WO2020111613A1 - Novel compound and organic light-emitting diode comprising same - Google Patents

Novel compound and organic light-emitting diode comprising same Download PDF

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WO2020111613A1
WO2020111613A1 PCT/KR2019/015685 KR2019015685W WO2020111613A1 WO 2020111613 A1 WO2020111613 A1 WO 2020111613A1 KR 2019015685 W KR2019015685 W KR 2019015685W WO 2020111613 A1 WO2020111613 A1 WO 2020111613A1
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group
layer
compound
substituted
light emitting
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PCT/KR2019/015685
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French (fr)
Korean (ko)
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정민우
이동훈
장분재
홍완표
서상덕
이정하
한수진
박슬찬
황성현
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주식회사 엘지화학
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Priority claimed from KR1020190145978A external-priority patent/KR102352825B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US17/278,406 priority Critical patent/US20210363132A1/en
Priority to CN201980060834.2A priority patent/CN112714763A/en
Publication of WO2020111613A1 publication Critical patent/WO2020111613A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems

Definitions

  • the present invention relates to a novel compound and an organic light emitting device comprising the same.
  • the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material.
  • the organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies have been conducted.
  • the organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode.
  • the organic material layer is often formed of a multi-layered structure composed of different materials, for example, may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like.
  • Patent Document 1 Korean Patent Publication No. 10-2000-0051826
  • the present invention relates to a novel organic light emitting material and an organic light emitting device comprising the same.
  • X 1 to X 6 are each independently CH or N, provided that at least one of X 1 to X 6 is N,
  • Ar 1 to Ar 4 are each independently, substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 2-60 heteroaryl including any one or more selected from the group consisting of N, O and S, provided that at least one of Ar 1 to Ar 4 is selected from the group consisting of: Which one;
  • R 3 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 2-60 heteroaryl including any one or more selected from the group consisting of N, O and S,
  • a is an integer from 0 to 8
  • R 1 is hydrogen; heavy hydrogen; Substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 2-60 heteroaryl including any one or more selected from the group consisting of N, O and S,
  • n is an integer from 0 to 8.
  • the present invention is a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a compound represented by Chemical Formula 1, and provides an organic light emitting device. .
  • FIG. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
  • Figure 2 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), light emitting layer (3), hole blocking layer (7), electron transport layer (8), electron injection layer (9) And an example of an organic light-emitting device comprising the cathode 4.
  • FIG. 3 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), electron blocking layer (10), light emitting layer (3), hole blocking layer (7), electron transport layer (8) ,
  • An example of an organic light-emitting device consisting of an electron injection layer 9 and a cathode 4 is shown.
  • the present invention provides a compound represented by Formula 1 above.
  • substituted or unsubstituted refers to deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amino group; Phosphine oxide group; Alkoxy groups; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Aryl sulfoxyl group; Silyl group; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Ar alkenyl group; Alkyl aryl groups; Alkylamine groups; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more
  • 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 oxygen of the ester group may be substituted with a straight chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.
  • the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.
  • the boron group is specifically a trimethyl boron group, a triethyl boron group, a t-butyl dimethyl boron group, a triphenyl boron group, a phenyl boron group, and the like, but is not limited thereto.
  • examples of the halogen group include fluorine, chlorine, bromine or iodine.
  • 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 aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 20.
  • the aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, a terphenyl 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 heterocyclic group is a heterocyclic group containing one or more of O, N, Si and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms.
  • the heterocyclic group include thiophene group, furan group, pyrrol group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, Acridil group, pyridazine group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazino pyrazinyl group, isoquinoline group , Indole group,
  • an aryl group in an aralkyl group, an alkenyl group, an alkylaryl group, and an arylamine group is the same as the exemplified aryl group described above.
  • the alkyl group among the aralkyl group, alkylaryl group, and alkylamine group is the same as the above-described example of the alkyl group.
  • heteroarylamine among heteroarylamines may be applied to the description of the aforementioned heterocyclic group.
  • the alkenyl group in the alkenyl group is the same as the exemplified alkenyl group.
  • 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 two substituents are formed by bonding.
  • the heterocycle is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied, except that two substituents are formed by bonding.
  • X 1 to X 6 are each independently CH or N, provided that at least one of X 1 to X 3 is N, and at least one of X 4 to X 6 is N.
  • X 1 to X 6 may each be N.
  • Ar 1 to Ar 4 are each independently, substituted or unsubstituted C 6-20 aryl; Or C 2-20 heteroaryl including any one or more selected from the group consisting of substituted or unsubstituted N, O and S, provided that at least one of Ar 1 to Ar 4 is selected from the group consisting of: Can be any one;
  • R 2 is hydrogen; heavy hydrogen; Substituted or unsubstituted C 6-20 aryl; Or C 2-20 heteroaryl containing any one or more selected from the group consisting of substituted or unsubstituted N, O and S,
  • R 3 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 6-20 aryl; Or C 2-20 heteroaryl containing any one or more selected from the group consisting of substituted or unsubstituted N, O and S,
  • a is an integer from 0 to 8.
  • R 2 and R 3 may each independently be hydrogen, deuterium, phenyl, or phenyl substituted with 5 deuterium.
  • Ar 1 to Ar 4 are each independently phenyl, biphenylyl, naphthyl, phenanthrenyl, triphenylenyl, dibenzofuranyl, dibenzothiophenyl, dimethylfluorenyl, carbazolyl, Phenyl carbazolyl, phenyl substituted with 5 deuterium, carbazolyl substituted with phenyl substituted with 5 deuterium, or
  • at least one of Ar 1 to Ar 4 may be any one selected from the group consisting of:
  • R 1 is hydrogen; heavy hydrogen; Substituted or unsubstituted C 6-20 aryl; Or C 2-20 heteroaryl containing any one or more selected from the group consisting of substituted or unsubstituted N, O and S,
  • R 1 may be hydrogen, phenyl, or phenyl substituted with 1 to 5 deuterium.
  • n can be 0 or 1.
  • the compound represented by the formula (1) for example, can be prepared by the same method as in Scheme 1, and other compounds can be similarly prepared.
  • X 1 to X 6 , Ar 1 to Ar 4 , R 1 and n are as defined in Chemical Formula 1, and Z 1 and Z 2 are each independently halogen, preferably Z 1 and Z 2 are each independently chloro or fluoro.
  • the first reaction of Reaction Scheme 1 is a Suzuki coupling reaction, and is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be modified as known in the art.
  • the second reaction of Reaction Scheme 1 is an amine substitution reaction, and is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art.
  • the manufacturing method may be more specific in the manufacturing examples to be described later.
  • the present invention provides an organic light emitting device comprising the compound represented by the formula (1).
  • the present invention is a first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including at least one layer of an organic material provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a compound represented by Chemical Formula 1, and an organic light emitting device is provided. do.
  • the organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked.
  • the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, an electron transport layer, an electron injection layer as an organic material layer.
  • the structure of the organic light emitting device is not limited thereto, and may include a smaller number of organic material layers.
  • the organic material layer may include a light emitting layer, and the light emitting layer may include a compound represented by Chemical Formula 1.
  • the organic material layer may include a hole transport layer, a hole injection layer, or a layer simultaneously performing hole transport and hole injection
  • the hole transport layer, a hole injection layer, or a layer simultaneously performing hole transport and hole injection may have the formula It may contain a compound represented by 1.
  • the electron transport layer, the electron injection layer, or a layer that simultaneously performs electron transport and electron injection may include a compound represented by Chemical Formula 1.
  • the organic light emitting device according to the present invention may be an organic light emitting device having a structure (normal type) in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. Further, the organic light emitting device according to the present invention may be an organic light emitting device of an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of the organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.
  • FIG. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
  • the compound represented by Chemical Formula 1 may be included in the light emitting layer.
  • Figure 2 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), light emitting layer (3), hole blocking layer (7), electron transport layer (8), electron injection layer (9) And an example of an organic light-emitting device comprising the cathode 4.
  • the compound represented by Chemical Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the light emitting layer, the blocking layer, the electron transport layer and the electron injection layer.
  • FIG. 3 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), electron blocking layer (10), light emitting layer (3), hole blocking layer (7), electron transport layer (8) ,
  • An example of an organic light-emitting device consisting of an electron injection layer 9 and a cathode 4 is shown.
  • the compound represented by Chemical Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the blocking layer, the electron transport layer, and the electron injection layer.
  • the organic light-emitting device according to the present invention can be made of materials and methods known in the art, except that at least one layer of the organic material layer contains the compound represented by Chemical Formula 1.
  • the organic material layers may be formed of the same material or different materials.
  • the organic light emitting device can be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate.
  • a positive electrode is formed by depositing metal or conductive metal oxides or alloys thereof on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation.
  • PVD physical vapor deposition
  • an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed thereon, and a material that can be used as a cathode is deposited thereon.
  • an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.
  • the compound represented by Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device.
  • the solution application method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited to these.
  • an organic light emitting device may be manufactured by sequentially depositing an organic material layer and a cathode material from a cathode material on a substrate (WO 2003/012890).
  • the manufacturing method is not limited thereto.
  • the first electrode is an anode
  • the second electrode is a cathode
  • the first electrode is a cathode
  • the second electrode is an anode
  • the positive electrode material is preferably a material having a large work function so that hole injection into the organic material layer is smooth.
  • the positive electrode material include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of metal and oxide such as ZnO:Al or SnO 2 :Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.
  • the cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer.
  • the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof;
  • a multilayer structure material such as LiF/Al or LiO 2 /Al, but is not limited thereto.
  • the hole injection layer is a layer for injecting holes from an electrode, and has the ability to transport holes as a hole injection material, and thus has a hole injection effect at an anode, an excellent hole injection effect for a light emitting layer or a light emitting material, and is generated in the light emitting layer.
  • a compound that prevents migration of the excitons to the electron injection layer or the electron injection material and has excellent thin film formation ability is preferred.
  • the high occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic layer.
  • hole injection material examples include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based substances.
  • Organic anthraquinone and polyaniline and polythiophene-based conductive polymers are not limited thereto.
  • the hole transport layer is a layer that receives holes from the hole injection layer and transports holes from the hole injection layer to the light emitting layer. It is a material that transports holes from the anode or the hole injection layer as a hole transport material and transfers them to the light emitting layer. This is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, but are not limited thereto.
  • the electron blocking layer is a layer between the hole transport layer and the light emitting layer to prevent electrons injected from the cathode from being recombined in the light emitting layer and passing over the hole transport layer, and is also referred to as an electron blocking layer.
  • the electron blocking layer is preferably a material having a smaller electron affinity than the electron transport layer.
  • a material capable of emitting light in the visible region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively is preferably a material having good quantum efficiency for fluorescence or phosphorescence.
  • Specific examples include 8-hydroxy-quinoline aluminum complex (Alq 3 ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole compounds; Poly(p-phenylenevinylene) (PPV) polymers; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited to these.
  • a compound in which at least one arylvinyl group is substituted with the arylamine, a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group is substituted or unsubstituted.
  • a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group is substituted or unsubstituted.
  • styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like but are not limited thereto.
  • examples of the metal complex include an iridium complex, a platinum complex, and the like, but are not limited thereto.
  • the electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an electron injection effect from a cathode, an excellent electron injection effect for a light emitting layer or a light emitting material, and injects holes generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film forming ability is preferred.
  • the organic light emitting device may be a front emission type, a back emission type, or a double-sided emission type depending on the material used.
  • the compound A1 (14.0 g, 30 mmol), bis (pinacolato) diboron (8.5 g, 33 mmol) and potassium acetate (5.9 g, 61 mmol) are mixed, added to 210 ml of dioxane and stirred. While heating. In reflux, bis(dibenzylidineacetone)palladium (0.52 g, 0.9 mmol) and tricyclohexylphosphine (0.51 g, 1.8 mmol) were added and heated and stirred for 6 hours. After the reaction was completed, the temperature was reduced to room temperature and filtered.
  • Triazine is 2-chloro-4-(dibenzothiophen-4-yl)-6-phenyl-1,3,5 instead of 2-chloro-4,6-diphenyl-1,3,5-triazine -Compound 6 was prepared by the same method as Production Example 1, except that triazine was used.
  • 2-chloro-4,6-diphenyl-1,3,5-triazine (50.0 g, 19 mmol) and (3-chloro-4-fluorophenyl)boronic acid (32.6 g, 19 mmol) are tetrahydro Dissolved in 1000 mL of furan. After adding a potassium carbonate 2M solution (200 mL), tetrakis-(triphenylphosphine)palladium (2.2 g, 1.9 mmol) was added and refluxed for 2 hours.
  • ITO Indium Tin Oxide
  • distilled water filtered secondarily by a filter of Millipore Co.
  • ultrasonic washing was repeated for 2 minutes with distilled water twice.
  • ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, followed by drying and then transported to a plasma cleaner.
  • the substrate was washed for 5 minutes using oxygen plasma, and then transferred to a vacuum evaporator.
  • the following compound HI-A was thermally vacuum-deposited to a thickness of 100 ⁇ on the prepared ITO transparent electrode to form a hole injection layer. Subsequently, only the compound HT-A was thermally vacuum-deposited to a thickness of 800 ,, and the compound HT-B was subsequently vacuum-deposited to a thickness of 500 ⁇ to form a hole transport layer. Subsequently, as the first host of the light emitting layer, Compound 1 and the second host prepared in Preparation Example 1 were vacuum-deposited at a weight ratio of 50:50 and 6% by weight of the compound GD of the two host weights at a thickness of 350 MPa. .
  • the following ET-A was vacuum-deposited to a thickness of 50 MPa as a hole blocking layer.
  • the following ET-B and Liq as the electron transport and injection layer were thermally vacuum-deposited to a thickness of 250 MPa at a weight ratio of 1:1, and then LiF was vacuum-deposited to a thickness of 30 MPa.
  • the electron injection layer was deposited to a thickness of 1000 ⁇ to form a cathode, thereby manufacturing an organic light emitting device.
  • the organic light emitting devices of Examples 2 to 11 were manufactured in the same manner as in Example 1, except that the compound shown in Table 1 below was used instead of Compound 1 as a host material.
  • the organic light emitting device manufactured by using the compound according to the present invention as a host of the light emitting layer exhibits excellent performance in terms of voltage, efficiency, and lifetime compared to the organic light emitting device of Comparative Example. .
  • This is presumed to be because when an aryl or heteroaryl condensed ring substituent is substituted on a nitrogen-containing heterocyclic group such as triazine, it is advantageous for electron and hole transport and molecular stability can be enhanced.
  • Example 1 and Comparative Example 2 it was confirmed that the difference in voltage and life was observed depending on the presence or absence of a phenylene linker between carbazole and triazine.
  • substrate 2 anode

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Abstract

The present invention provides a novel compound and an organic light-emitting diode using same.

Description

신규한 화합물 및 이를 포함하는 유기발광 소자Novel compounds and organic light-emitting devices comprising the same
관련 출원(들)과의 상호 인용Cross-citation with relevant application(s)
본 출원은 2018년 11월 27일자 한국 특허 출원 제10-2018-0148563호 및 2019년 11월 14일자 한국 특허 출원 제10-2019-0145978호에 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. 10-2018-0148563 dated November 27, 2018 and Korean Patent Application No. 10-2019-0145978 dated November 14, 2019. All content disclosed in the literature is incorporated as part of this specification.
본 발명은 신규한 화합물 및 이를 포함하는 유기 발광 소자에 관한 것이다.The present invention relates to a novel compound and an organic light emitting device comprising the same.
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 that converts electrical energy into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies have been conducted.
유기 발광 소자는 일반적으로 양극과 음극 및 상기 양극과 음극 사이에 유기물 층을 포함하는 구조를 가진다. 상기 유기물 층은 유기 발광 소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층 등으로 이루어질 수 있다. 이러한 유기 발광 소자의 구조에서 두 전극 사이에 전압을 걸어주게 되면 양극에서는 정공이, 음극에서는 전자가 유기물층에 주입되게 되고, 주입된 정공과 전자가 만났을 때 엑시톤(exciton)이 형성되며, 이 엑시톤이 다시 바닥상태로 떨어질 때 빛이 나게 된다.The organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode. In order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often formed of a multi-layered structure composed of different materials, for example, may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied between two electrodes in the structure of the organic light emitting device, holes are injected at the anode, and electrons are injected at the cathode, and an exciton is formed when the injected holes meet the electrons. When it falls to the ground again, it 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.
[선행기술문헌][Advanced technical literature]
[특허문헌][Patent Document]
(특허문헌 1) 한국특허 공개번호 제10-2000-0051826호(Patent Document 1) Korean Patent Publication No. 10-2000-0051826
본 발명은 신규한 유기발광 재료 및 이를 포함하는 유기 발광 소자에 관한 것이다.The present invention relates to a novel organic light emitting material and an organic light emitting device comprising the same.
본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다:The present invention provides a compound represented by Formula 1:
[화학식 1][Formula 1]
Figure PCTKR2019015685-appb-I000001
Figure PCTKR2019015685-appb-I000001
상기 화학식 1에서,In Chemical Formula 1,
X1 내지 X6는 각각 독립적으로, CH 또는 N이고, 단 X1 내지 X6 중 적어도 하나는 N이고,X 1 to X 6 are each independently CH or N, provided that at least one of X 1 to X 6 is N,
Ar1 내지 Ar4는 각각 독립적으로, 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴이고, 단 Ar1 내지 Ar4 중 적어도 하나는 하기로 구성되는 군으로부터 선택되는 어느 하나이고;Ar 1 to Ar 4 are each independently, substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 2-60 heteroaryl including any one or more selected from the group consisting of N, O and S, provided that at least one of Ar 1 to Ar 4 is selected from the group consisting of: Which one;
Figure PCTKR2019015685-appb-I000002
Figure PCTKR2019015685-appb-I000002
상기 군에서,In the above group,
R2는 수소; 중수소; 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴이고,R 2 is hydrogen; heavy hydrogen; Substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 2-60 heteroaryl including any one or more selected from the group consisting of N, O and S,
R3는 각각 독립적으로, 수소; 중수소; 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴이고,R 3 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 2-60 heteroaryl including any one or more selected from the group consisting of N, O and S,
a는 0 내지 8의 정수이고,a is an integer from 0 to 8,
R1은 수소; 중수소; 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴이고,R 1 is hydrogen; heavy hydrogen; Substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 2-60 heteroaryl including any one or more selected from the group consisting of N, O and S,
n은 0 내지 8의 정수이다.n is an integer from 0 to 8.
또한, 본 발명은 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 상기 화학식 1로 표시되는 화합물을 포함하는, 유기 발광 소자를 제공한다.In addition, the present invention is a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a compound represented by Chemical Formula 1, and provides an organic light emitting device. .
상술한 화학식 1로 표시되는 화합물은 유기 발광 소자의 유기물 층의 재료로서 사용될 수 있으며, 유기 발광 소자에서 효율의 향상, 낮은 구동전압 및/또는 수명 특성을 향상시킬 수 있다. 특히, 상술한 화학식 1로 표시되는 화합물은 정공주입, 정공수송, 정공주입 및 수송, 발광, 전자수송, 또는 전자주입 재료로 사용될 수 있다.The compound represented by Chemical Formula 1 may be used as a material for an organic material layer of an organic light emitting device, and may improve efficiency, low driving voltage, and/or life characteristics in the organic light emitting device. In particular, the compound represented by Formula 1 may be used as a hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection material.
도 1은 기판(1), 양극(2), 발광층(3) 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다.1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
도 2는 기판 (1), 양극(2), 정공주입층(5), 정공수송층(6), 발광층(3), 정공저지층(7), 전자수송층(8), 전자주입층(9) 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다.Figure 2 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), light emitting layer (3), hole blocking layer (7), electron transport layer (8), electron injection layer (9) And an example of an organic light-emitting device comprising the cathode 4.
도 3은 기판 (1), 양극(2), 정공주입층(5), 정공수송층(6), 전자차단층(10), 발광층(3), 정공저지층(7), 전자수송층(8), 전자주입층(9) 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다.3 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), electron blocking layer (10), light emitting layer (3), hole blocking layer (7), electron transport layer (8) , An example of an organic light-emitting device consisting of an electron injection layer 9 and a cathode 4 is shown.
이하, 본 발명의 이해를 돕기 위하여 보다 상세히 설명한다.Hereinafter, it will be described in more detail in order to help the understanding of the present invention.
본 발명은 상기 화학식 1로 표시되는 화합물을 제공한다.The present invention provides a compound represented by Formula 1 above.
본 명세서에서,
Figure PCTKR2019015685-appb-I000003
또는
Figure PCTKR2019015685-appb-I000004
는 다른 치환기에 연결되는 결합을 의미한다.In this specification,
Figure PCTKR2019015685-appb-I000003
or
Figure PCTKR2019015685-appb-I000004
Means a linkage 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.The term "substituted or unsubstituted" as used herein refers to deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amino group; Phosphine oxide group; Alkoxy groups; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Aryl sulfoxyl group; Silyl group; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Ar alkenyl group; Alkyl aryl groups; Alkylamine groups; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more substituents among the exemplified substituents above . For example, "a substituent having two or more substituents" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.
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 this 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 PCTKR2019015685-appb-I000005
Figure PCTKR2019015685-appb-I000005
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 oxygen of the ester group may be substituted with a straight chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.
Figure PCTKR2019015685-appb-I000006
Figure PCTKR2019015685-appb-I000006
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 this 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 PCTKR2019015685-appb-I000007
Figure PCTKR2019015685-appb-I000007
본 명세서에 있어서, 실릴기는 구체적으로 트리메틸실릴기, 트리에틸실릴기, t-부틸디메틸실릴기, 비닐디메틸실릴기, 프로필디메틸실릴기, 트리페닐실릴기, 디페닐실릴기, 페닐실릴기 등이 있으나 이에 한정되지 않는다.In the present specification, the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.
본 명세서에 있어서, 붕소기는 구체적으로 트리메틸붕소기, 트리에틸붕소기, t-부틸디메틸붕소기, 트리페닐붕소기, 페닐붕소기 등이 있으나 이에 한정되지 않는다.In the present specification, the boron group is specifically a trimethyl boron group, a triethyl boron group, a t-butyl dimethyl boron group, a triphenyl boron group, a phenyl boron group, and the like, but is not limited thereto.
본 명세서에 있어서, 할로겐기의 예로는 불소, 염소, 브롬 또는 요오드가 있다.In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.
본 명세서에 있어서, 상기 알킬기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나 1 내지 40인 것이 바람직하다. 일 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 20이다. 또 하나의 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 10이다. 또 하나의 실시상태에 따르면, 상기 알킬기의 탄소수는 1 내지 6이다. 알킬기의 구체적인 예로는 메틸, 에틸, 프로필, n-프로필, 이소프로필, 부틸, n-부틸, 이소부틸, tert-부틸, sec-부틸, 1-메틸-부틸, 1-에틸-부틸, 펜틸, n-펜틸, 이소펜틸, 네오펜틸, tert-펜틸, 헥실, n-헥실, 1-메틸펜틸, 2-메틸펜틸, 4-메틸-2-펜틸, 3,3-디메틸부틸, 2-에틸부틸, 헵틸, n-헵틸, 1-메틸헥실, 사이클로펜틸메틸, 사이클로헥실메틸, 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 carbon number is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group are 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, and the like, 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 a straight chain or a branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the carbon number of the alkenyl group is 2 to 20. 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, styrenyl group, styrenyl group, and the like, but are not limited thereto.
본 명세서에 있어서, 사이클로알킬기는 특별히 한정되지 않으나, 탄소수 3 내지 60인 것이 바람직하며, 일 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 30이다. 또 하나의 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 20이다. 또 하나의 실시상태에 따르면, 상기 사이클로알킬기의 탄소수는 3 내지 6이다. 구체적으로 사이클로프로필, 사이클로부틸, 사이클로펜틸, 3-메틸사이클로펜틸, 2,3-디메틸사이클로펜틸, 사이클로헥실, 3-메틸사이클로헥실, 4-메틸사이클로헥실, 2,3-디메틸사이클로헥실, 3,4,5-트리메틸사이클로헥실, 4-tert-부틸사이클로헥실, 사이클로헵틸, 사이클로옥틸 등이 있으나, 이에 한정되지 않는다.In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.
본 명세서에 있어서, 아릴기는 특별히 한정되지 않으나 탄소수 6 내지 60인 것이 바람직하며, 단환식 아릴기 또는 다환식 아릴기일 수 있다. 일 실시상태에 따르면, 상기 아릴기의 탄소수는 6 내지 30이다. 일 실시상태에 따르면, 상기 아릴기의 탄소수는 6 내지 20이다. 상기 아릴기가 단환식 아릴기로는 페닐기, 바이페닐기, 터페닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다. 상기 다환식 아릴기로는 나프틸기, 안트라세닐기, 페난트릴기, 파이레닐기, 페릴레닐기, 크라이세닐기, 플루오레닐기 등이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, a terphenyl 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 PCTKR2019015685-appb-I000008
등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may combine with each other to form a spiro structure. When the fluorenyl group is substituted,
Figure PCTKR2019015685-appb-I000008
It can be back. 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, 트리아졸기, 아크리딜기, 피리다진기, 피라지닐기, 퀴놀리닐기, 퀴나졸린기, 퀴녹살리닐기, 프탈라지닐기, 피리도 피리미디닐기, 피리도 피라지닐기, 피라지노 피라지닐기, 이소퀴놀린기, 인돌기, 카바졸기, 벤조옥사졸기, 벤조이미다졸기, 벤조티아졸기, 벤조카바졸기, 벤조티오펜기, 디벤조티오펜기, 벤조퓨라닐기, 페난쓰롤린기(phenanthroline), 티아졸릴기, 이소옥사졸릴기, 옥사디아졸릴기, 티아디아졸릴기, 벤조티아졸릴기, 페노티아지닐기 및 디벤조퓨라닐기 등이 있으나, 이들에만 한정되는 것은 아니다.In the present specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrol group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, Acridil group, pyridazine group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazino pyrazinyl group, isoquinoline group , Indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, Isooxazolyl groups, oxadiazolyl groups, thiadiazolyl groups, benzothiazolyl groups, phenothiazinyl groups, and dibenzofuranyl groups, 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 aryl group in an aralkyl group, an alkenyl group, an alkylaryl group, and an arylamine group is the same as the exemplified aryl group described above. In the present specification, the alkyl group among the aralkyl group, alkylaryl group, and alkylamine group is the same as the above-described example of the alkyl group. In the present specification, heteroarylamine among heteroarylamines may be applied to the description of the aforementioned heterocyclic group. In the present specification, the alkenyl group in the alkenyl group is the same as the exemplified alkenyl group. 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 two substituents are formed by bonding. In this specification, the heterocycle is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied, except that two substituents are formed by bonding.
바람직하게는, X1 내지 X6는 각각 독립적으로, CH 또는 N이고, 단 X1 내지 X3 중 적어도 하나는 N이고, X4 내지 X6 중 적어도 하나는 N일 수 있다.Preferably, X 1 to X 6 are each independently CH or N, provided that at least one of X 1 to X 3 is N, and at least one of X 4 to X 6 is N.
바람직하게는, X1 내지 X6는 각각 N일 수 있다.Preferably, X 1 to X 6 may each be N.
바람직하게는, Ar1 내지 Ar4는 각각 독립적으로, 치환 또는 비치환된 C6-20 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-20 헤테로아릴이고, 단 Ar1 내지 Ar4 중 적어도 하나는 하기로 구성되는 군으로부터 선택되는 어느 하나일 수 있고;Preferably, Ar 1 to Ar 4 are each independently, substituted or unsubstituted C 6-20 aryl; Or C 2-20 heteroaryl including any one or more selected from the group consisting of substituted or unsubstituted N, O and S, provided that at least one of Ar 1 to Ar 4 is selected from the group consisting of: Can be any one;
Figure PCTKR2019015685-appb-I000009
Figure PCTKR2019015685-appb-I000009
상기 군에서,In the above group,
R2는 수소; 중수소; 치환 또는 비치환된 C6-20 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-20 헤테로아릴이고,R 2 is hydrogen; heavy hydrogen; Substituted or unsubstituted C 6-20 aryl; Or C 2-20 heteroaryl containing any one or more selected from the group consisting of substituted or unsubstituted N, O and S,
R3는 각각 독립적으로, 수소; 중수소; 치환 또는 비치환된 C6-20 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-20 헤테로아릴이고,R 3 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 6-20 aryl; Or C 2-20 heteroaryl containing any one or more selected from the group consisting of substituted or unsubstituted N, O and S,
a는 0 내지 8의 정수이다.a is an integer from 0 to 8.
바람직하게는, R2 및 R3는 각각 독립적으로, 수소, 중수소, 페닐, 또는 5 개의 중수소로 치환된 페닐일 수 있다.Preferably, R 2 and R 3 may each independently be hydrogen, deuterium, phenyl, or phenyl substituted with 5 deuterium.
가장 바람직하게는, Ar1 내지 Ar4는 각각 독립적으로, 페닐, 비페닐릴, 나프틸, 페난트레닐, 트리페닐레닐, 디벤조퓨라닐, 디벤조티오페닐, 디메틸플루오레닐, 카바졸릴, 페닐 카바졸릴, 5 개의 중수소로 치환된 페닐, 5 개의 중수소로 치환된 페닐로 치환된 카바졸릴, 또는
Figure PCTKR2019015685-appb-I000010
이고, 단, Ar1 내지 Ar4 중 적어도 하나는 하기로 구성되는 군으로부터 선택되는 어느 하나일 수 있다:Most preferably, Ar 1 to Ar 4 are each independently phenyl, biphenylyl, naphthyl, phenanthrenyl, triphenylenyl, dibenzofuranyl, dibenzothiophenyl, dimethylfluorenyl, carbazolyl, Phenyl carbazolyl, phenyl substituted with 5 deuterium, carbazolyl substituted with phenyl substituted with 5 deuterium, or
Figure PCTKR2019015685-appb-I000010
However, provided that at least one of Ar 1 to Ar 4 may be any one selected from the group consisting of:
Figure PCTKR2019015685-appb-I000011
Figure PCTKR2019015685-appb-I000011
바람직하게는, R1은 수소; 중수소; 치환 또는 비치환된 C6-20 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-20 헤테로아릴이고,Preferably, R 1 is hydrogen; heavy hydrogen; Substituted or unsubstituted C 6-20 aryl; Or C 2-20 heteroaryl containing any one or more selected from the group consisting of substituted or unsubstituted N, O and S,
보다 바람직하게는, R1은 수소, 페닐, 또는 1 개 내지 5 개의 중수소로 치환된 페닐일 수 있다.More preferably, R 1 may be hydrogen, phenyl, or phenyl substituted with 1 to 5 deuterium.
바람직하게는, n은 0 또는 1일 수 있다.Preferably, n can be 0 or 1.
상기 화학식 1로 표시되는 화합물의 대표적인 예는 다음과 같다:Representative examples of the compound represented by Formula 1 are as follows:
Figure PCTKR2019015685-appb-I000012
Figure PCTKR2019015685-appb-I000012
Figure PCTKR2019015685-appb-I000013
Figure PCTKR2019015685-appb-I000013
Figure PCTKR2019015685-appb-I000014
Figure PCTKR2019015685-appb-I000014
Figure PCTKR2019015685-appb-I000015
Figure PCTKR2019015685-appb-I000015
Figure PCTKR2019015685-appb-I000016
Figure PCTKR2019015685-appb-I000016
Figure PCTKR2019015685-appb-I000017
Figure PCTKR2019015685-appb-I000017
Figure PCTKR2019015685-appb-I000018
Figure PCTKR2019015685-appb-I000018
상기 화학식 1로 표시되는 화합물은, 일례로 하기 반응식 1과 같은 제조 방법으로 제조할 수 있으며, 그 외 나머지 화합물도 유사하게 제조할 수 있다.The compound represented by the formula (1), for example, can be prepared by the same method as in Scheme 1, and other compounds can be similarly prepared.
[반응식 1][Scheme 1]
Figure PCTKR2019015685-appb-I000019
Figure PCTKR2019015685-appb-I000019
상기 반응식 1에서, X1 내지 X6, Ar1 내지 Ar4, R1 및 n은 상기 화학식 1에서 정의한 바와 같으며, Z1 및 Z2는 각각 독립적으로 할로겐이고, 바람직하게는 Z1 및 Z2는 각각 독립적으로, 클로로 또는 플루오로이다.In Reaction Scheme 1, X 1 to X 6 , Ar 1 to Ar 4 , R 1 and n are as defined in Chemical Formula 1, and Z 1 and Z 2 are each independently halogen, preferably Z 1 and Z 2 are each independently chloro or fluoro.
상기 반응식 1의 첫 번째 반응은 스즈키 커플링 반응으로서, 팔라듐 촉매와 염기 존재 하에 수행하는 것이 바람직하며, 스즈키 커플링 반응을 위한 반응기는 당업계에 알려진 바에 따라 변경이 가능하다. 또한, 상기 반응식 1의 두 번째 반응은 아민 치환 반응으로서, 팔라듐 촉매와 염기 존재 하에 수행하는 것이 바람직하며, 아민 치환 반응을 위한 반응기는 당업계에 알려진 바에 따라 변경이 가능하다. 상기 제조 방법은 후술할 제조예에서 보다 구체화될 수 있다.The first reaction of Reaction Scheme 1 is a Suzuki coupling reaction, and is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be modified as known in the art. In addition, the second reaction of Reaction Scheme 1 is an amine substitution reaction, and is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art. The manufacturing method may be more specific in the manufacturing examples to be described later.
또한, 본 발명은 상기 화학식 1로 표시되는 화합물을 포함하는 유기 발광 소자를 제공한다. 일례로, 본 발명은 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 이상의 유기물 층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 상기 화학식 1로 표시되는 화합물을 포함하는, 유기 발광 소자를 제공한다.In addition, the present invention provides an organic light emitting device comprising the compound represented by the formula (1). In one example, the present invention is a first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including at least one layer of an organic material provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a compound represented by Chemical Formula 1, and an organic light emitting device is provided. do.
본 발명의 유기 발광 소자의 유기물 층은 단층 구조로 이루어질 수도 있으나, 2층 이상의 유기물층이 적층된 다층 구조로 이루어질 수 있다. 예컨대, 본 발명의 유기 발광 소자는 유기물 층으로서 정공주입층, 정공수송층, 발광층, 전자차단층, 전자수송층, 전자주입층 등을 포함하는 구조를 가질 수 있다. 그러나 유기 발광 소자의 구조는 이에 한정되지 않고 더 적은 수의 유기물층을 포함할 수 있다.The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, an electron transport layer, an electron injection layer as an organic material layer. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number of organic material layers.
또한, 상기 유기물 층은 발광층을 포함할 수 있고, 상기 발광층은 상기 화학식 1로 표시되는 화합물을 포함할 수 있다.In addition, the organic material layer may include a light emitting layer, and the light emitting layer may include a compound represented by Chemical Formula 1.
또한, 상기 유기물 층은 정공수송층, 정공주입층, 또는 정공수송 및 정공주입을 동시에 하는 층을 포함할 수 있고, 상기 정공수송층, 정공주입층, 또는 정공수송 및 정공주입을 동시에 하는 층은 상기 화학식 1로 표시되는 화합물을 포함할 수 있다.In addition, the organic material layer may include a hole transport layer, a hole injection layer, or a layer simultaneously performing hole transport and hole injection, and the hole transport layer, a hole injection layer, or a layer simultaneously performing hole transport and hole injection may have the formula It may contain a compound represented by 1.
또한, 상기 전자수송층, 전자주입층, 또는 전자수송 및 전자주입을 동시에 하는 층은 상기 화학식 1로 표시되는 화합물을 포함할 수 있다.Further, the electron transport layer, the electron injection layer, or a layer that simultaneously performs electron transport and electron injection may include a compound represented by Chemical Formula 1.
또한, 상기 유기물 층은 발광층 및 정공수송층을 포함하고, 상기 발광층또는 정공수송층은 상기 화학식 1로 표시되는 화합물을 포함할 수 있다.In addition, the organic material layer includes a light emitting layer and a hole transport layer, and the light emitting layer or the hole transport layer may include a compound represented by Chemical Formula 1.
또한, 본 발명에 따른 유기 발광 소자는, 기판 상에 양극, 1층 이상의 유기물 층 및 음극이 순차적으로 적층된 구조(normal type)의 유기 발광 소자일 수 있다. 또한, 본 발명에 따른 유기 발광 소자는 기판 상에 음극, 1층 이상의 유기물 층 및 양극이 순차적으로 적층된 역방향 구조(inverted type)의 유기 발광 소자일 수 있다. 예컨대, 본 발명의 일실시예에 따른 유기 발광 소자의 구조는 도 1 및 2에 예시되어 있다.Further, the organic light emitting device according to the present invention may be an organic light emitting device having a structure (normal type) in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. Further, the organic light emitting device according to the present invention may be an organic light emitting device of an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of the organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.
도 1은 기판(1), 양극(2), 발광층(3) 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다. 이와 같은 구조에 있어서, 상기 화학식 1로 표시되는 화합물은 상기 발광층에 포함될 수 있다.1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. In such a structure, the compound represented by Chemical Formula 1 may be included in the light emitting layer.
도 2는 기판 (1), 양극(2), 정공주입층(5), 정공수송층(6), 발광층(3), 정공저지층(7), 전자수송층(8), 전자주입층(9) 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다. 이와 같은 구조에 있어서, 상기 화학식 1로 표시되는 화합물은 상기 정공주입층, 정공수송층, 발광층, 저지층, 전자수송층 및 전자주입층 중 1층 이상에 포함될 수 있다.Figure 2 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), light emitting layer (3), hole blocking layer (7), electron transport layer (8), electron injection layer (9) And an example of an organic light-emitting device comprising the cathode 4. In such a structure, the compound represented by Chemical Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the light emitting layer, the blocking layer, the electron transport layer and the electron injection layer.
도 3은 기판 (1), 양극(2), 정공주입층(5), 정공수송층(6), 전자차단층(10), 발광층(3), 정공저지층(7), 전자수송층(8), 전자주입층(9) 및 음극(4)으로 이루어진 유기 발광 소자의 예를 도시한 것이다. 이와 같은 구조에 있어서, 상기 화학식 1로 표시되는 화합물은 상기 정공주입층, 정공수송층, 전자차단층, 발광층, 저지층, 전자수송층 및 전자주입층 중 1층 이상에 포함될 수 있다.3 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), electron blocking layer (10), light emitting layer (3), hole blocking layer (7), electron transport layer (8) , An example of an organic light-emitting device consisting of an electron injection layer 9 and a cathode 4 is shown. In such a structure, the compound represented by Chemical Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the blocking layer, the electron transport layer, and the electron injection layer.
본 발명에 따른 유기 발광 소자는, 상기 유기물 층 중 1층 이상이 상기 화학식 1로 표시되는 화합물을 포함하는 것을 제외하고는 당 기술분야에 알려져 있는 재료와 방법으로 제조될 수 있다. 또한, 상기 유기 발광 소자가 복수개의 유기물층을 포함하는 경우, 상기 유기물층은 동일한 물질 또는 다른 물질로 형성될 수 있다.The organic light-emitting device according to the present invention can be made of materials and methods known in the art, except that at least one layer of the organic material layer contains the compound represented by Chemical Formula 1. In addition, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.
예컨대, 본 발명에 따른 유기 발광 소자는 기판 상에 제1 전극, 유기물층 및 제2 전극을 순차적으로 적층시켜 제조할 수 있다. 이때, 스퍼터링법(sputtering)이나 전자빔 증발법(e-beam evaporation)과 같은 PVD(physical Vapor Deposition)방법을 이용하여, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 정공주입층, 정공수송층, 발광층 및 전자수송층을 포함하는 유기물 층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시켜 제조할 수 있다. 이와 같은 방법 외에도, 기판 상에 음극 물질부터 유기물층, 양극 물질을 차례로 증착시켜 유기 발광 소자를 만들 수 있다.For example, the organic light emitting device according to the present invention can be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, a positive electrode is formed by depositing metal or conductive metal oxides or alloys thereof on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. Then, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed thereon, and a material that can be used as a cathode is deposited thereon. In addition to this method, an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.
또한, 상기 화학식 1로 표시되는 화합물은 유기 발광 소자의 제조시 진공 증착법 뿐만 아니라 용액 도포법에 의하여 유기물 층으로 형성될 수 있다. 여기서, 용액 도포법이라 함은 스핀 코팅, 딥코팅, 닥터 블레이딩, 잉크젯 프린팅, 스크린 프린팅, 스프레이법, 롤 코팅 등을 의미하지만, 이들만으로 한정되는 것은 아니다.In addition, the compound represented by Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution application method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited to these.
이와 같은 방법 외에도, 기판 상에 음극 물질로부터 유기물층, 양극 물질을 차례로 증착시켜 유기 발광 소자를 제조할 수 있다(WO 2003/012890). 다만, 제조 방법이 이에 한정되는 것은 아니다.In addition to this method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and a cathode material from a cathode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.
일례로, 상기 제1 전극은 양극이고, 상기 제2 전극은 음극이거나, 또는 상기 제1 전극은 음극이고, 상기 제2 전극은 양극이다.In one example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode, and the second electrode is an anode.
상기 양극 물질로는 통상 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.The positive electrode material is preferably a material having a large work function so that hole injection into the organic material layer is smooth. Specific examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of metal and oxide such as ZnO:Al or SnO 2 :Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.
상기 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 to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; There is a multilayer structure material such as LiF/Al or LiO 2 /Al, but is not limited thereto.
상기 정공주입층은 전극으로부터 정공을 주입하는 층으로, 정공 주입 물질로는 정공을 수송하는 능력을 가져 양극에서의 정공 주입효과, 발광층 또는 발광재료에 대하여 우수한 정공 주입 효과를 갖고, 발광층에서 생성된 여기자의 전자주입층 또는 전자주입재료에의 이동을 방지하며, 또한, 박막 형성 능력이 우수한 화합물이 바람직하다. 정공 주입 물질의 HOMO(highest occupied molecular orbital)가 양극 물질의 일함수와 주변 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 한정 되는 것은 아니다.The hole injection layer is a layer for injecting holes from an electrode, and has the ability to transport holes as a hole injection material, and thus has a hole injection effect at an anode, an excellent hole injection effect for a light emitting layer or a light emitting material, and is generated in the light emitting layer. A compound that prevents migration of the excitons to the electron injection layer or the electron injection material and has excellent thin film formation ability is preferred. It is preferred that the high occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based substances. , Organic anthraquinone and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.
상기 정공수송층은 정공주입층으로부터 정공을 수취하여 발광층까지 정공을 수송하는 층으로, 정공 수송 물질로 양극이나 정공주입층으로부터 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 is a layer that receives holes from the hole injection layer and transports holes from the hole injection layer to the light emitting layer. It is a material that transports holes from the anode or the hole injection layer as a hole transport material and transfers them to the light emitting layer. This is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, but are not limited thereto.
상기 전자차단층은 음극에서 주입된 전자가 발광층에서 재결합되지 않고 정공수송층으로 넘어가는 것을 방지하기 위해 정공수송층과 발광층의 사이에 두는 층으로는 층으로, 전자저지층으로 불리기도 한다. 전자차단층에는 전자수송층보다 전자 친화력이 작은 물질이 바람직하다.The electron blocking layer is a layer between the hole transport layer and the light emitting layer to prevent electrons injected from the cathode from being recombined in the light emitting layer and passing over the hole transport layer, and is also referred to as an electron blocking layer. The electron blocking layer is preferably a material having a smaller electron affinity than the electron transport layer.
상기 발광 물질로는 정공수송층과 전자수송층으로부터 정공과 전자를 각각 수송받아 결합시킴으로써 가시광선 영역의 빛을 낼 수 있는 물질로서, 형광이나 인광에 대한 양자 효율이 좋은 물질이 바람직하다. 구체적인 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.As the light-emitting material, a material capable of emitting light in the visible region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, is preferably a material having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq 3 ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole compounds; Poly(p-phenylenevinylene) (PPV) polymers; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited to these.
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. 특히, 바람직하게는 상기 화학식 1로 표시되는 화합물을 호스트로 포함할 수 있다.The light emitting layer may include a host material and a dopant material. The host material may be a condensed aromatic ring derivative or a heterocyclic compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic compounds include carbazole derivatives, dibenzofuran derivatives, and ladder types Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto. In particular, preferably, the compound represented by Chemical Formula 1 may be included as a host.
상기 화학식 1로 표시되는 화합물을 포함하는 유기물층은 화학식 1로 표시되는 화합물 외의 화합물을 동시에 포함할 수 있다. 상기 화학식 1로 표시되는 화합물과 그 외의 화합물의 중량비는 1:99 내지 99:1일 수 있고, 보다 바람직하게는 10:90 내지 90:10일 수 있다.The organic material layer including the compound represented by Formula 1 may include compounds other than the compound represented by Formula 1 at the same time. The weight ratio of the compound represented by Chemical Formula 1 and other compounds may be 1:99 to 99:1, and more preferably 10:90 to 90:10.
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.Examples of the dopant material include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periplanene, etc. having an arylamino group, and substituted or unsubstituted as a styrylamine compound. A compound in which at least one arylvinyl group is substituted with the arylamine, a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group is substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. Further, examples of the metal complex include an iridium complex, a platinum complex, and the like, but are not limited thereto.
상기 정공저지층은 양극에서 주입된 정공이 발광층에서 재결합되지 않고 전자수송층으로 넘어가는 것을 방지하기 위해 전자수송층과 발광층의 사이에 두는 층으로, 정공억제층으로 불리기도 한다. 정공저지층에는 이온화에너지가 큰 물질이 바람직하다.The hole blocking layer is a layer placed between the electron transport layer and the light emitting layer to prevent the holes injected from the anode from being recombined in the light emitting layer and passing into the electron transport layer, and is also referred to as a hole suppressing layer. The hole blocking layer is preferably a material having a large ionization energy.
상기 전자수송층은 전자주입층으로부터 전자를 수취하여 발광층까지 전자를 수송하는 층으로 전자 수송 물질로는 음극으로부터 전자를 잘 주입 받아 발광층으로 옮겨줄 수 있는 물질로서, 전자에 대한 이동성이 큰 물질이 적합하다. 구체적인 예로는 8-히드록시퀴놀린의 Al 착물; Alq3를 포함한 착물; 유기 라디칼 화합물; 히드록시플라본-금속 착물 등이 있으나, 이들에만 한정되는 것은 아니다. 전자수송층은 종래기술에 따라 사용된 바와 같이 임의의 원하는 캐소드 물질과 함께 사용할 수 있다. 특히, 적절한 캐소드 물질의 예는 낮은 일함수를 가지고 알루미늄층 또는 실버층이 뒤따르는 통상적인 물질이다. 구체적으로 세슘, 바륨, 칼슘, 이테르븀 및 사마륨이고, 각 경우 알루미늄 층 또는 실버층이 뒤따른다.The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable. Do. Specific examples include the Al complex of 8-hydroxyquinoline; Complexes including Alq 3 ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are those that have a low work function and are followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, followed by an aluminum layer or a silver layer in each case.
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 화합물이 바람직하다. 구체적으로는 플루오레논, 안트라퀴노다이메탄, 다이페노퀴논, 티오피란 다이옥사이드, 옥사졸, 옥사다이아졸, 트리아졸, 이미다졸, 페릴렌테트라카복실산, 프레오레닐리덴 메탄, 안트론 등과 그들의 유도체, 금속 착체 화합물 및 질소 함유 5원환 유도체 등이 있으나, 이에 한정되지 않는다.The electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an electron injection effect from a cathode, an excellent electron injection effect for a light emitting layer or a light emitting material, and injects holes generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and their derivatives, metal Complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.
상기 금속 착체 화합물로서는 8-하이드록시퀴놀리나토 리튬, 비스(8-하이드록시퀴놀리나토)아연, 비스(8-하이드록시퀴놀리나토)구리, 비스(8-하이드록시퀴놀리나토)망간, 트리스(8-하이드록시퀴놀리나토)알루미늄, 트리스(2-메틸-8-하이드록시퀴놀리나토)알루미늄, 트리스(8-하이드록시퀴놀리나토)갈륨, 비스(10-하이드록시벤조[h]퀴놀리나토)베릴륨, 비스(10-하이드록시벤조[h]퀴놀리나토)아연, 비스(2-메틸-8-퀴놀리나토)클로로갈륨, 비스(2-메틸-8-퀴놀리나토)(o-크레졸라토)갈륨, 비스(2-메틸-8-퀴놀리나토)(1-나프톨라토)알루미늄, 비스(2-메틸-8-퀴놀리나토)(2-나프톨라토)갈륨 등이 있으나, 이에 한정되지 않는다.Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato) zinc, bis(8-hydroxyquinolinato) copper, and 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, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, It is not limited to this.
본 발명에 따른 유기 발광 소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a double-sided emission type depending on the material used.
또한, 상기 화학식 1로 표시되는 화합물은 유기 발광 소자 외에도 유기 태양 전지 또는 유기 트랜지스터에 포함될 수 있다.In addition, the compound represented by Chemical Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.
이하, 본 발명의 이해를 돕기 위하여 보다 상세히 설명한다. 단, 하기의 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기의 실시예에 의하여 한정되는 것은 아니다.Hereinafter, it will be described in more detail in order to help the understanding of the present invention. However, the following examples are only illustrative of the present invention, and the contents of the present invention are not limited by the following examples.
[제조예][Production example]
제조예 1: 화합물 1의 제조Preparation Example 1 Preparation of Compound 1
Figure PCTKR2019015685-appb-I000020
Figure PCTKR2019015685-appb-I000020
1) 화합물 A1의 제조1) Preparation of Compound A1
2-클로로-4-(페난스렌-2-일)-6-페닐-1,3,5-트리아진(15.0 g, 41 mmol)과 (3-클로로-4-플루오로페닐)보론산(7.1 g, 41 mmol)을 테트라하이드로퓨란 200 mL에 녹였다. 여기에 탄산칼륨 2 M 용액(80 mL)을 추가 후 테트라키스-(트리페닐포스핀)팔라듐(0.47 g, 0.4 mmol)을 넣고 1.5 시간 환류시켰다. 반응이 끝난 후 상온으로 냉각시키고, 물 층을 분리하여 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시킨 혼합물을 클로로포름과 에탄올을 이용하여 재결정화시켜 화합물 A1(14.0 g, 수율 74 %)을 얻었다.2-Chloro-4-(phenanthren-2-yl)-6-phenyl-1,3,5-triazine (15.0 g, 41 mmol) and (3-chloro-4-fluorophenyl)boronic acid (7.1 g, 41 mmol) was dissolved in 200 mL of tetrahydrofuran. After adding a 2 M solution of potassium carbonate (80 mL), tetrakis-(triphenylphosphine)palladium (0.47 g, 0.4 mmol) was added and refluxed for 1.5 hours. After the reaction was completed, the mixture was cooled to room temperature, the water layer was separated and removed, dried over anhydrous magnesium sulfate, and the mixture concentrated under reduced pressure was recrystallized using chloroform and ethanol to obtain compound A1 (14.0 g, yield 74%).
MS:[M+H]+=462MS:[M+H] + =462
2) 화합물 A2의 제조2) Preparation of Compound A2
질소 분위기에서 화학식 화합물 A1(14.0 g, 30 mmol), 비스(피나콜라토)다이보론(8.5 g, 33 mmol) 및 아세트산칼륨(5.9 g, 61 mmol)을 섞고, 다이옥세인 210 ml에 첨가하고 교반하면서 가열하였다. 환류되는 상태에서 비스(디벤질리딘아세톤)팔라듐(0.52g, 0.9 mmol)과 트리사이클로헥실포스핀(0.51 g, 1.8 mmol)을 넣고 6 시간 동안 가열 및 교반하였다. 반응 종료 후, 상온으로 온도를 낮춘 후 여과하였다. 여과액에 물을 붓고 클로로포름으로 추출하고, 유기층을 무수황산마그네슘으로 건조하였다. 감압 증류 후 에틸아세테이트로 재결정하여 상기 화합물 A2(11.9 g, 수율 71 %)를 제조하였다.In a nitrogen atmosphere, the compound A1 (14.0 g, 30 mmol), bis (pinacolato) diboron (8.5 g, 33 mmol) and potassium acetate (5.9 g, 61 mmol) are mixed, added to 210 ml of dioxane and stirred. While heating. In reflux, bis(dibenzylidineacetone)palladium (0.52 g, 0.9 mmol) and tricyclohexylphosphine (0.51 g, 1.8 mmol) were added and heated and stirred for 6 hours. After the reaction was completed, the temperature was reduced to room temperature and filtered. Water was poured into the filtrate, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure and recrystallization with ethyl acetate, Compound A2 (11.9 g, yield 71%) was prepared.
MS:[M+H]+=554MS:[M+H] + =554
3) 화합물 A3의 제조3) Preparation of compound A3
질소 분위기에서 둥근 바닥 플라스크에 화합물 A2(11.9 g, 22 mmol)와 2-클로로-4,6-디페닐-1,3,5-트리아진(5.8 g, 22 mmol)을 테트라하이드로퓨란 160 ml에 녹인 후 탄산칼륨(5.9 g, 43 mmol)을 물 90 mL에 녹여 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.25 g, 0.2 mmol)을 넣은 후 2 시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 반응 중 생성된 고체를 여과하여 물과 테트라하이드로퓨란을 이용하여 씻어준 뒤 건조하여 상기 화합물 A3(12.3 g, 수율 87 %)를 제조하였다.Compound A2 (11.9 g, 22 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (5.8 g, 22 mmol) were added to 160 ml of tetrahydrofuran in a round bottom flask in a nitrogen atmosphere. After dissolving, potassium carbonate (5.9 g, 43 mmol) was dissolved in 90 mL of water and added, and tetrakis-(triphenylphosphine)palladium (0.25 g, 0.2 mmol) was added, followed by heating and stirring for 2 hours. After lowering the temperature to room temperature, the solid produced during the reaction was filtered, washed with water and tetrahydrofuran, and then dried to prepare Compound A3 (12.3 g, yield 87%).
MS:[M+H]+= 659MS:[M+H] + = 659
4) 화합물 1의 제조4) Preparation of compound 1
9H-카바졸(3.1 g, 18.7 mmol)과 포타슘-tert-부톡사이드(3.6 g, 37.4 mmol)를 디메틸포름아마이드 120 mL에 넣고 교반하며 가열하였다. 환류가 시작되면 화합물 A3(12.3 g, 18.7 mmol)를 넣고 5 시간 환류시켰다. 상온으로 온도를 낮추고 물에 역침전시켜 필터하였다. 여과물을 클로로포름으로 녹여 물로 씻어주고, 물 층을 분리하여 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시킨 혼합물을 테트라하이드로퓨란를 이용하여 재결정화시켜 화합물 1(9.6 g, 수율 64 %)을 얻었다.9H-carbazole (3.1 g, 18.7 mmol) and potassium-tert-butoxide (3.6 g, 37.4 mmol) were added to 120 mL of dimethylformamide and heated with stirring. When reflux was started, Compound A3 (12.3 g, 18.7 mmol) was added and refluxed for 5 hours. It was filtered by lowering the temperature to room temperature and reprecipitating it in water. The filtrate was dissolved in chloroform, washed with water, and the water layer was separated, dried, dried over anhydrous magnesium sulfate, and the mixture concentrated under reduced pressure was recrystallized using tetrahydrofuran to obtain compound 1 (9.6 g, yield 64%).
MS:[M+H]+=806MS:[M+H] + =806
제조예 2: 화합물 2의 제조Preparation Example 2: Preparation of compound 2
Figure PCTKR2019015685-appb-I000021
Figure PCTKR2019015685-appb-I000021
2-클로로-4-(페난스렌-2-일)-6-페닐-1,3,5-트리아진 대신 2-클로로-4-(9,9-디메틸-9H-플루오렌-2-일)-6-페닐-1,3,5-트리아진을 사용한 것을 제외하고는, 제조예 1과 동일한 제조 방법으로 화합물 2를 제조하였다.2-chloro-4-(9,9-dimethyl-9H-fluoren-2-yl) instead of 2-chloro-4-(phenanthren-2-yl)-6-phenyl-1,3,5-triazine Compound 6 was prepared by the same method as Production Example 1, except that -6-phenyl-1,3,5-triazine was used.
MS[M+H]+= 822MS[M+H] + = 822
제조예 3: 화합물 3의 제조Preparation Example 3: Preparation of compound 3
Figure PCTKR2019015685-appb-I000022
Figure PCTKR2019015685-appb-I000022
2-클로로-4-(페난스렌-2-일)-6-페닐-1,3,5-트리아진 대신 4-(4-클로로-6-페닐-1,3,5-트리아진-2-일)-9-페닐-9H-카바졸을 사용한 것을 제외하고는, 제조예 1과 동일한 제조 방법으로 화합물 3을 제조하였다.2-Chloro-4-(phenanthren-2-yl)-6-phenyl-1,3,5-triazine instead of 4-(4-chloro-6-phenyl-1,3,5-triazine-2- 1) Compound 3 was prepared by the same method as Production Example 1, except that 9-phenyl-9H-carbazole was used.
MS[M+H]+= 871MS[M+H] + = 871
제조예 4: 화합물 4의 제조Preparation Example 4 Preparation of Compound 4
Figure PCTKR2019015685-appb-I000023
Figure PCTKR2019015685-appb-I000023
2-클로로-4-(페난스렌-2-일)-6-페닐-1,3,5-트리아진 대신 2-클로로-4-(디벤조퓨란-4-일)-6-페닐-1,3,5-트리아진을, 2-클로로-4,6-디페닐-1,3,5-트리아진 대신 2-클로로-4-페닐-6-(페닐-d5)-1,3,5-트리아진을 사용한 것을 제외하고는, 제조예 1과 동일한 제조 방법으로 화합물 4를 제조하였다.2-chloro-4-(dibenzofuran-4-yl)-6-phenyl-1, instead of 2-chloro-4-(phenanthren-2-yl)-6-phenyl-1,3,5-triazine 3,5-triazine, 2-chloro-4-phenyl-6-(phenyl-d 5 )-1,3,5 instead of 2-chloro-4,6-diphenyl-1,3,5-triazine -Compound 4 was prepared by the same method as Production Example 1, except that triazine was used.
MS[M+H]+= 801MS[M+H] + = 801
제조예 5: 화합물 5의 제조Preparation Example 5: Preparation of compound 5
Figure PCTKR2019015685-appb-I000024
Figure PCTKR2019015685-appb-I000024
2-클로로-4-(페난스렌-2-일)-6-페닐-1,3,5-트리아진 대신 2-클로로-4-(나프탈렌-2-일)-6-페닐-1,3,5-트리아진을, 2-클로로-4,6-디페닐-1,3,5-트리아진 대신 2-([1,1’-바이페닐]-3-일)-4-클로로-6-페닐-1,3,5-트리아진을 사용한 것을 제외하고는, 제조예 1과 동일한 제조 방법으로 화합물 5를 제조하였다.2-chloro-4-(naphthalen-2-yl)-6-phenyl-1,3, instead of 2-chloro-4-(phenanthren-2-yl)-6-phenyl-1,3,5-triazine 5-triazine, 2-([1,1'-biphenyl]-3-yl)-4-chloro-6- instead of 2-chloro-4,6-diphenyl-1,3,5-triazine Compound 5 was prepared by the same method as Production Example 1, except that phenyl-1,3,5-triazine was used.
MS[M+H]+= 832MS[M+H] + = 832
제조예 6: 화합물 6의 제조Preparation Example 6: Preparation of compound 6
Figure PCTKR2019015685-appb-I000025
Figure PCTKR2019015685-appb-I000025
2-클로로-4-(페난스렌-2-일)-6-페닐-1,3,5-트리아진 대신 2-클로로-4,6-비스(페닐-d5)-1,3,5-트리아진을, 2-클로로-4,6-디페닐-1,3,5-트리아진 대신 2-클로로-4-(디벤조싸이오펜-4-일)-6-페닐-1,3,5-트리아진을 사용한 것을 제외하고는, 제조예 1과 동일한 제조 방법으로 화합물 6를 제조하였다.2-Chloro-4-,6-bis(phenyl-d 5 )-1,3,5- instead of 2-chloro-4-(phenanthren-2-yl)-6-phenyl-1,3,5-triazine Triazine is 2-chloro-4-(dibenzothiophen-4-yl)-6-phenyl-1,3,5 instead of 2-chloro-4,6-diphenyl-1,3,5-triazine -Compound 6 was prepared by the same method as Production Example 1, except that triazine was used.
MS[M+H]+= 822MS[M+H] + = 822
제조예 7: 화합물 7의 제조Preparation Example 7: Preparation of compound 7
Figure PCTKR2019015685-appb-I000026
Figure PCTKR2019015685-appb-I000026
2-클로로-4-(페난스렌-2-일)-6-페닐-1,3,5-트리아진 대신 2-클로로-4,6-디페닐피리미딘을, 2-클로로-4,6-디페닐-1,3,5-트리아진 대신 2-클로로-4-(디벤조퓨란-4-일)-6-페닐-1,3,5-트리아진을 사용한 것을 제외하고는, 제조예 1과 동일한 제조 방법으로 화합물 7을 제조하였다.2-chloro-4-,6-diphenylpyrimidine instead of 2-chloro-4-(phenanthren-2-yl)-6-phenyl-1,3,5-triazine, 2-chloro-4,6- Preparation Example 1, except that 2-chloro-4-(dibenzofuran-4-yl)-6-phenyl-1,3,5-triazine was used instead of diphenyl-1,3,5-triazine Compound 7 was prepared by the same method as in Preparation.
MS[M+H]+= 795MS[M+H] + = 795
제조예 8: 화합물 8의 제조Preparation Example 8: Preparation of compound 8
Figure PCTKR2019015685-appb-I000027
Figure PCTKR2019015685-appb-I000027
1) 화합물 B1의 제조1) Preparation of compound B1
2-클로로-4,6-디페닐-1,3,5-트리아진(50.0 g, 19 mmol)과(3-클로로-4-플루오로페닐)보론산(32.6 g, 19 mmol)을 테트라하이드로퓨란 1000 mL에 녹였다. 여기에 탄산칼륨 2 M 용액(200 mL)을 추가 후 테트라키스-(트리페닐포스핀)팔라듐(2.2 g, 1.9 mmol)을 넣고 2 시간 환류시켰다. 반응이 끝난 후 상온으로 냉각시키고, 물 층을 분리하여 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시킨 혼합물을 클로로포름과 에탄올을 이용하여 재결정화시켜 화합물 B1(51.9 g, 수율 77 %)을 얻었다.2-chloro-4,6-diphenyl-1,3,5-triazine (50.0 g, 19 mmol) and (3-chloro-4-fluorophenyl)boronic acid (32.6 g, 19 mmol) are tetrahydro Dissolved in 1000 mL of furan. After adding a potassium carbonate 2M solution (200 mL), tetrakis-(triphenylphosphine)palladium (2.2 g, 1.9 mmol) was added and refluxed for 2 hours. After the reaction was completed, the mixture was cooled to room temperature, separated by removing the water layer, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to recrystallize the mixture using chloroform and ethanol to obtain compound B1 (51.9 g, yield 77%).
MS:[M+H]+=362MS:[M+H] + =362
2) 화합물 B2의 제조2) Preparation of compound B2
질소 분위기에서 화학식 화합물 B1(51.9 g, 143 mmol), 비스(피나콜라토)다이보론(40.1 g, 158 mmol) 및 아세트산칼륨(28.1 g, 287 mmol)을 섞고, 다이옥세인 950 ml에 첨가하고 교반하면서 가열하였다. 환류되는 상태에서 비스(디벤질리딘아세톤)팔라듐(2.5g, 4.3 mmol)과 트리사이클로헥실포스핀(2.41 g, 8.6 mmol)을 넣고 8 시간 동안 가열 및 교반하였다. 반응 종료 후, 상온으로 온도를 낮춘 후 여과하였다. 여과액에 물을 붓고 클로로포름으로 추출하고, 유기층을 무수황산마그네슘으로 건조하였다. 감압 증류 후 에틸아세테이트로 재결정하여 상기 화합물 B2(46.1 g, 수율 71 %)를 제조하였다.In a nitrogen atmosphere, the compound of formula B1 (51.9 g, 143 mmol), bis(pinacolato)diboron (40.1 g, 158 mmol) and potassium acetate (28.1 g, 287 mmol) are mixed, added to 950 ml of dioxane and stirred While heating. In reflux, bis(dibenzylideneacetone)palladium (2.5g, 4.3 mmol) and tricyclohexylphosphine (2.41 g, 8.6 mmol) were added and heated and stirred for 8 hours. After the reaction was completed, the temperature was reduced to room temperature and filtered. Water was poured into the filtrate, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, the mixture was recrystallized with ethyl acetate to prepare the compound B2 (46.1 g, yield 71%).
MS:[M+H]+=454MS:[M+H] + =454
3) 화합물 B3의 제조3) Preparation of compound B3
질소 분위기에서 둥근 바닥 플라스크에 화합물 B2(10.0 g, 22.1 mmol)와 2-클로로-4-페닐-6-(트리페닐렌-2-일)-1,3,5-트리아진(9.2 g, 22.1 mmol)을 테트라하이드로퓨란 200 ml에 녹인 후 탄산칼륨(6.1 g, 44 mmol)을 물 100 mL에 녹여 첨가하고, 테트라키스-(트리페닐포스핀)팔라듐(0.25 g, 0.2 mmol)을 넣은 후 2 시간 동안 가열 교반하였다. 상온으로 온도를 낮추고 반응 중 생성된 고체를 여과하여 물과 테트라하이드로퓨란을 이용하여 씻어준 뒤 건조하여 상기 화합물 B3(13.5 g, 수율 86 %)를 제조하였다.Compound B2 (10.0 g, 22.1 mmol) and 2-chloro-4-phenyl-6-(triphenylen-2-yl)-1,3,5-triazine (9.2 g, 22.1) in a round bottom flask in a nitrogen atmosphere. mmol) was dissolved in 200 ml of tetrahydrofuran, potassium carbonate (6.1 g, 44 mmol) was dissolved in 100 mL of water, and tetrakis-(triphenylphosphine)palladium (0.25 g, 0.2 mmol) was added, followed by 2 The mixture was stirred for an hour. After lowering the temperature to room temperature, the solid produced during the reaction was filtered, washed with water and tetrahydrofuran, and then dried to prepare the compound B3 (13.5 g, yield 86%).
MS:[M+H]+= 709MS:[M+H] + = 709
4) 화합물 8의 제조4) Preparation of compound 8
9H-카바졸(3.2 g, 19.0 mmol)과 포타슘-tert-부톡사이드(3.7 g, 38.1 mmol) 을 디메틸포름아마이드 135 mL에 넣고 교반하며 가열하였다. 환류가 시작되면 화합물 B3(13.5 g, 19.0 mmol)를 넣고 6시간 환류시켰다. 상온으로 온도를 낮추고 물에 역침전시켜 필터한다. 여과물을 클로로포름으로 녹여 물로 씻어주고, 물 층을 분리하여 제거하고 무수황산마그네슘으로 건조한 후 감압농축 시킨 혼합물을 테트라하이드로퓨란를 이용하여 재결정화시켜 화합물 8(10.7 g, 수율 65 %)을 얻었다.9H-carbazole (3.2 g, 19.0 mmol) and potassium-tert-butoxide (3.7 g, 38.1 mmol) were added to 135 mL of dimethylformamide and heated with stirring. When reflux started, compound B3 (13.5 g, 19.0 mmol) was added and refluxed for 6 hours. Filter by lowering the temperature to room temperature and reprecipitating it in water. The filtrate was dissolved with chloroform, washed with water, and the water layer was separated and removed, dried over anhydrous magnesium sulfate, and the mixture concentrated under reduced pressure was recrystallized using tetrahydrofuran to obtain compound 8 (10.7 g, yield 65%).
MS:[M+H]+=857MS:[M+H] + =857
제조예 9: 화합물 9의 제조Preparation Example 9: Preparation of compound 9
Figure PCTKR2019015685-appb-I000028
Figure PCTKR2019015685-appb-I000028
2-클로로-4-페닐-6-(트리페닐렌-2-일)-1,3,5-트리아진 대신 2-클로로-4-(디벤조퓨란-3-일)-6-페닐-1,3,5-트리아진을 사용한 것을 제외하고는, 제조예 8과 동일한 제조 방법으로 화합물 9를 제조하였다.2-Chloro-4-(dibenzofuran-3-yl)-6-phenyl-1 instead of 2-chloro-4-phenyl-6-(triphenylen-2-yl)-1,3,5-triazine Compound 3 was prepared by the same method as in Production Example 8, except that, 3,5-triazine was used.
MS[M+H]+= 796MS[M+H] + = 796
제조예 10: 화합물 10의 제조Preparation Example 10 Preparation of Compound 10
Figure PCTKR2019015685-appb-I000029
Figure PCTKR2019015685-appb-I000029
2-클로로-4-페닐-6-(트리페닐렌-2-일)-1,3,5-트리아진 대신 2-(4-클로로-6-페닐-1,3,5-트리아진-2-일)-9-페닐-9H-카바졸을 사용한 것을 제외하고는, 제조예 8과 동일한 제조 방법으로 화합물 10을 제조하였다.2-(4-chloro-6-phenyl-1,3,5-triazine-2 instead of 2-chloro-4-phenyl-6-(triphenylen-2-yl)-1,3,5-triazine -Yl) Compound 10 was prepared by the same method as Production Example 8, except that 9-phenyl-9H-carbazole was used.
MS[M+H]+= 871MS[M+H] + = 871
제조예 11: 화합물 11의 제조Preparation Example 11 Preparation of Compound 11
Figure PCTKR2019015685-appb-I000030
Figure PCTKR2019015685-appb-I000030
2-클로로-4-페닐-6-(트리페닐렌-2-일)-1,3,5-트리아진 대신 9-(4-클로로-6-페닐-1,3,5-트리아진-2-일)-9H-카바졸을 사용한 것을 제외하고는, 제조예 8과 동일한 제조 방법으로 화합물 11을 제조하였다.9-(4-chloro-6-phenyl-1,3,5-triazine-2 instead of 2-chloro-4-phenyl-6-(triphenylen-2-yl)-1,3,5-triazine -Day) Compound 11 was prepared by the same method as Production Example 8, except that -9H-carbazole was used.
MS[M+H]+= 876MS[M+H] + = 876
[실시예][Example]
실시예 1Example 1
ITO(Indium Tin Oxide)가 1,300Å의 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 30 분간 세척한 후 증류수로 2 회 반복하여 초음파 세척을 10 분간 진행하였다. 증류수 세척이 끝난 후, 이소프로필알콜, 아세톤, 메탄올의 용제로 초음파 세척을 하고 건조시킨 후 플라즈마 세정기로 수송시켰다. 또한, 산소 플라즈마를 이용하여 상기 기판을 5 분간 세정한 후 진공 증착기로 기판을 수송시켰다.ITO (Indium Tin Oxide) was coated with a thin film coated with a thickness of 1,300 Å in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, Fischer Co. was used as a detergent, and distilled water filtered secondarily by a filter of Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic washing was repeated for 2 minutes with distilled water twice. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, followed by drying and then transported to a plasma cleaner. In addition, the substrate was washed for 5 minutes using oxygen plasma, and then transferred to a vacuum evaporator.
이렇게 준비된 ITO 투명 전극 위에 하기 화합물 HI-A를 100 Å의 두께로 열 진공 증착하여 정공주입층을 형성하였다. 이어서 화합물 HT-A만 800 Å의 두께로 열 진공증착하고, 순차적으로 화합물 HT-B를 500 Å 두께로 진공 증착하여 정공수송층을 형성하였다. 이어서 발광층의 제1 호스트로 앞서 제조예 1에서 제조한 화합물 1과 제2 호스트로 화합물 H1을 50:50의 중량비로, 두 호스트 중량 합의 6 중량%의 화합물 GD를 350 Å 의 두께로 진공 증착하였다. 이어서, 정공저지층으로 하기 ET-A를 50 Å의 두께로 진공 증착하였다. 이어서 전자 수송 및 주입층으로 하기 ET-B와 Liq를 1:1의 중량비로 250 Å의 두께로 열 진공 증착하고 이어서 LiF를 30 Å의 두께로 진공 증착하였다. 상기 전자주입층 1000 Å 두께로 알루미늄을 증착하여 음극을 형성하여, 유기 발광 소자를 제조하였다.The following compound HI-A was thermally vacuum-deposited to a thickness of 100 증착 on the prepared ITO transparent electrode to form a hole injection layer. Subsequently, only the compound HT-A was thermally vacuum-deposited to a thickness of 800 ,, and the compound HT-B was subsequently vacuum-deposited to a thickness of 500 Å to form a hole transport layer. Subsequently, as the first host of the light emitting layer, Compound 1 and the second host prepared in Preparation Example 1 were vacuum-deposited at a weight ratio of 50:50 and 6% by weight of the compound GD of the two host weights at a thickness of 350 MPa. . Subsequently, the following ET-A was vacuum-deposited to a thickness of 50 MPa as a hole blocking layer. Subsequently, the following ET-B and Liq as the electron transport and injection layer were thermally vacuum-deposited to a thickness of 250 MPa at a weight ratio of 1:1, and then LiF was vacuum-deposited to a thickness of 30 MPa. The electron injection layer was deposited to a thickness of 1000 알루미늄 to form a cathode, thereby manufacturing an organic light emitting device.
Figure PCTKR2019015685-appb-I000031
Figure PCTKR2019015685-appb-I000031
실시예 2 내지 실시예 11 Examples 2 to 11
호스트 물질로 화합물 1 대신 하기 표 1에 기재된 화합물을 사용한 것을제외하고, 상기 실시예 1과 동일한 방법으로 실시예 2 내지 실시예 11의 유기 발광 소자를 각각 제작하였다.The organic light emitting devices of Examples 2 to 11 were manufactured in the same manner as in Example 1, except that the compound shown in Table 1 below was used instead of Compound 1 as a host material.
비교예 1 및 비교예 2Comparative Example 1 and Comparative Example 2
호스트 물질로 화합물 1 대신 하기 표 1에 기재된 화합물을 사용한 것을제외하고, 상기 실시예 1과 동일한 방법으로 비교예 1 및 비교예 2의 유기 발광 소자를 각각 제작하였다. 하기 표 1에서, 화합물 C1 및 C2는 각각 아래와 같다.The organic light emitting devices of Comparative Example 1 and Comparative Example 2 were manufactured in the same manner as in Example 1, except that the compound shown in Table 1 below was used instead of Compound 1 as a host material. In Table 1, compounds C1 and C2 are as follows.
Figure PCTKR2019015685-appb-I000032
Figure PCTKR2019015685-appb-I000032
[실험예][Experimental Example]
상기 실시예 1 내지 실시예 11 및 비교예 1 내지 비교예 2에서 제작된 유기 발광 소자에 전류를 인가하여, 전압, 효율, 수명(T95)을 측정하고 그 결과를 하기 표 1에 나타내었다. 이때, 전압, 효율은 10 mA/cm2의 전류 밀도를 인가하여 측정되었으며, T95은 전류 밀도 20 mA/cm2에서 초기휘도가 95%로 저하할 때까지의 측정시간을 의미한다.By applying a current to the organic light-emitting device prepared in Examples 1 to 11 and Comparative Examples 1 to 2, voltage, efficiency, and lifetime (T95) were measured and the results are shown in Table 1 below. At this time, the voltage and efficiency were measured by applying a current density of 10 mA/cm 2 , and T95 means the measurement time from the current density of 20 mA/cm 2 until the initial luminance decreased to 95%.
Figure PCTKR2019015685-appb-T000001
Figure PCTKR2019015685-appb-T000001
상기 표 1에 나타난 바와 같이, 본 발명에 따른 화합물을 발광층의 호스트로 사용하여 제조된 유기 발광 소자의 경우에 비교예의 유기 발광 소자에 비하여 전압, 효율 및 수명측면에서 우수한 성능을 나타내는 것을 알 수 있었다. 이는 트리아진과 같은 함질소헤테로고리기에 아릴 혹은 헤테로아릴 축합고리치환기가 치환되면, 전자 및 정공수송에 유리하고 분자 구조적으로 분자의 안정성을 높일 수 있기 때문으로 추측된다. 또한, 실시예 1과 비교예 2를 비교하면 카바졸과 트리아진 사이에 페닐렌 링커의 유무에 따라 전압 및 수명 차이가 나타남을 확인할 수 있었다.As shown in Table 1, it was found that the organic light emitting device manufactured by using the compound according to the present invention as a host of the light emitting layer exhibits excellent performance in terms of voltage, efficiency, and lifetime compared to the organic light emitting device of Comparative Example. . This is presumed to be because when an aryl or heteroaryl condensed ring substituent is substituted on a nitrogen-containing heterocyclic group such as triazine, it is advantageous for electron and hole transport and molecular stability can be enhanced. In addition, when comparing Example 1 and Comparative Example 2, it was confirmed that the difference in voltage and life was observed depending on the presence or absence of a phenylene linker between carbazole and triazine.
[부호의 설명][Description of codes]
1: 기판 2: 양극1: substrate 2: anode
3: 발광층 4: 음극3: light emitting layer 4: cathode
5: 정공주입층 6: 정공수송층5: hole injection layer 6: hole transport layer
7: 정공저지층 8: 전자수송층7: hole blocking layer 8: electron transport layer
9: 전자주입층 10: 전자차단층9: electron injection layer 10: electron blocking layer

Claims (8)

  1. 하기 화학식 1로 표시되는 화합물:Compound represented by the formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2019015685-appb-I000033
    Figure PCTKR2019015685-appb-I000033
    상기 화학식 1에서,In Chemical Formula 1,
    X1 내지 X6는 각각 독립적으로, CH 또는 N이고, 단 X1 내지 X6 중 적어도 하나는 N이고,X 1 to X 6 are each independently CH or N, provided that at least one of X 1 to X 6 is N,
    Ar1 내지 Ar4는 각각 독립적으로, 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴이고, 단 Ar1 내지 Ar4 중 적어도 하나는 하기로 구성되는 군으로부터 선택되는 어느 하나이고;Ar 1 to Ar 4 are each independently, substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 2-60 heteroaryl including any one or more selected from the group consisting of N, O and S, provided that at least one of Ar 1 to Ar 4 is selected from the group consisting of: Which one;
    Figure PCTKR2019015685-appb-I000034
    Figure PCTKR2019015685-appb-I000034
    상기 군에서,In the above group,
    R2는 수소; 중수소; 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴이고,R 2 is hydrogen; heavy hydrogen; Substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 2-60 heteroaryl including any one or more selected from the group consisting of N, O and S,
    R3는 각각 독립적으로, 수소; 중수소; 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴이고,R 3 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 2-60 heteroaryl including any one or more selected from the group consisting of N, O and S,
    a는 0 내지 8의 정수이고,a is an integer from 0 to 8,
    R1은 수소; 중수소; 치환 또는 비치환된 C6-60 아릴; 또는 치환 또는 비치환된 N, O 및 S로 구성되는 군으로부터 선택되는 어느 하나 이상을 포함하는 C2-60 헤테로아릴이고,R 1 is hydrogen; heavy hydrogen; Substituted or unsubstituted C 6-60 aryl; Or a substituted or unsubstituted C 2-60 heteroaryl including any one or more selected from the group consisting of N, O and S,
    n은 0 내지 8의 정수이다.n is an integer from 0 to 8.
  2. 제1항에 있어서,According to claim 1,
    X1 내지 X6는 각각 독립적으로, CH 또는 N이고, 단 X1 내지 X3 중 적어도 하나는 N이고, X4 내지 X6 중 적어도 하나는 N인,X 1 to X 6 are each independently CH or N, provided that at least one of X 1 to X 3 is N, and at least one of X 4 to X 6 is N,
    화합물.compound.
  3. 제1항에 있어서,According to claim 1,
    R2 및 R3는 각각 독립적으로, 수소, 중수소, 페닐, 또는 5 개의 중수소로 치환된 페닐인,R 2 and R 3 are each independently hydrogen, deuterium, phenyl, or phenyl substituted with 5 deuteriums,
    화합물.compound.
  4. 제1항에 있어서,According to claim 1,
    Ar1 내지 Ar4는 각각 독립적으로, 페닐, 비페닐릴, 나프틸, 페난트레닐,트리페닐레닐, 디벤조퓨라닐, 디벤조티오페닐, 디메틸플루오레닐, 카바졸릴, 페닐 카바졸릴, 5 개의 중수소로 치환된 페닐, 5 개의 중수소로 치환된 페닐로 치환된 카바졸릴, 또는
    Figure PCTKR2019015685-appb-I000035
    이고, 단, Ar1 내지 Ar4 중 적어도 하나는 하기로 구성되는 군으로부터 선택되는 어느 하나인,    Ar 1 to Ar 4 are each independently phenyl, biphenylyl, naphthyl, phenanthrenyl, triphenylenyl, dibenzofuranyl, dibenzothiophenyl, dimethylfluorenyl, carbazolyl, phenyl carbazolyl, 5 Phenyl substituted with 5 deuterium, carbazolyl substituted with phenyl substituted with 5 deuterium, or
    Figure PCTKR2019015685-appb-I000035
    However, provided that at least one of Ar 1 to Ar 4 is any one selected from the group consisting of,
    화합물:compound:
    Figure PCTKR2019015685-appb-I000036
    Figure PCTKR2019015685-appb-I000036
  5. 제1항에 있어서,According to claim 1,
    R1은 수소, 페닐, 또는 1 개 내지 5 개의 중수소로 치환된 페닐인,R 1 is hydrogen, phenyl, or phenyl substituted with 1 to 5 deuteriums,
    화합물.compound.
  6. 제1항에 있어서,According to claim 1,
    n은 0 또는 1인,n is 0 or 1,
    화합물.compound.
  7. 제1항에 있어서,According to claim 1,
    상기 화학식 1로 표시되는 화합물은 하기로 구성되는 군으로부터 선택되는 어느 하나인,The compound represented by Formula 1 is any one selected from the group consisting of,
    화합물:compound:
    Figure PCTKR2019015685-appb-I000037
    Figure PCTKR2019015685-appb-I000037
    Figure PCTKR2019015685-appb-I000038
    Figure PCTKR2019015685-appb-I000038
    Figure PCTKR2019015685-appb-I000039
    Figure PCTKR2019015685-appb-I000039
    Figure PCTKR2019015685-appb-I000040
    Figure PCTKR2019015685-appb-I000040
    Figure PCTKR2019015685-appb-I000041
    Figure PCTKR2019015685-appb-I000041
    Figure PCTKR2019015685-appb-I000042
    Figure PCTKR2019015685-appb-I000042
    Figure PCTKR2019015685-appb-I000043
    Figure PCTKR2019015685-appb-I000043
  8. 제1 전극; 상기 제1 전극과 대향하여 구비된 제2 전극; 및 상기 제1 전극과 상기 제2 전극 사이에 구비된 1층 이상의 유기물층을 포함하는 유기 발광 소자로서, 상기 유기물층 중 1층 이상은 제1항 내지 제7항 중 어느 하나의 항에 따른 화합물을 포함하는,A first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the compound according to any one of claims 1 to 7. doing,
    유기 발광 소자.Organic light emitting device.
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KR20100131939A (en) * 2009-06-08 2010-12-16 에스에프씨 주식회사 Indolocarbazole derivatives and organoelectroluminescent device using the same
KR20160041768A (en) * 2014-10-08 2016-04-18 주식회사 알파켐 New host material and organic electroluminescent device using the same
KR20160066339A (en) * 2014-12-02 2016-06-10 주식회사 두산 Organic compounds and organic electro luminescence device comprising the same
KR20170049291A (en) * 2015-10-28 2017-05-10 희성소재 (주) Hetero-cyclic compound and organic light emitting device using the same
CN107954922A (en) * 2017-11-28 2018-04-24 上海道亦化工科技有限公司 A kind of two carbazole derivates of xenyl and application thereof and organic electroluminescence device

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Publication number Priority date Publication date Assignee Title
KR20100131939A (en) * 2009-06-08 2010-12-16 에스에프씨 주식회사 Indolocarbazole derivatives and organoelectroluminescent device using the same
KR20160041768A (en) * 2014-10-08 2016-04-18 주식회사 알파켐 New host material and organic electroluminescent device using the same
KR20160066339A (en) * 2014-12-02 2016-06-10 주식회사 두산 Organic compounds and organic electro luminescence device comprising the same
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