Novel compound and organic light-emitting device using same

Abstract

The invention provides a novel compound and an organic light-emitting device using the same.

Description

Technical Field

[0001] Cross - reference to related applications

[0002] This application claims priority based on Korean Patent Application No. 10-2023-0189857 filed on December 22, 2023, and includes all the content disclosed in the document of the Korean patent application as part of this specification.

[0003] The present invention relates to novel compounds and organic light-emitting devices containing the same. Background Art

[0004] Generally, organic electroluminescence refers to the phenomenon of converting electrical energy into light energy using organic substances. Organic light-emitting devices using organic electroluminescence have a wide viewing angle, excellent contrast, fast response time, and excellent brightness, driving voltage, and response speed characteristics, and thus a large amount of research is being conducted.

[0005] An organic light-emitting device generally has a structure including an anode and a cathode and an organic layer located between the anode and the cathode. In order to improve the efficiency and stability of the organic light-emitting device, the organic layer is mostly formed of a multilayer structure composed of different substances respectively. For example, it can be formed of a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc. For such a structure of an organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode into the organic layer, and electrons are injected from the cathode into the organic layer. When the injected holes and electrons meet, excitons are formed, and light is emitted when the excitons return to the ground state again.

[0006] There is a continuous demand for the development of new materials for the organic substances used in the organic light-emitting devices as described above.

[0007] Prior Art Documents

[0008] Patent Documents

[0009] (Patent Document 1) Korean Patent Publication No. 10-2000-0051826 Summary of the Invention

[0010] Technical Problem

[0011] The present invention relates to novel compounds and organic light-emitting devices containing the same.

[0012] Solution to the Problem

[0013] The present invention provides a compound represented by the following Chemical Formula 1:

[0014] [Chemical Formula 1]

[0015]

[0016] In the above Chemical Formula 1,

[0017] A is a benzene ring fused to two adjacent five-membered rings,

[0018] X is O or S,

[0019] L is a single bond, or a substituted or unsubstituted C 6-60 arylene,

[0020] Ar is a substituted or unsubstituted C 6-60 aryl; or a substituted or unsubstituted C containing any one or more selected from N, O, and S 2-60 heteroaryl,

[0021] R1 to R4 are each independently hydrogen or deuterium,

[0022] R5 is each independently hydrogen or deuterium, but at least one of R5 is deuterium,

[0023] n1 is an integer from 1 to 4,

[0024] n2 is 1 or 2,

[0025] n3 and n4 are each independently an integer from 1 to 4,

[0026] n5 is an integer from 1 to 3,

[0027] n6 is an integer from 1 to 4.

[0028] In addition, the present invention provides an organic light-emitting device, which includes: a first electrode, a second electrode disposed opposite to the first electrode, and one or more organic layers disposed between the first electrode and the second electrode, and one or more of the organic layers contain a compound represented by the above Chemical Formula 1.

[0029] Advantages of the Invention

[0030] The compound represented by the above Chemical Formula 1 can be used as a material for the organic layer of an organic light-emitting device, and an improvement in efficiency, a lower driving voltage, and / or an improvement in lifetime characteristics can be achieved in the organic light-emitting device. In particular, the compound represented by the above Chemical Formula 1 can be used as a material for hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection. Brief Description of the Drawings

[0031] Figure 1 An example of an organic light-emitting device composed of a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4 is illustrated.

[0032] Figure 2An example of an organic light-emitting device composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron transport layer 8, and a cathode 4 is illustrated.

[0033] Symbol Explanation

[0034] 1: Substrate 2: Anode

[0035] 3: Light-emitting layer 4: Cathode

[0036] 5: Hole injection layer 6: Hole transport layer

[0037] 7: Light-emitting layer 8: Electron transport layer Detailed Embodiment

[0038] Hereinafter, a more detailed description will be given to help understand the present invention.

[0039] In this specification, or represents a bond connected to other substituents.

[0040] In this specification, the term "substituted or unsubstituted" means being substituted or unsubstituted by one or more substituents selected from deuterium; a halogen group; a nitrile group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; an alkylthio group an arylthio group an alkylsulfonyl group an arylsulfonyl group a silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; an aralkyl group; an aralkenyl group; an alkylaryl group; an alkylamino group; an aralkylamino group; a heteroarylamino group; an arylamino group; an arylphosphine group; or a heterocyclic group containing one or more of N, O, and S atoms, or being substituted or unsubstituted by a substituent formed by connecting two or more of the above-exemplified substituents, or being substituted or unsubstituted by a substituent formed by connecting two or more of the above-exemplified substituents. For example, the "substituent formed by connecting two or more substituents" can be a biphenyl group. That is, the biphenyl group can be an aryl group or can also be interpreted as a substituent formed by connecting two phenyl groups.

[0041] In this specification, the number of carbon atoms in the carbonyl group is not particularly limited, but preferably the number of carbon atoms is 1 to 40. Specifically, it can be a compound having the following structure, but is not limited thereto.

[0042]

[0043] In this specification, in the ester group, the oxygen of the ester group can be substituted by a linear, branched, or cyclic alkyl group having 1 to 25 carbon atoms; or an aryl group having 6 to 25 carbon atoms. Specifically, it can be a compound having the following structural formula, but is not limited thereto.

[0044]

[0045] In the present specification, the number of carbon atoms of the imide group is not particularly limited, but preferably it has 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

[0046]

[0047] In the present specification, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, etc., but is not limited thereto.

[0048] In the present specification, examples of the halogen group include fluorine, chlorine, bromine, or iodine.

[0049] In the present specification, the above alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but preferably it has 1 to 40 carbon atoms. According to one embodiment, the above alkyl group has 1 to 20 carbon atoms. According to another embodiment, the above alkyl group has 1 to 10 carbon atoms. According to another embodiment, the above alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a n-propyl group, an isopropyl group, a butyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a 1-methyl-butyl group, a 1-ethyl-butyl group, a pentyl group, a n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, a n-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 4-methyl-2-pentyl group, a 3,3-dimethylbutyl group, a 2-ethylbutyl group, a heptyl group, a n-heptyl group, a 1-methylhexyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, an octyl group, a n-octyl group, a tert-octyl group, a 1-methylheptyl group, a 2-ethylhexyl group, a 2-propylpentyl group, a nonyl group, a 2,2-dimethylheptyl group, a 1-ethyl-propyl group, a 1,1-dimethyl-propyl group, an isohexyl group, a 2-methylpentyl group, a 4-methylhexyl group, a 5-methylhexyl group, etc., but is not limited thereto.

[0050] In the present specification, the above alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but preferably it has 2 to 40 carbon atoms. According to one embodiment, the above alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the above alkenyl group has 2 to 10 carbon atoms. According to another embodiment, the above alkenyl group has 2 to 6 carbon atoms. Specific examples include a vinyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 3-methyl-1-butenyl group, a 1,3-butadienyl group, an allyl group, a 1-phenylethen-1-yl group, a 2-phenylethen-1-yl group, a 2,2-diphenylethen-1-yl group, a 2-phenyl-2-(naphthalen-1-yl)ethen-1-yl group, a 2,2-bis(diphenyl-1-yl)ethen-1-yl group, a stilbenyl group, a styryl group, etc., but is not limited thereto.

[0051] In this specification, the cycloalkyl group is not particularly limited, but is preferably a cycloalkyl group having 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, there are 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, etc., but are not limited thereto.

[0052] In this specification, the aryl group is not particularly limited, but is preferably an aryl group having 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. Regarding the above aryl group, as the monocyclic aryl group, it may be phenyl, biphenyl, terphenyl, etc., but is not limited thereto. As the above polycyclic aryl group, it may be naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, yl, fluorenyl, etc., but is not limited thereto.

[0053] In this specification, the fluorenyl group may be substituted, and two substituents may be combined with each other to form a spiro structure. When the above fluorenyl group is substituted, it may be etc. But it is not limited thereto.

[0054] In this specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si, and S as hetero elements, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. As examples of the heterocyclic group, there are thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, azolyl, diazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolinyl, indolyl, carbazolyl, benzo azolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, benzofuryl, phenanthroline, iso azolyl, thiadiazolyl, phenothiazinyl, and dibenzofuryl, etc., but are not limited thereto.

[0055] In this specification, the aryl groups in aralkyl, aralkenyl, alkylaryl, and arylamino groups are the same as the exemplified aryl groups described above. In this specification, the alkyl groups in aralkyl, alkylaryl, and alkylamino groups are the same as the exemplified alkyl groups described above. In this specification, the heteroaryl groups in heteroarylamino groups may be applied to the description of heterocyclic groups described above. In this specification, the alkenyl groups in aralkenyl groups are the same as the exemplified alkenyl groups described above. In this specification, an arylene group is a divalent group, and other than that, the description of aryl groups described above may be applied. In this specification, a heteroarylene group is a divalent group, and other than that, the description of heterocyclic groups described above may be applied. In this specification, a hydrocarbon ring is not a monovalent group, but is formed by combining two substituents, and other than that, the description of aryl groups or cycloalkyl groups described above may be applied. In this specification, a heterocyclic ring is not a monovalent group, but is formed by combining two substituents, and other than that, the description of heterocyclic groups described above may be applied.

[0056] In the above Chemical Formula 1, one or more hydrogens may be replaced by deuterium.

[0057] Preferably, the above Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-5:

[0058] [Chemical Formula 1-1]

[0059]

[0060] [Chemical Formula 1-2]

[0061]

[0062] [Chemical Formula 1-3]

[0063]

[0064] [Chemical Formula 1-4]

[0065]

[0066] [Chemical Formula 1-5]

[0067]

[0068] In the above Chemical Formulas 1-1 to 1-5,

[0069] X, L, Ar, R1 to R5, and n1 to n6 are the same as defined above.

[0070] Preferably, L is a single bond or a phenylene group,

[0071] The above phenylene group is unsubstituted or substituted by one or more deuteriums.

[0072] Preferably, Ar is phenyl, biphenyl, dibenzofuranyl, dibenzothiophenyl, 9-phenyl-carbazolyl or carbazol-9-yl,

[0073] The above-mentioned Ar is unsubstituted or substituted by more than one deuterium.

[0074] Preferably, n1 is 4, n2 is 2, n3 is 4, and R1 to R3 are all deuterium.

[0075] Preferably, n4 is 4 and R4 are all deuterium.

[0076] Preferably, n5 is 3, n6 is 4, and R5 are all deuterium.

[0077] Representative examples of the compound represented by the above Chemical Formula 1 are shown below:

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088] In addition, the present invention provides a method for manufacturing the compound represented by the above Chemical Formula 1 as shown in the following Reaction Formula 1.

[0089] [Reaction Formula 1]

[0090]

[0091] In the above Reaction Formula 1, A, X, L, Ar, R1 to R5, and n1 to n6 are the same as defined above.

[0092] The above step 1 is an amine substitution reaction, preferably carried out in the presence of a palladium catalyst and a base, and the reactive groups for the amine substitution reaction can be changed according to the techniques known in the art. The above step 2 is a Suzuki coupling reaction, preferably carried out in the presence of a palladium catalyst and a base, and the reactive groups for the Suzuki coupling reaction can be changed according to the techniques known in the art. The above manufacturing method can be further specified in the manufacturing examples described later.

[0093] In addition, the present invention provides an organic light-emitting device comprising a compound represented by the above Chemical Formula 1. As an example, the present invention provides an organic light-emitting device, which includes: a first electrode, a second electrode disposed opposite to the first electrode, and one or more organic layers disposed between the first electrode and the second electrode, and one or more of the organic layers contain a compound represented by the above Chemical Formula 1.

[0094] The organic layer of the organic light-emitting device of the present invention can be formed of a single-layer structure or a multilayer structure in which two or more organic layers are stacked. For example, the organic light-emitting device of the present invention can have a structure including a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc. as organic layers. However, the structure of the organic light-emitting device is not limited thereto, and it can include a smaller number of organic layers.

[0095] In addition, the above organic layer may include a light-emitting layer, and the light-emitting layer contains a compound represented by the above Chemical Formula 1. In particular, the compound according to the present invention can be used as a dopant for the light-emitting layer.

[0096] In addition, the above organic layer may include an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer contains a compound represented by the above Chemical Formula 1.

[0097] In addition, the above electron transport layer, electron injection layer, or a layer that simultaneously conducts electron transport and electron injection contains a compound represented by the above Chemical Formula 1.

[0098] In addition, the above organic layer includes a light-emitting layer and an electron transport layer, and the electron transport layer may contain a compound represented by the above Chemical Formula 1.

[0099] In addition, the organic light-emitting device according to the present invention can be an organic light-emitting device of a structure (normal type) in which an anode, one or more organic layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light-emitting device according to the present invention can be an inverted structure (inverted type) organic light-emitting device in which a cathode, one or more organic layers, and an anode are sequentially stacked on a substrate. For example, a structural example of the organic light-emitting device according to an embodiment of the present invention is illustrated inFigure 1 and 2 。

[0100] Figure 1 FIG. illustrates an example of an organic light-emitting device composed of a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4. In the structure described above, the compound represented by the above Chemical Formula 1 may be included in the above light-emitting layer.

[0101] Figure 2 FIG. illustrates an example of an organic light-emitting device composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron transport layer 8, and a cathode 4. In the structure described above, the compound represented by the above Chemical Formula 1 may be included in one or more of the above hole injection layer, hole transport layer, light-emitting layer, and electron transport layer.

[0102] The organic light-emitting device according to the present invention can be manufactured using materials and methods known in the art, except that one or more of the above organic layers contain the compound represented by the above Chemical Formula 1. In addition, when the above organic light-emitting device includes a plurality of organic layers, the above organic layers may be formed of the same substance or different substances.

[0103] For example, the organic light-emitting device according to the present invention can be manufactured by sequentially laminating a first electrode, an organic layer, and a second electrode on a substrate. At this time, it can be manufactured as follows: using a PVD (Physical Vapor Deposition) method such as sputtering or e-beam evaporation, depositing a metal, a conductive metal oxide, or an alloy thereof on the substrate to form an anode, and then forming an organic layer including a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer on the anode, and then depositing a substance that can be used as a cathode on the organic layer. In addition to this method, the organic light-emitting device can also be manufactured by sequentially depositing a cathode substance, an organic layer, and an anode substance on the substrate.

[0104] In addition, the compound represented by the above Chemical Formula 1 can form an organic layer not only by vacuum evaporation but also by solution coating method when manufacturing an organic light-emitting device. Here, the solution coating method refers to spin coating, dip coating, blade coating, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited thereto.

[0105] In addition to these methods, the organic light-emitting device can also be manufactured by sequentially depositing a cathode substance, an organic layer, and an anode substance on the substrate (WO 2003 / 012890). However, the manufacturing method is not limited thereto.

[0106] As an example, the first electrode described above is an anode, and the second electrode described above is a cathode, or the first electrode described above is a cathode, and the second electrode described above is an anode.

[0107] As the anode material, generally, in order to enable holes to be smoothly injected into the organic layer, a material with a large work function is preferred. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, gold, or their alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; and conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylenedioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

[0108] As the cathode material, generally, in order to enable electrons to be easily injected into the organic layer, a material with a small work function is preferred. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or their alloys; multilayer structure materials such as LiF / Al or LiO2 / Al, but are not limited thereto.

[0109] The hole injection layer described above is a layer that injects holes from the electrode. As the hole injection material, a compound is preferably used: a compound having the ability to transport holes, having the effect of injecting holes from the anode, having an excellent hole injection effect on the light-emitting layer or the light-emitting material, preventing excitons generated in the light-emitting layer from migrating to the electron injection layer or the electron injection material, and having excellent thin film forming ability. It is preferred that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic compounds, hexanitrile hexaazatriphenylene-based organic compounds, quinacridone-based organic compounds, perylene-based organic compounds, anthraquinone, and conductive polymers such as polyaniline and polythiophene, but are not limited thereto.

[0110] The hole transport layer described above is a layer that receives holes from the hole injection layer and transports the holes to the light-emitting layer. The hole transport material is a material that can receive holes from the anode or the hole injection layer and transfer them to the light-emitting layer, and a material with a large hole mobility is suitable. Specific examples include arylamine-based organic compounds, conductive polymers, and block copolymers having both a conjugated part and a non-conjugated part, but are not limited thereto.

[0111] The above-mentioned light-emitting material is a material that can receive holes and electrons from the hole transport layer and the electron transport layer respectively and combine them to emit light in the visible light region, and is preferably a material with high quantum efficiency for fluorescence or phosphorescence. As a specific example, there is tris(8-hydroxyquinoline)aluminum (Alq3); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; benzo azole, benzothiazole, and benzimidazole-based compounds; poly(p-phenylene vinylene) (PPV)-based polymers; spiro compounds; polyfluorene, rubrene, etc., but not limited thereto.

[0112] The above-mentioned light-emitting layer may contain a host material and a dopant material. The host material includes aromatic condensed ring derivatives or heterocyclic compounds, etc. Specifically, as aromatic condensed ring derivatives, there are anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and as heterocyclic compounds, there are carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds pyrimidine derivatives, etc., but not limited thereto.

[0113] As the dopant material, there are aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, etc. Specifically, the aromatic amine derivative is an aromatic condensed ring derivative having a substituted or unsubstituted arylamino group, and there are pyrene, anthracene, perylene, diindenoperylene, etc. having an arylamino group. The styrylamine compound is a compound in which at least one arylvinyl group is substituted on a substituted or unsubstituted arylamine, and is substituted or unsubstituted by one or more substituents selected from aryl, silyl, alkyl, cycloalkyl, and arylamino groups. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetramine, etc., but not limited thereto. In addition, as the metal complex, there are iridium complexes, platinum complexes, etc., but not limited thereto.

[0114] The above-mentioned electron transport layer is a layer that receives electrons from the electron injection layer and transports the electrons to the light-emitting layer. The electron transport material is a material that can receive electrons well from the cathode and transfer them to the light-emitting layer, and a material with a large electron mobility is suitable. As a specific example, there are Al complexes of 8-hydroxyquinoline, complexes containing Alq3, organic radical compounds, hydroxyflavone-metal complexes, etc., but not limited thereto. The electron transport layer can be used together with any desired cathode material as used in the prior art. In particular, examples of suitable cathode materials are common materials having a low work function and accompanied by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium, and samarium, each accompanied by an aluminum layer or a silver layer in each case.

[0115] The above-mentioned electron injection layer is a layer that injects electrons from the electrode, and preferably uses the following compounds: compounds having the ability to transport electrons, having the effect of injecting electrons from the cathode, having an excellent electron injection effect on the light-emitting layer or light-emitting material, preventing excitons generated in the light-emitting layer from migrating to the hole injection layer, and having excellent thin-film forming ability. Specifically, there are fluorenone, anthraquinodimethane, biphenylquinone, thiopyran dioxide, azole, diazole, triazole, imidazole, perylene tetracarboxylic acid, fluoreneylidene methane, anthrone, etc. and their derivatives, metal coordination compounds, and nitrogen-containing five-membered ring derivatives, etc., but are not limited thereto.

[0116] As the above-mentioned metal coordination compounds, there are lithium 8-hydroxyquinoline, zinc bis(8-hydroxyquinoline), copper bis(8-hydroxyquinoline), manganese bis(8-hydroxyquinoline), aluminum tris(8-hydroxyquinoline), aluminum tris(2-methyl-8-hydroxyquinoline), gallium tris(8-hydroxyquinoline), beryllium bis(10-hydroxybenzo[h]quinoline), zinc bis(10-hydroxybenzo[h]quinoline), gallium bis(2-methyl-8-quinoline) chloride, gallium bis(2-methyl-8-quinoline)(o-cresol), aluminum bis(2-methyl-8-quinoline)(1-naphthol), gallium bis(2-methyl-8-quinoline)(2-naphthol), etc., but are not limited thereto.

[0117] According to the materials used, the organic light-emitting device according to the present invention can be a top-emitting type, a bottom-emitting type, or a bidirectional-emitting type.

[0118] In addition, the compound represented by the above chemical formula 1 can be included not only in the organic light-emitting device but also in an organic solar cell or an organic transistor.

[0119] The manufacture of the compound represented by the above chemical formula 1 and the organic light-emitting device containing the same will be specifically described in the following examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

[0120] [Examples]

[0121] Example 1: Manufacture of Compound 1

[0122]

[0123] (Step 1) Manufacture of Compound 1-1

[0124] Under nitrogen atmosphere, 5-phenyl-5,8-dihydroindole [2,3-c] carbazole (10 g, 30.1 mmol) and 1-chloro-2-fluorobenzene (3.9 g, 30.1 mmol) were added to DMAc (200 ml), stirred and refluxed. Then, sodium tert-butoxide (8.7 g, 90.2 mmol) was added. After reacting for 5 hours, the solid was cooled to room temperature and filtered. The solid was dissolved in chloroform (400 ml), washed with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column using chloroform and ethyl acetate to produce a white solid compound 1-1 (8.4 g, yield 63%).

[0125] MS:[M+H] + =444

[0126] (Step 2) Preparation of Compound 1

[0127] Under nitrogen atmosphere, compound 1-1 (20 g, 46.2 mmol) and (dibenzo[b,d]furan-4-yl-d7)boronic acid (10.1 g, 46.2 mmol) were added to distilled water. alkane (Diox) (400ml), stirring and reflux. Then, potassium phosphate (29.4g, 138.5mmol) was dissolved in water (29ml) and added. After sufficient stirring, bis(dibenzylideneacetone)palladium (0) (0.8g, 1.4mmol) and tricyclohexylphosphine (0.8g, 2.8mmol) were added. After reacting for 5 hours, the generated solid was filtered after cooling to room temperature. The solid was dissolved in chloroform (806ml), washed with water twice, the organic layer was separated, anhydrous magnesium sulfate was added, filtered after stirring, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized using chloroform and ethyl acetate to produce a white solid compound 1 (16.5g, yield 62%).

[0128] MS:[M+H] + =582.7

[0129] Example 2: Preparation of Compound 2

[0130]

[0131] (Step 1) Preparation of Compound 2-1

[0132] Under a nitrogen atmosphere, 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole (10 g, 30.1 mmol) and TfOH (2 ml) were added to C6D6 (100 ml), and the mixture was stirred at 40 °C for 4 hours. After the reaction was completed, the temperature was lowered to room temperature, D2O (20 ml) was added, and after stirring for 30 minutes, trimethylamine (2.4 ml) was added dropwise. The reaction solution was transferred to a separatory funnel and extracted with water and chloroform. The extract was dried over MgSO4 and recrystallized from ethanol to obtain compound 2-1 (7.5 g, yield 72%).

[0133] MS: [M+H] + = 348.5

[0134] (Step 2) Preparation of compound 2-2

[0135] Using compound 2-1 instead of 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole, a white solid compound 2-2 (9.9 g, yield 75%) was prepared by the same method as in Step 1 of Example 1 except for this substitution.

[0136] MS: [M+H] + = 459

[0137] (Step 3) Preparation of compound 2

[0138] Using compound 2-2 instead of compound 1-1 and using (dibenzothiophen-4-yl-d7)boronic acid instead of (dibenzofuran-4-yl-d7)boronic acid, a white solid compound 2 (14.7 g, yield 55%) was prepared by the same method as in Step 2 of Example 1 except for these substitutions.

[0139] MS: [M+H] + = 613.9

[0140] Example 3: Preparation of compound 3

[0141]

[0142] (Step 1) Preparation of compound 3-1

[0143] Using 5-([1,1'-biphenyl]-2-yl)-5,8-dihydroindolo[2,3-c]carbazole instead of 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole, a white solid compound 3-1 (13.8 g, yield 66%) was prepared by the same method as in Step 1 of Example 2 except for this substitution.

[0144] MS: [M+H] + = 428.6

[0145] (Step 2) Preparation of Compound 3-2

[0146] Using compound 3-1 instead of 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole, a white solid compound 3-2 (8.7 g, yield 69%) was prepared in the same manner as in Step 1 of Example 1 except for this change.

[0147] MS: [M+H] + = 539.2

[0148] (Step 3) Preparation of Compound 3

[0149] Using compound 3-2 instead of compound 1-1 and using (dibenzo[b,d]thiophen-4-yl-d7)boronic acid instead of (dibenzo[b,d]furan-4-yl-d7)boronic acid, a white solid compound 3 (9 g, yield 70%) was prepared in the same manner as in Step 2 of Example 1 except for these changes.

[0150] MS: [M+H] + = 693

[0151] Example 4: Preparation of Compound 4

[0152]

[0153] (Step 1) Preparation of Compound 4-1

[0154] Using 1-phenyl-11,12-dihydroindolo[2,3-a]carbazole instead of 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole, a white solid compound 4-1 (34.6 g, yield 52%) was prepared in the same manner as in Step 1 of Example 1 except for this change.

[0155] MS: [M+H] + = 444

[0156] (Step 2) Preparation of Compound 4-2

[0157] Using compound 4-2 instead of compound 1-1 and using dibenzo[b,d]furan-4-ylboronic acid instead of (dibenzo[b,d]furan-4-yl-d7)boronic acid, a white solid compound 4-2 (18.4 g, yield 71%) was prepared in the same manner as in Step 2 of Example 1 except for these changes.

[0158] MS: [M+H] + = 575.7

[0159] (Step 3) Preparation of Compound 4

[0160] Compound 4-2 was used in place of 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole, and otherwise, a white solid compound 4 (11.7 g, yield 56%) was produced in the same manner as in Step 1 of Example 2.

[0161] MS: [M+H] + = 601.8

[0162] Example 5: Preparation of Compound 5

[0163]

[0164] (Step 1) Preparation of Compound 5-1

[0165] 11-([1,1'-Biphenyl]-3-yl)-11,12-dihydroindolo[2,3-a]carbazole was used in place of 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole, and otherwise, a white solid compound 5-1 (9.1 g, yield 72%) was produced in the same manner as in Step 1 of Example 1.

[0166] MS: [M+H] + = 520

[0167] (Step 2) Preparation of Compound 5

[0168] Compound 5-1 was used in place of Compound 1-1, and (dibenzo[b,d]furan-4-yl-d7)boronic acid was used in place of (dibenzo[b,d]furan-4-yl-d7)boronic acid, and otherwise, a white solid compound 5 (14.4 g, yield 57%) was produced in the same manner as in Step 2 of Example 1.

[0169] MS: [M+H] + = 658.8

[0170] Example 6: Preparation of Compound 6

[0171]

[0172] (Step 1) Preparation of Compound 6-1

[0173] 5,12-Dihydroindolo[3,2-a]carbazole was used in place of 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole, and otherwise, a white solid compound 6-1 (10.4 g, yield 73%) was produced in the same manner as in Step 1 of Example 1.

[0174] MS: [M+H] + = 367.9

[0175] (Step 2) Preparation of Compound 6-2

[0176] Using compound 6-1 instead of compound 1-1 and using (dibenz[b,d]furan-4-yl)boronic acid instead of (dibenz[b,d]furan-4-yl-d7)boronic acid, a white solid compound 6-2 (15.5 g, yield 57%) was prepared by the same method as in Step 2 of Example 1.

[0177] MS: [M+H] + = 499.6

[0178] (Step 3) Preparation of Compound 6-3

[0179] Using compound 6-2 instead of 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole, a white solid compound 6-3 (30.2 g, yield 58%) was prepared by the same method as in Step 1 of Example 2.

[0180] MS: [M+H] + = 520.7

[0181] (Step 4) Preparation of Compound 6

[0182] Under a nitrogen atmosphere, 6-3 (10 g, 19.2 mmol) and 4-bromo-1,1'-biphenyl (4.5 g, 19.2 mmol) were added to xylene (200 ml), and the mixture was stirred and refluxed. Then, sodium tert-butoxide (5.5 g, 57.7 mmol) was added, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium (0.3 g, 0.6 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the resulting solid was filtered. The solid was dissolved in chloroform (388 ml), washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column using chloroform and ethyl acetate to obtain a white solid compound 6 (9.3 g, yield 72%).

[0183] MS: [M+H] + = 672.9

[0184] Example 7: Preparation of Compound 7

[0185]

[0186] (Step 1) Preparation of Compound 7-1

[0187] Using 5-([1,1'-biphenyl]-3-yl)-5,11-dihydroindolo[3,2-b]carbazole in place of 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole, a white solid compound 7-1 (9.4 g, yield 74%) was produced in the same manner as in Step 1 of Example 1, except for this substitution.

[0188] MS: [M+H] + = 520

[0189] (Step 2) Preparation of Compound 7-2

[0190] Using compound 7-1 in place of compound 1-1 and using (dibenzo[b,d]furan-4-yl)boronic acid in place of (dibenzo[b,d]furan-4-yl-d7)boronic acid, a white solid compound 7-2 (16.3 g, yield 65%) was produced in the same manner as in Step 2 of Example 1, except for these substitutions.

[0191] MS: [M+H] + = 651.8

[0192] (Step 3) Preparation of Compound 7

[0193] Using compound 7-2 in place of 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole, a white solid compound 7 (41.3 g, yield 79%) was produced in the same manner as in Step 1 of Example 2, except for this substitution.

[0194] MS: [M+H] + = 682

[0195] Example 8: Preparation of Compound 8

[0196]

[0197] (Step 1) Preparation of Compound 8-1

[0198] Using 5-phenyl-5,11-dihydroindolo[3,2-b]carbazole in place of 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole, a white solid compound 8-1 (8.4 g, yield 63%) was produced in the same manner as in Step 1 of Example 1, except for this substitution.

[0199] MS: [M+H] + = 444

[0200] (Step 2) Preparation of Compound 8-2

[0201] Compound 8-1 was used instead of compound 1-1, and dibenzo[b,d]thiophen-4-ylboronic acid was used instead of (dibenzo[b,d]furan-4-yl-d7)boronic acid. Otherwise, a white solid compound 8-2 (18.7 g, yield 70%) was prepared by the same method as in Step 2 of Example 1.

[0202] MS: [M+H] + = 591.7

[0203] (Step 3) Preparation of compound 8

[0204] Compound 8-2 was used instead of 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole. Otherwise, a white solid compound 8 (35 g, yield 67%) was prepared by the same method as in Step 1 of Example 2.

[0205] MS: [M+H] + = 617.9

[0206] Example 9: Preparation of compound 9

[0207]

[0208] (Step 1) Preparation of compound 9-1

[0209] 5-([1,1'-Biphenyl]-2-yl)-5,12-dihydroindolo[3,2-a]carbazole was used instead of 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole. Otherwise, a white solid compound 9-1 (7.6 g, yield 60%) was prepared by the same method as in Step 1 of Example 1.

[0210] MS: [M+H] + = 520

[0211] (Step 2) Preparation of compound 9

[0212] Compound 9-1 was used instead of compound 1-1, and (dibenzo[b,d]furan-4-yl-d7)boronic acid was used instead of (dibenzo[b,d]furan-4-yl-d7)boronic acid. Otherwise, a white solid compound 9 (7.6 g, yield 60%) was prepared by the same method as in Step 2 of Example 1.

[0213] MS: [M+H] + = 658.8

[0214] Example 10: Preparation of compound 10

[0215]

[0216] (Step 1) Preparation of Compound 10-1

[0217] Using 5-phenyl-5,12-dihydroindolo[3,2-a]carbazole instead of 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole, a white solid compound 10-1 (9.5 g, yield 71%) was prepared by the same method as in Step 1 of Example 1 except for this.

[0218] MS: [M+H] + = 444

[0219] (Step 2) Preparation of Compound 10-2

[0220] Using compound 10-1 instead of compound 1-1 and using dibenzo[b,d]thiophen-4-ylboronic acid instead of (dibenzo[b,d]furan-4-yl-d7)boronic acid, a white solid compound 10-2 (16 g, yield 60%) was prepared by the same method as in Step 2 of Example 1 except for this.

[0221] MS: [M+H] + = 591.7

[0222] (Step 3) Preparation of Compound 10

[0223] Using compound 10-2 instead of 5-phenyl-5,8-dihydroindolo[2,3-c]carbazole, a white solid compound 10 (38.6 g, yield 74%) was prepared by the same method as in Step 1 of Example 2 except for this.

[0224] MS: [M+H] + = 617.9

[0225] [Experimental Example]

[0226] Experimental Example 1

[0227] A glass substrate coated with a 100-nm-thick ITO (indium tin oxide) film was placed in distilled water dissolved with a detergent and washed using ultrasonic waves. At this time, the detergent was a product of Fischer Co., and the distilled water used was the distilled water filtered twice using a filter manufactured by Millipore Co. After washing the ITO for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After the distilled water washing was completed, ultrasonic washing was performed with solvents of isopropyl alcohol, acetone, and methanol and then dried, and then it was transported to a plasma cleaner. In addition, using oxygen plasma, the above substrate was cleaned for 5 minutes, and then the substrate was transported to a vacuum evaporator.

[0228] On the thus-prepared ITO transparent electrode, the following compound HI-A was thermally vacuum-evaporated to a thickness of 60 nm to form a hole injection layer. On the above hole injection layer, the following compound HAT was vacuum-evaporated to form a first hole transport layer with a thickness of 5 nm. On the above first hole transport layer, the following compound HT-A was vacuum-evaporated to form a second hole transport layer with a thickness of 50 nm. On the above second hole transport layer, the following compound HT-B was thermally vacuum-evaporated to a thickness of 45 nm to form an electron blocking layer. On the above electron blocking layer, the previously fabricated compound 1, the following compound GH-H, and the following compound GD were vacuum-evaporated at a weight ratio of 45:45:10 to a thickness of 40 nm to form a light-emitting layer. On the above light-emitting layer, the following compound ET-A was vacuum-evaporated to a thickness of 5 nm to form a hole blocking layer. On the above hole blocking layer, the following compound ET-B and the following compound LiQ were vacuum-evaporated at a weight ratio of 1:1 to form an electron injection and transport layer with a thickness of 35 nm. After evaporating lithium fluoride (LiF) to a thickness of 1 nm on the above electron injection and transport layer, then, aluminum was evaporated to a thickness of 100 nm to form a cathode, thereby fabricating an organic light-emitting device.

[0229] In the above process, the evaporation rate of the organic matter was maintained at 0.04 nm / sec to 0.09 nm / sec, the evaporation rate of lithium fluoride was maintained at 0.03 nm / sec, and the evaporation rate of aluminum was maintained at 0.2 nm / sec. During evaporation, the vacuum degree was maintained at 1×10 -7 Torr to 5×10 -5 Torr.

[0230]

[0231] Experimental Examples 2 to 10

[0232] In the above Experimental Example 1, the compounds described in Table 1 below were used instead of compound 1, and except for this, an organic light-emitting device was fabricated by the same method as in Experimental Example 1.

[0233] Comparative Experimental Examples 1 to 5

[0234] In the above Experimental Example 1, the compounds described in Table 1 below were used instead of compound 1, and except for this, an organic light-emitting device was fabricated by the same method as in Example 1. The compounds GH-A to GH-E used in Table 1 below are shown as follows.

[0235]

[0236] An electric current was applied to the organic light-emitting devices fabricated in the above Experimental Examples and Comparative Experimental Examples, and the voltage and efficiency were measured (10 mA / cm 2Reference), and lifespan (20 mA / cm 2 Reference), and the results are shown in Table 1 below. Here, the lifespan T95 refers to the time required for the luminance to decrease from the initial luminance (6000 nits) to 95%.

[0237]

Table 1

[0238]

[0239] In order to exhibit the high-efficiency characteristics of 4-dibenzofuran or dibenzothiophene while maintaining the excellent hole injection and mobility characteristics of indolocarbazole, it is important to design the molecule in such a way that steric hindrance is provided between the two substituents so that the two characteristics do not cancel each other out. For this purpose, an o-phenyl linking group is introduced to cause steric hindrance, and thus low-voltage and high-efficiency characteristics can be exhibited. However, due to steric hindrance, there is a problem of relatively reduced stability of 4-dibenzofuran (dibenzothiophene). In order to overcome the above problem, when deuterium substitution is carried out at the corresponding position, it can be confirmed that the improvement in lifespan is excellent compared to other positions.

[0240] For compounds GH-A and GH-B, it can be confirmed that the lifespan is significantly reduced due to the absence of deuterium substitution. Compound GH-C is linked with a m-phenyl linking group, and it is confirmed that no steric hindrance is generated, so the effects of indolocarbazole and dibenzothiophene cancel each other out. Compound GH-D does not exhibit high-efficiency characteristics by introducing a 3-dibenzofuran substituent, and when compound GH-E introduces benzofurancarbazole instead of indolocarbazole, it can be confirmed that the performance is reduced due to changes in energy level and hole injection characteristics.

Claims

1. A compound represented by the following chemical formula 1: [Chemical formula 1] In the chemical formula 1, A is a benzene ring fused to two adjacent five-membered rings, X is O or S, L is a single bond, or a substituted or unsubstituted C 6-60 Arylene, Ar is substituted or unsubstituted C 6-60 Aryl; or a substituted or unsubstituted C 2-60 Heteroaryl, R1 to R4 are each independently hydrogen or deuterium, R5 are each independently hydrogen or deuterium, but at least one of R5 is deuterium, n1 is an integer from 1 to 4, n2 is 1 or 2, n3 and n4 are each independently an integer from 1 to 4, n5 is an integer from 1 to 3, n6 is an integer of 1 to 4.

2. The compound according to claim 1, wherein The chemical formula 1 is represented by any one of the following chemical formulas 1-1 to 1-5: [Chemical formula 1-1] [Chemical formula 1-2] [Chemical formula 1-3] [Chemical formula 1-4] [Chemical formula 1-5] In the chemical formulas 1-1 to 1-5, X, L, Ar, R1 to R5 and n1 to n6 are the same as defined in claim 1.

3. The compound according to claim 1, wherein L is a single bond or a phenylene group, The phenylene group is unsubstituted or substituted with one or more deuterium groups.

4. The compound according to claim 1, wherein Ar is phenyl, biphenyl, dibenzofuranyl, dibenzothiophenyl, 9-phenyl-carbazolyl or carbazole-9-yl, The Ar is unsubstituted or substituted with more than one deuterium.

5. The compound according to claim 1, wherein n1 is 4, n2 is 2, n3 is 4, R1 to R3 are all deuterium.

6. The compound according to claim 1, wherein n4 is 4, R4 is deuterium.

7. The compound according to claim 1, wherein n5 is 3, n6 is 4, R5 is deuterium.

8. The compound according to claim 1, wherein The compound represented by the chemical formula 1 is any one selected from the following compounds:

9. An organic light emitting device, comprising: A first electrode, a second electrode disposed opposite to the first electrode, and one or more organic layers disposed between the first electrode and the second electrode, wherein one or more of the organic layers comprises the compound according to any one of claims 1 to 8.

10. The organic light emitting device according to claim 9, wherein: The organic layer containing the compound is a light-emitting layer.

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