022007243-appb-img-000112
    Figure PCTKR2022007243-appb-img-000112
    Figure PCTKR2022007243-appb-img-000113
    Figure PCTKR2022007243-appb-img-000113
    Figure PCTKR2022007243-appb-img-000114
    Figure PCTKR2022007243-appb-img-000114
    Figure PCTKR2022007243-appb-img-000115
    Figure PCTKR2022007243-appb-img-000115
  8. 제1항에 있어서,According to claim 1,
    상기 화학식 2는 하기 화학식 2-1로 표시되고,Formula 2 is represented by Formula 2-1 below,
    상기 화학식 3은 하기 화학식 3-1로 표시되는, Formula 3 is represented by the following Formula 3-1,
    유기 발광 소자:Organic Light-Emitting Elements:
    [화학식 2-1][Formula 2-1]
    Figure PCTKR2022007243-appb-img-000116
    Figure PCTKR2022007243-appb-img-000116
    [화학식 3-1][Formula 3-1]
    Figure PCTKR2022007243-appb-img-000117
    Figure PCTKR2022007243-appb-img-000117
    상기 화학식 2-1, 또는 화학식 3-1에서, In Formula 2-1 or Formula 3-1,
    L4, L5, Ar4 및 Ar5는 제1항에서 정의한 바와 같다. L 4 , L 5 , Ar 4 and Ar 5 are as defined in claim 1.
  9. 제1항에 있어서,According to claim 1,
    L4 및 L5는 각각 독립적으로 직접 결합, 페닐렌, 또는 비페닐디일인,L 4 and L 5 are each independently a direct bond, phenylene, or biphenyldiyl;
    유기 발광 소자.organic light emitting device.
  10. 제1항에 있어서,According to claim 1,
    Ar4 및 Ar5는 각각 독립적으로, 하기로 구성되는 군으로부터 선택되는 어느 하나인,Ar 4 and Ar 5 are each independently selected from the group consisting of:
    유기 발광 소자:Organic Light-Emitting Elements:
    Figure PCTKR2022007243-appb-img-000118
    Figure PCTKR2022007243-appb-img-000118
    상기 군에서,In the group,
    R5는 제1항에서 정의한 바와 같다.R 5 is as defined in claim 1.
  11. 제1항에 있어서,According to claim 1,
    R5는 각각 독립적으로, 수소, 중수소, 메틸, tert-부틸, 페닐, 비페닐릴, 터페닐릴, 나프틸, 피리디닐, 퓨라닐, 또는 티오페닐이거나, 이들 중 인접한 2개의 R5가 결합하여 벤젠 고리를 형성하고,Each R 5 is independently hydrogen, deuterium, methyl, tert-butyl, phenyl, biphenylyl, terphenylyl, naphthyl, pyridinyl, furanyl, or thiophenyl, or two adjacent R 5 are a bond to form a benzene ring,
    상기 페닐, 비페닐릴, 터페닐릴, 나프틸, 피리디닐, 퓨라닐, 또는 티오페닐은 각각 독립적으로 비치환되거나, 중수소, 메틸, 또는 tert-부틸로 치환된,The phenyl, biphenylyl, terphenylyl, naphthyl, pyridinyl, furanyl, or thiophenyl are each independently unsubstituted or substituted with deuterium, methyl, or tert-butyl,
    유기 발광 소자.organic light emitting device.
  12. 제1항에 있어서,According to claim 1,
    Ar4 및 Ar5는 각각 독립적으로, 하기로 구성되는 군으로부터 선택되는 어느 하나인,Ar 4 and Ar 5 are each independently selected from the group consisting of:
    유기 발광 소자:Organic Light-Emitting Elements:
    Figure PCTKR2022007243-appb-img-000119
    Figure PCTKR2022007243-appb-img-000119
    Figure PCTKR2022007243-appb-img-000120
    Figure PCTKR2022007243-appb-img-000120
  13. 제1항에 있어서,According to claim 1,
    상기 화학식 2로 또는 3으로 표시되는 화합물은 하기 화합물로 구성되는 군으로부터 선택되는 어느 하나인,The compound represented by Formula 2 or 3 is any one selected from the group consisting of the following compounds,
    유기 발광 소자:Organic Light-Emitting Elements:
    Figure PCTKR2022007243-appb-img-000121
    Figure PCTKR2022007243-appb-img-000121
    Figure PCTKR2022007243-appb-img-000122
    Figure PCTKR2022007243-appb-img-000122
    Figure PCTKR2022007243-appb-img-000123
    Figure PCTKR2022007243-appb-img-000123
    Figure PCTKR2022007243-appb-img-000124
    Figure PCTKR2022007243-appb-img-000124
    Figure PCTKR2022007243-appb-img-000125
    Figure PCTKR2022007243-appb-img-000125
PCT/KR2022/007243 2021-05-25 2022-05-20 Organic light-emitting device WO2022250386A1 (en)

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