WO2020022779A1 - Novel heterocyclic compound and organic light-emitting device using same - Google Patents

Abstract

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

Description

Novel heterocyclic compound and organic light emitting device using the same

This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0086192 dated July 24, 2018 and Korean Patent Application No. 10-2019-0089573 dated July 24, 2019. All content disclosed in the literature is included as part of this specification.

The present invention relates to a novel heterocyclic compound and an organic light emitting device comprising the same.

In general, organic light emitting phenomenon refers to a phenomenon of converting 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, fast response time, excellent brightness, driving voltage and response speed characteristics, many studies have been conducted.

The organic light emitting device generally has a structure including an anode and a cathode and an organic layer between the anode and the cathode. The organic layer is often formed of a multi-layered structure composed of different materials to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode, and electrons are injected into the organic material layer, and excitons are formed when the injected holes and the electrons meet each other. When it falls back to the ground, it glows.

There is a continuous demand for the development of new materials for organic materials used in such organic light emitting devices.

[Preceding technical literature]

[Patent Documents]

(Patent Document 1) Korean Patent Publication No. 10-2000-0051826

The present invention relates to a novel heterocyclic compound and an organic light emitting device comprising the same.

The present invention provides a compound represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

Each X is independently N or CH, at least two of X is N,

Y ₁ is N, O or S,

Y ₂ and Y ₃ are each independently O or S,

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl including any one or more hetero atoms selected from the group consisting of substituted or unsubstituted N, O, S and Si,

R ₁ to R ₆ are each independently halogen; Hydroxy; Cyano; Nitrile; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Or C _2-60 heteroaryl containing one or more of substituted or unsubstituted O, N, Si, and S,

a, b, c, d and e are each independently an integer of 0 to 3,

f is an integer of 0-4.

In addition, the present invention is a first electrode; A second electrode provided to face the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises a compound represented by Chemical Formula 1. do.

The compound represented by Chemical Formula 1 may be used as a material of the organic material layer of the organic light emitting diode, and may improve efficiency, low driving voltage, and / or lifetime characteristics in the organic light emitting diode. In particular, the compound represented by Chemical Formula 1 may be used as a hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection material.

FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.

2 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 3, an electron transport layer 8, an electron injection layer 9. And an example of an organic light emitting element composed of a cathode 4.

Hereinafter, the present invention will be described in more detail to help understand the present invention.

The present invention provides a compound represented by Chemical Formula 1.

In this specification,

And

Means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" is deuterium; Halogen group; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide groups; An alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Silyl groups; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkylaryl group; Alkylamine group; Aralkyl amine groups; Heteroarylamine group; Arylamine group; Aryl phosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups including one or more of N, O, and S atoms, or two or more substituents connected to the substituents exemplified above. . For example, "a substituent to which two or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and can be interpreted as a substituent to which two phenyl groups are linked.

Although carbon number of a carbonyl group in this specification is not specifically limited, It is preferable that it is C1-C40. Specifically, it may be a compound having a structure as follows, but is not limited thereto.

In the present specification, the ester group may be substituted with oxygen of the ester group having 1 to 25 carbon atoms, a straight chain, branched chain or cyclic alkyl group 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.

In this specification, although carbon number of an imide group is not specifically limited, It is preferable that it is C1-C25. Specifically, it may be a compound having a structure as follows, but is not limited thereto.

In the present specification, specifically, the silyl group includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like. However, the present invention is not limited thereto.

In the present specification, the boron group specifically includes, but is not limited to, trimethylboron group, triethylboron group, t-butyldimethylboron group, triphenylboron group, phenylboron group and the like.

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

In the present specification, the alkyl group may be linear or branched chain, 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 include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

In the present specification, the alkenyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc. as the monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

In the present specification, a fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

And so on. However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si, and S as a dissimilar element, and the carbon number is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridil group , Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , Carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia There may be a sleepy group, a phenothiazinyl group, a dibenzofuranyl group, and the like, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the example of the alkyl group described above. In the present specification, the heteroaryl of the heteroarylamine may be applied to the description of the aforementioned heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the example of the alkenyl group described above. In the present specification, except that the arylene is a divalent group, the description of the aryl group described above may be applied. In the present specification, the description of the aforementioned heterocyclic group may be applied except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aforementioned aryl group or cycloalkyl group may be applied except that two substituents are formed by bonding. In the present specification, the heterocyclic group is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied except that two substituents are formed by bonding.

Preferably, X is all N.

Preferably, Ar ₁ and Ar ₂ are phenyl.

Preferably, Y ₁ is O or S.

Preferably, a, b, c, d, e and f are zero.

Preferably, the compound represented by Formula 1 may be selected from the group consisting of the following compounds.

The compound represented by Chemical Formula 1 may be prepared by the same method as in Scheme 1 below. The manufacturing method may be more specific in the production examples to be described later.

Scheme 1

In Scheme 1, the remaining definitions except for X 'are as defined above, and X' is halogen and more preferably bromo or chloro. The reaction is a Suzuki coupling reaction, preferably performed in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be changed as known in the art. The manufacturing method may be more specific in the production examples to be described later.

In another aspect, the present invention provides an organic light emitting device comprising a compound represented by the formula (1). In one embodiment, the present invention is a first electrode; A second electrode provided to face the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises a compound represented by Chemical Formula 1. do.

The organic material layer of the organic light emitting device of the present invention may be formed of a single layer structure, but may be formed of a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting 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 layers.

In addition, the organic layer may include a hole injection layer, a hole transport layer, an electron blocking layer, or a layer for simultaneously injecting and transporting the hole, and the hole injection layer, the hole transport layer, the electron blocking layer, or the hole injection and transport At the same time, the layer comprises a compound represented by the formula (1).

In addition, the organic layer may include a light emitting layer, and the light emitting layer includes a compound represented by Chemical Formula 1.

In addition, the organic layer may include an electron transport layer, an electron injection layer, or a layer for simultaneously transporting and transporting electrons, and the electron transport layer, the electron injection layer, or the layer for simultaneously transporting and transporting electrons is represented by Formula 1 above. It includes a compound represented by.

In addition, the organic layer may include a light emitting layer and an electron transport layer, the electron transport layer may include a compound represented by the formula (1).

In addition, the organic light emitting device according to the present invention may be an organic light emitting device having a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting diode according to the present invention may be an organic light emitting diode having an inverted type structure in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.

FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. In such a structure, the compound represented by Formula 1 may be included in the light emitting layer.

2 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 3, an electron transport layer 8, an electron injection layer 9. And an example of an organic light emitting element composed of a cathode 4. In such a structure, the compound represented by Formula 1 may be included in at least one layer of the hole injection layer, hole transport layer, electron blocking layer, light emitting layer, electron transport layer, electron injection layer.

Specifically, the organic material layer may include a light emitting layer, and the light emitting layer may include two or more host materials.

In this case, the two or more host materials may include a compound represented by Chemical Formula 1.

The organic light emitting device according to the present invention may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer includes the compound represented by Chemical Formula 1. In addition, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on the substrate to form an anode. In addition, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer may be formed thereon, and then a material that may be used as a cathode may be deposited thereon. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

In addition, the compound represented by Chemical Formula 1 may be formed as an organic layer by a solution coating method as well as a vacuum deposition method in the manufacture of the organic light emitting device. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.

In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material on a substrate from a cathode material (WO 2003/012890). However, the manufacturing method is not limited thereto.

In one example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode, the second electrode is an anode.

As the anode material, a material having a large work function is generally preferred to facilitate hole injection into the organic material layer. 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), indium zinc oxide (IZO); Combinations of oxides with metals 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, and the like, but are not limited thereto.

It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

The hole injection material is a layer for injecting holes from an electrode, and the hole injection material has a capability of transporting holes. The hole injection material has a hole injection effect at an anode, and has an excellent hole injection effect for a light emitting layer or a light emitting material. The compound which prevents the movement of the excited excitons to the electron injection layer or the electron injection material, and is excellent in thin film formation ability is preferable. Preferably, the highest 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 material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based Organic materials, anthraquinone and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer for receiving holes from the hole injection layer and transporting holes to the light emitting layer. A hole transporting material is a material capable of transporting holes from an anode or a hole injection layer and transferring them to the light emitting layer. This is suitable. Specific examples thereof include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable. Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq ₃ ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.

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 hetero ring-containing compound. Specifically, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and the heterocyclic containing compounds include carbazole derivatives, dibenzofuran derivatives and ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Dopant materials include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, and include pyrene, anthracene, chrysene and periplanthene having an arylamino group, and a styrylamine compound may be substituted or unsubstituted. At least one arylvinyl group is substituted with the above-described arylamine, and one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group and arylamino group are substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.

The electron transporting material is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. The electron transporting material is a material that can inject electrons well from the cathode and transfer them to the light emitting layer. This is suitable. Specific examples include Al complexes 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 conventional materials having a low work function followed by an aluminum or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, followed by aluminum layers or silver layers in each case.

The electron injection layer is a layer for injecting electrons from an electrode, has a capability of transporting electrons, has an electron injection effect from the cathode, excellent electron injection effect to the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer The compound which prevents the movement to a layer and is excellent in thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the derivatives thereof, metal Complex compounds, nitrogen-containing five-membered ring derivatives, and the like, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtolato) gallium, etc. It is not limited to this.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used.

In addition, the compound represented by Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

Preparation of the compound represented by Chemical Formula 1 and an organic light emitting device including the same will be described in detail in the following Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Preparation Example 1 Preparation of Intermediate A-2

a) Preparation of Intermediate A-1

4-bromodibenzo [b, d] furan (50 g, 122.0 mmol) and dibenzo [b, d] furan-4-ylboronic acid (25.9 g, 122.0 mmol) were dissolved in 500 ml of tetrahydrofuran (THF). . Add calcium carbonate (K ₂ CO ₃ ) 2 M solution (183 mL), tetrakis (triphenylphosphine) palladium (0) [Pd (PPh ₃ ) ₄ ] (4.2 g, 3 mol%), and add 12 hours. It was refluxed. After the reaction was completed, the mixture was cooled to room temperature, and the resulting mixture was extracted three times with water and toluene. The toluene layer was separated, dried over magnesium sulfate, and the filtrate was filtered and distilled under reduced pressure. The mixture was recrystallized once with chloroform and ethyl acetate, to obtain Intermediate A-1 (27.3 g, Yield 67%; MS: [M + H] ⁺ = 335).

b) Preparation of Intermediate A-2

Dissolve Intermediate A-1 (25.0 g, 74.8 mmol) in tetrahydrofuran (250 ml), lower the temperature to -78 ° C and slowly add 2.5 M n-butyllithium (t-BuLi) (35.9 ml, 89.8 mmol). Added. After stirring at the same temperature for 1 hour, triisopropylborate (B (OiPr) ₃ ) (21.1 ml, 112.2 mmol) was added thereto, and the mixture was stirred for 3 hours while gradually raising the temperature to room temperature. 2N aqueous hydrochloric acid solution (100 ml) was added to the reaction mixture, which was stirred for 1.5 hours at room temperature. The resulting precipitate was filtered off, washed sequentially with water and ethyl ether, and dried in vacuo. After drying, the mixture was dispersed in ethyl ether, stirred for 2 hours, filtered, and dried to prepare intermediate A-2 (23.8 g, yield 84%; MS: [M + H] ⁺ = 379).

Preparation Example 2 Preparation of Intermediate B-2

a) Preparation of Intermediate B-1

4-bromodibenzo [b, d] furan (50 g, 122.0 mmol) and dibenzo [b, d] thiophen-4-ylboronic acid (27.8 g, 122.0 mmol) were added to 500 ml of tetrahydrofuran (THF). Melted. Add calcium carbonate (K ₂ CO ₃ ) 2 M solution (183 mL), tetrakis (triphenylphosphine) palladium (0) [Pd (PPh ₃ ) ₄ ] (4.2 g, 3 mol%), and add 12 hours. It was refluxed. After the reaction was completed, the mixture was cooled to room temperature, and the resulting mixture was extracted three times with water and toluene. The toluene layer was separated, dried over magnesium sulfate, and the filtrate was filtered and distilled under reduced pressure. The mixture was recrystallized once with chloroform and ethyl acetate, to obtain Intermediate B-1 (34.1 g, Yield 71%; MS: [M + H] ⁺ = 352).

b) Preparation of Intermediate B-2

Dissolve Intermediate B-1 (25.0 g, 74.8 mmol) in tetrahydrofuran (250 ml), lower the temperature to -78 ° C and slowly add 2.5 M n-butyllithium (t-BuLi) (35.9 ml, 89.8 mmol). Added. After stirring at the same temperature for 1 hour, triisopropylborate (B (OiPr) ₃ ) (21.1 ml, 112.2 mmol) was added thereto, and the mixture was stirred for 3 hours while gradually raising the temperature to room temperature. 2N aqueous hydrochloric acid solution (100 ml) was added to the reaction mixture, which was stirred for 1.5 hours at room temperature. The resulting precipitate was filtered off, washed sequentially with water and ethyl ether, and dried in vacuo. After drying, the mixture was dispersed in ethyl ether, stirred for 2 hours, filtered, and dried to prepare intermediate B-2 (24.5 g, yield 87%; MS: [M + H] ⁺ = 395).

Preparation Example 3 Preparation of Intermediate C-2

1) Preparation of Intermediate C-1

500 ml of tetrahydrofuran (THF) with 4-bromodibenzo [b, d] thiophene (50 g, 114.5 mmol) and dibenzo [b, d] thiophen-4-ylboronic acid (26.1 g, 114.5 mmol) Dissolved in. To this was added calcium carbonate (K ₂ CO ₃ ) 2 M solution (172 mL), tetrakis (triphenylphosphine) palladium (0) [Pd (PPh ₃ ) ₄ ] (4.0 g, 3 mol%) and 12 hours It was refluxed. After the reaction was completed, the mixture was cooled to room temperature, and the resulting mixture was extracted three times with water and toluene. The toluene layer was separated, dried over magnesium sulfate, and the filtrate was filtered and distilled under reduced pressure. The mixture was recrystallized once with chloroform and ethyl acetate to give intermediate C-1 (28.9 g, yield 69%; MS: [M + H] ⁺ = 367).

2) Preparation of Intermediate C-2

Dissolve Intermediate C-1 (25.0 g, 68.3 mmol) in tetrahydrofuran (250 ml), lower the temperature to -78 ° C and slowly add 2.5 M n-butyllithium (t-BuLi) (32.8 ml, 82.0 mmol). Added. After stirring for 1 hour at the same temperature, triisopropylborate (B (OiPr) ₃ ) (23.6 ml, 102.5 mmol) was added, and the mixture was stirred for 3 hours while gradually raising the temperature to room temperature. 2N aqueous hydrochloric acid solution (100 ml) was added to the reaction mixture, which was stirred for 1.5 hours at room temperature. The resulting precipitate was filtered off, washed sequentially with water and ethyl ether, and dried in vacuo. After drying, the mixture was dispersed in ethyl ether, stirred for 2 hours, filtered, and dried to prepare intermediate C-2 (21.5 g, yield 77%; MS: [M + H] ⁺ = 411).

Preparation Example 4 Preparation of Intermediate D-2

1) Preparation of Intermediate D-1

4,6-dibromodibenzo [b, d] furan (50 g, 154.4 mmol), dibenzo [b, d] furan-4-ylboronic acid (68.7 g, 324.4 mmol) was added to tetrahydrofuran (THF) 500 dissolved in ml. Add calcium carbonate (K ₂ CO ₃ ) 2 M solution (463 mL), tetrakis (triphenylphosphine) palladium (0) [Pd (PPh ₃ ) ₄ ] (10.7 g, 3 mol%), and add 12 hours. It was refluxed. After the reaction was completed, the mixture was cooled to room temperature, and the resulting mixture was extracted three times with water and toluene. The toluene layer was separated, dried over magnesium sulfate, and the filtrate was filtered and distilled under reduced pressure. The mixture was recrystallized once with chloroform and ethyl acetate to give intermediate D-1 (56.4 g, yield 73%; MS: [M + H] ⁺ = 501).

2) Preparation of Intermediate D-2

Dissolve Intermediate D-1 (25.0 g, 50.0 mmol) in tetrahydrofuran (250 ml), lower the temperature to -78 ° C and slowly add 2.5 M n-butyllithium (t-BuLi) (24.0 ml, 60.0 mmol). Added. After stirring at the same temperature for 1 hour, triisopropylborate (B (OiPr) ₃ ) (17.3 ml, 75.0 mmol) was added thereto, and the mixture was stirred for 3 hours while gradually raising the temperature to room temperature. 2N aqueous hydrochloric acid solution (100 ml) was added to the reaction mixture, which was stirred for 1.5 hours at room temperature. The resulting precipitate was filtered off, washed sequentially with water and ethyl ether, and dried in vacuo. After drying, the mixture was dispersed in ethyl ether, stirred for 2 hours, filtered, and dried to prepare intermediate D-2 (16.6 g, yield 61%; MS: [M + H] ⁺ = 545).

Preparation Example 5 Preparation of Intermediate E-2

1) Preparation of Intermediate E-1

4,6-dibromobenzo [b, d] thiophene (50 g, 147.1 mmol), dibenzo [b, d] furan-4-ylboronic acid (65.5 g, 309.0 mmol) was added to tetrahydrofuran (THF). Dissolved in 500 ml. To this was added calcium carbonate (K ₂ CO ₃ ) 2 M solution (441 mL), tetrakis (triphenylphosphine) palladium (0) [Pd (PPh ₃ ) ₄ ] (10.2 g, 3 mol%) and 12 hours It was refluxed. After the reaction was completed, the mixture was cooled to room temperature, and the resulting mixture was extracted three times with water and toluene. The toluene layer was separated and dried over magnesium sulfate, and the filtrate was filtered and distilled under reduced pressure. The mixture was recrystallized once with chloroform and ethyl acetate to give Intermediate E-1 (46.3 g, 61% yield; MS: [M + H] ⁺ = 517).

2) Preparation of Intermediate E-2

Dissolve Intermediate E-1 (25.0 g, 48.4 mmol) in tetrahydrofuran (250 ml), lower the temperature to -78 ° C and slowly add 2.5 M n-butyllithium (t-BuLi) (23.3 ml, 58.1 mmol). Added. After stirring at the same temperature for 1 hour, triisopropylborate (B (OiPr) ₃ ) (16.8 ml, 72.7 mmol) was added, and the mixture was stirred for 3 hours while gradually raising the temperature to room temperature. 2N aqueous hydrochloric acid solution (100 ml) was added to the reaction mixture, which was stirred for 1.5 hours at room temperature. The resulting precipitate was filtered off, washed sequentially with water and ethyl ether, and dried in vacuo. After drying, the mixture was dispersed in ethyl ether, stirred for 2 hours, filtered, and dried to prepare intermediate E-2 (18.7 g, yield 69%; MS: [M + H] ⁺ = 561).

Preparation Example 6 Preparation of Intermediate F-2

1) Preparation of Intermediate F-1

4,6-dibromodibenzo [b, d] furan (50 g, 154.4 mmol), dibenzo [b, d] thiophen-4-ylboronic acid (73.9 g, 324.4 mmol) was added to tetrahydrofuran (THF). Dissolved in 500 ml. Add calcium carbonate (K ₂ CO ₃ ) 2 M solution (463 mL), tetrakis (triphenylphosphine) palladium (0) [Pd (PPh ₃ ) ₄ ] (10.7 g, 3 mol%), and add 12 hours. It was refluxed. After the reaction was completed, the mixture was cooled to room temperature, and the resulting mixture was extracted three times with water and toluene. The toluene layer was separated and dried over magnesium sulfate, and the filtrate was filtered and distilled under reduced pressure. The mixture was recrystallized once with chloroform and ethyl acetate to give Intermediate F-1 (44.4 g, Yield 50%; MS: [M + H] ⁺ = 577).

2) Preparation of Intermediate F-2

Dissolve Intermediate F-1 (25.0 g, 43.4 mmol) in tetrahydrofuran (250 ml), lower the temperature to -78 ° C and slowly add 2.5 M n-butyllithium (t-BuLi) (20.8 ml, 43.4 mmol). Added. After stirring for 1 hour at the same temperature, triisopropylborate (B (OiPr) ₃ ) (15.0 ml, 65.1 mmol) was added, and the mixture was stirred for 3 hours while gradually raising the temperature to room temperature. 2N aqueous hydrochloric acid solution (100 ml) was added to the reaction mixture, which was stirred for 1.5 hours at room temperature. The resulting precipitate was filtered off, washed sequentially with water and ethyl ether, and dried in vacuo. After drying, the mixture was dispersed in ethyl ether, stirred for 2 hours, filtered, and dried to prepare intermediate F-2 (19.1 g, yield 70%; MS: [M + H] ⁺ = 577).

Preparation Example 6 Preparation of Intermediate G-2

1) Preparation of Intermediate G-1

4,6-dibromobenzo [b, d] thiophene (50 g, 48.4 mmol), dibenzo [b, d] thiophen-4-ylboronic acid (70.5 g, 309.0 mmol) was added to tetrahydrofuran (THF Dissolved in 500 ml. To this was added calcium carbonate (K ₂ CO ₃ ) 2 M solution (441 mL), tetrakis (triphenylphosphine) palladium (0) [Pd (PPh ₃ ) ₄ ] (10.2 g, 3 mol%) and 12 hours It was refluxed. After the reaction was completed, the mixture was cooled to room temperature, and the resulting mixture was extracted three times with water and toluene. The toluene layer was separated, dried over magnesium sulfate, and the filtrate was filtered and distilled under reduced pressure. The mixture was recrystallized once with chloroform and ethyl acetate, to obtain Intermediate G-1 (48.4 g, Yield 60%; MS: [M + H] ⁺ = 549).

2) Preparation of Intermediate G-2

Intermediate G-1 (25.0 g, 45.6 mmol) was dissolved in tetrahydrofuran (250 ml), then the temperature was lowered to -78 ° C and 2.5 M n-butyllithium (t-BuLi) (21.9 ml, 45.6 mmol) was slowly added. Added. After stirring at the same temperature for 1 hour, triisopropylborate (B (OiPr) ₃ ) (15.8 ml, 68.4 mmol) was added thereto, and the mixture was stirred for 3 hours while gradually raising the temperature to room temperature. 2N aqueous hydrochloric acid solution (100 ml) was added to the reaction mixture, which was stirred for 1.5 hours at room temperature. The resulting precipitate was filtered off, washed sequentially with water and ethyl ether, and dried in vacuo. After drying, the mixture was dispersed in ethyl ether, stirred for 2 hours, filtered, and dried to prepare intermediate G-2 (15.9 g, yield 59%; MS: [M + H] ⁺ = 593).

Preparation Example 7 Preparation of Intermediate P-5

a) Preparation of Intermediate P-1

1-bromo-3-fluoro-2-iodobenzene (100 g, 333.5 mmol), 5-chloro-2-methoxyphenylboronic acid ((5-chloro- 2-methoxyphenyl) boronic acid) (62.2 g, 333.5 mmol) was dissolved in 800 ml of tetrahydrofuran (THF). Sodium carbonate (Na ₂ CO ₃ ) 2 M solution (500 mL) and tetrakis (triphenylphosphine) palladium (0) [Pd (PPh ₃ ) ₄ ] (7.7 g, 6.7 mmol) were added and refluxed for 12 hours. . After the reaction was completed, the mixture was cooled to room temperature, and the resulting mixture was extracted three times with water and toluene. The toluene layer was separated, dried over magnesium sulfate, and the filtrate was filtered and distilled under reduced pressure. The mixture was recrystallized three times with chloroform and ethanol to give intermediate P-1 (53.7 g, yield 51%; MS: [ M + H] ⁺ = 314).

b) preparation of intermediate P-2

Intermediate P-1 (50.0 g, 158.5 mmol) was dissolved in Dichlorometahne (600 ml) and cooled to 0 ° C. Boron tribromide (15.8 ml, 166.4 mmol) was slowly added dropwise and stirred for 12 hours. After the reaction was completed, washed three times with water, dried over magnesium sulfate (magnesium sulfate) and the filtrate was filtered under reduced pressure and purified by column chromatography to give the intermediate P-2 (47.4 g, 99% yield; MS: [M + H] ⁺ = 300).

c) preparation of intermediate P-3

Intermediate P-2 (40.0 g, 132.7 mmol) is dissolved in distilled dimethylformamide (DMF) (400 ml). It was cooled to 0 ° C., and sodium hydride (3.5 g, 145.9 mmol) was slowly added dropwise thereto. After stirring for 20 minutes, the mixture was stirred at 100 ° C. for 1 hour. After the reaction was completed and cooled to room temperature, 100 ml of ethanol (Ethanol) was slowly added. The mixture obtained by distillation under reduced pressure was recrystallized with chloroform and ethyl acetate to obtain intermediate P-3 (30.3 g, yield 81%; MS: [M + H] ⁺ = 280).

d) preparation of intermediate P-4

Intermediate P-3 (30.0 g, 106.6 mmol) was dissolved in tetrahydrofuran (300 ml), then cooled to -78 ° C and 1.7 M tert-butyllithium (t-BuLi) (62.7 ml, 106.6 mmol) was added. Slowly added. After stirring for 1 hour at the same temperature, triisopropylborate (B (OiPr) ₃ ) (28.3 ml, 213.1 mmol) was added, and the mixture was stirred for 3 hours while gradually raising the temperature to room temperature. 2N aqueous hydrochloric acid solution (200 ml) was added to the reaction mixture, which was stirred for 1.5 hours at room temperature. The resulting precipitate was filtered off, washed sequentially with water and ethyl ether, and dried in vacuo. After drying, the mixture was dispersed in ethyl ether, stirred for 2 hours, filtered, and dried to prepare intermediate P-4 (24.4 g, yield 93%; MS: [M + H] ⁺ = 247).

d) preparation of intermediate P-5

Intermediate P-4 (20.0 g, 81.2 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (21.8 g, 81.2 mmol) were dispersed in tetrahydrofuran (250 ml) , 2M aqueous potassium carbonate solution (aq. K ₂ CO ₃ ) (33.6 ml, 243.5 mmol) was added thereto, followed by tetrakistriphenylphosphinopalladium [Pd (PPh ₃ ) ₄ ] (1.9 g, 2 mol%), followed by 4 Stirring to reflux for hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized from tetrahydrofuran and ethyl acetate, filtered and dried to prepare intermediate P-5 (32.4 g, yield 92%; MS: [M + H] ⁺ = 434).

Preparation Example 8 Preparation of Intermediate Q-5

a) Preparation of Intermediate Q-1

1-bromo-3-fluoro-4-iodobenzene (50 g, 166.6 mmol), 5-chloro-2-methoxyphenylboronic acid ((5-chloro- 2-methoxyphenyl) boronic acid) (31.1 g, 166.6 mmol) was dissolved in 800 ml of tetrahydrofuran (THF). Add sodium carbonate (Na ₂ CO ₃ ) 2 M solution (250 mL), tetrakis (triphenylphosphine) palladium (0) [Pd (PPh ₃ ) ₄ ] (3.8 g, 3 mol%), and reflux for 12 hours. I was. After the reaction was completed, the mixture was cooled to room temperature, and the resulting mixture was extracted three times with water and toluene. The toluene layer was separated, dried over magnesium sulfate, and the filtrate was filtered and distilled under reduced pressure. The mixture was recrystallized three times with chloroform and ethanol to give an intermediate Q-1 (27.5 g, yield 51%; MS: [ M + H] ⁺ = 314).

b) Preparation of Intermediate Q-2

Intermediate Q-1 (25.0 g, 150 mmol) is dissolved in Dichlorometahne (300 ml) and cooled to 0 ° C. Boron tribromide (7.9 ml, 83.2 mmol) was slowly added dropwise and stirred for 12 hours. After completion of the reaction, the mixture was washed three times with water, dried over magnesium sulfate (magnesium sulfate), and the filtrate was filtered under reduced pressure and purified by column chromatography to give an intermediate Q-2 (23.7 g, yield 99%; MS: [M + H] ⁺ = 300).

c) preparation of intermediate Q-3

Intermediate Q-2 (20.0 g, 66.4 mmol) is dissolved in distilled dimethylformamide (DMF) (200 ml). It was cooled to 0 ° C. and sodium hydride (1.8 g, 72.9 mmol) was slowly added dropwise thereto. After stirring for 20 minutes, the mixture was stirred at 100 ° C. for 1 hour. After the reaction was completed and cooled to room temperature, 100 ml of ethanol (Ethanol) was slowly added. The mixture obtained by distillation under reduced pressure was recrystallized with chloroform and ethyl acetate to give an intermediate Q-3 (15.2 g, yield 81%; MS: [M + H] ⁺ = 280).

d) Preparation of Intermediate Q-4

Intermediate Q-3 (15.0 g, 53.3 mmol) was dissolved in tetrahydrofuran (150 ml), then the temperature was lowered to -78 ° C and 1.7 M tert-butyllithium (t-BuLi) (31.8 ml, 53.3 mmol) was added. Slowly added. After stirring for 1 hour at the same temperature, triisopropylborate (B (OiPr) ₃ ) (14.2 ml, 107.0 mmol) was added, and the mixture was stirred for 3 hours while gradually raising the temperature to room temperature. 2N aqueous hydrochloric acid solution (100 ml) was added to the reaction mixture, which was stirred for 1.5 hours at room temperature. The resulting precipitate was filtered off, washed sequentially with water and ethyl ether, and dried in vacuo. After drying, the mixture was dispersed in ethyl ether, stirred for 2 hours, filtered, and dried to prepare intermediate Q-4 (12.2 g, yield 93%; MS: [M + H] ⁺ = 247).

e) Preparation of Intermediate Q-5

Intermediate Q-4 (10.0 g, 40.6 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (10.9 g, 40.6 mmol) were dispersed in tetrahydrofuran (150 ml), followed by 2M. Aqueous potassium carbonate solution (aq. K ₂ CO ₃ ) (12 ml, 122 mmol) was added and tetrakistriphenylphosphinopalladium [Pd (PPh ₃ ) ₄ ] (1.0 g, 2 mol%) was added for 4 hours. Stirring to reflux. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized from tetrahydrofuran and ethyl acetate, filtered and dried to prepare intermediate Q-5 (16.2 g, yield 92%; MS: [M + H] ⁺ = 434).

Example 1 Preparation of Compound 1

Intermediate P-5 (15.0 g, 34.6 mmol) and Intermediate A-2 (13.1 g, 34.6 mmol) were dispersed in tetrahydrofuran (150 ml), followed by 2M aqueous potassium carbonate solution (aq. K ₂ CO ₃ ) (12 ml, 52 mmol) was added and bis (tri tert-butylphosphine) palladium [Pd (PPh ₃ ) ₄ ] (0.5 g, 3 mol%) was added thereto, followed by stirring under reflux for 4 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized with tetrahydrofuran and ethyl acetate, filtered and dried to give compound 1 (9.6 g, yield 38%; MS: [M + H] ⁺ = 732).

Example 2: Preparation of Compound 2

Compound 2 (11.4 g, yield 44%; MS: [M + H] ^{+ in the} same manner as in the preparation of compound 1 of Example 1, except that Intermediate B-2 (13.6 g, 34.6 mmol) was used instead of Intermediate A-2. = 748) was prepared.

Example 3: Preparation of Compound 3

Compound 3 (10.6 g, yield 40%; MS: [M + H] ^{+ in the} same manner as in the preparation of compound 1 of Example 1, except that Intermediate C-2 (14.2 g, 34.6 mmol) was used instead of Intermediate A-2. = 764) was prepared.

Example 4: Preparation of Compound 4

Intermediate Q-5 (15.0 g, 34.6 mmol) and Intermediate A-2 (13.1 g, 34.6 mmol) were dispersed in tetrahydrofuran (150 ml), followed by 2M aqueous potassium carbonate solution (aq. K ₂ CO ₃ ) (12 ml, 52 mmol) was added and bis (tri tert-butylphosphine) palladium [Pd (PPh ₃ ) ₄ ] (0.5 g, 3 mol%) was added thereto, followed by stirring under reflux for 4 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized with tetrahydrofuran and ethyl acetate, filtered and dried to give compound 4 (11.1 g, yield 44%; MS: [M + H] ⁺ = 732).

Example 5: Preparation of Compound 5

Compound 5 (13.2 g, yield 51%; MS: [M + H] ^{+ in the} same manner as in the preparation of compound 4 of Example 4, except that Intermediate B-2 (13.6 g, 34.6 mmol) was used instead of Intermediate A-2. = 748).

Example 6: Preparation of Compound 6

Compound 6 (7.1 g, yield 27%; MS: [M + H] ^{+ in the} same manner as in the preparation of compound 4 of Example 4, except that Intermediate C-2 (14.2 g, 34.6 mmol) was used instead of Intermediate A-2. = 764) was prepared.

Example 7: Preparation of Compound 7

2-chloro-4,6-diphenyl-1,3,5-triazine (10.0 g, 37.4 mmol) and intermediate D-2 (20.4 g, 34.6 mmol) were dispersed in tetrahydrofuran (150 ml) , 2M aqueous potassium carbonate solution (aq. K ₂ CO ₃ ) (56 ml, 112 mmol) was added and bis (tri tertary-butylphosphine) palladium [Pd (PPh ₃ ) ₄ ] (0.6 g, 3 mol%) After stirring, the mixture was refluxed for 4 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized with tetrahydrofuran and ethyl acetate, filtered and dried to give compound 7 (11.2 g, yield 41%; MS: [M + H] ⁺ = 732).

Example 8: Preparation of Compound 8

Compound 8 (14.8 g, yield 53%; MS: [M + H] ^{+ in the} same manner as in the preparation of compound 7 of Example 7, except that Intermediate E-2 (21.0 g, 37.4 mmol) was used instead of Intermediate D-2. = 748) was prepared.

Example 9: Preparation of Compound 9

Compound 9 (14.0 g, yield 49%; MS: [M + H] in the same manner as in the preparation of compound 7 of Example 7, except that Example F-2 (21.0 g, 37.4 mmol) was used instead of Example D-2. ] ⁺ = 764).

Example 10 Preparation of Compound 10

Compound 10 (12.8 g, yield 44%; MS: [M + H] in the same manner as in the preparation of compound 7 of Example 7, except that Example G-2 (21.0 g, 37.4 mmol) was used instead of Example D-2. ] ⁺ = 780).

Experimental Example 1

The glass substrate coated with ITO (indium tin oxide) having a thickness of 1,300 kPa was put in distilled water in which detergent was dissolved and ultrasonically cleaned. In this case, Fischer Co. was used as a detergent, and distilled water was filtered secondly as a filter of Millipore Co. as a distilled water. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After washing the distilled water, ultrasonic washing with a solvent of isopropyl alcohol, acetone, methanol, dried and transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.

On the ITO transparent electrode prepared as above, the following HI-1 compound was thermally vacuum deposited to a thickness of 50 kPa to form a hole injection layer. A hole transport layer was formed by thermal vacuum deposition of the following HT-1 compound to a thickness of 250 kPa on the hole injection layer, and an electron blocking layer was formed by vacuum depositing the following HT-2 compound to a thickness of 50 kPa on the hole transport layer. Compound 1, the following YGH-1 compound, and phosphorescent dopant YGD-1, which were prepared in Example 1 as a light emitting layer on the electron blocking layer, were co-deposited at a weight ratio of 44:44:12 to form a light emitting layer having a thickness of 400 kHz. The following ET-1 compound was vacuum deposited to a thickness of 250 kPa on the light emitting layer to form an electron transport layer. Formed. Aluminum was deposited to a thickness of 1000 Å on the electron injection layer to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7 Å / sec, the aluminum was maintained at the deposition rate of 2 Å / sec, the vacuum during deposition was maintained at 1 × 10 ^-7 ~ 5 × 10 ^-8 torr It was.

Experimental Examples 2 to 10

An organic light emitting diode was manufactured according to the same method as Experimental Example 1 except for using the compound described in Table 1 below instead of compound 1 in Experimental Example 1.

<Comparative Experimental Examples 1 to 4>

An organic light emitting diode was manufactured according to the same method as Experimental Example 1 except for using the compound described in Table 1 below instead of compound 1 in Experimental Example 1.

On the other hand, the compounds of CE1 to CE4 in Table 1 are as follows.

In the above experimental examples and comparative examples, the organic light emitting diodes were measured voltage and efficiency at a current density of 10 mA / cm ² , and lifespan was measured at a current density of 50 mA / cm ² , and the results are shown in Table 1 below. In this case, LT ₉₅ refers to a time (hr) that becomes 95% of the initial luminance.

As shown in Table 1, in the case of the experimental example using the compound of the present invention as a light emitting layer material, it was confirmed that the efficiency and life is superior to the comparative example. This is expected to increase the electrical stability as the dibenzofuran or dibenzothiophene group is substituted three.

[Description of the code]

1: substrate 2: anode

3: light emitting layer 4: cathode

5: hole injection layer 6: hole transport layer

7: electron blocking layer 8: electron transport layer

9: electron injection layer

Claims (9)

1. Compound represented by the following formula (1):

   [Formula 1]

   

   In Chemical Formula 1,

   Each X is independently N or CH, at least two of X is N,

   Y ₁ is N, O or S,

   Y ₂ and Y ₃ are each independently O or S,

   Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl including any one or more hetero atoms selected from the group consisting of substituted or unsubstituted N, O, S and Si,

   R ₁ to R ₆ are each independently halogen; Hydroxy; Cyano; Nitrile; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Or C _2-60 heteroaryl including one or more of substituted or unsubstituted O, N, Si, and S,

   a, b, c, d and e are each independently an integer of 0 to 3,

   f is an integer of 0-4.
2. The method of claim 1,

   X is all N.
3. The method of claim 1,

   Ar ₁ and Ar ₂ are phenyl.
4. The method of claim 1,

   Y ₁ is O or S.
5. The method of claim 1,

   wherein a, b, c, d, e and f are zero.
6. The method of claim 1,

   The compound represented by the formula (1) is characterized in that any one selected from the group consisting of the following compounds:

   

   

   

   

   

   
7. A first electrode; A second electrode provided to face the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises a compound according to any one of claims 1 to 6. That is, an organic light emitting device.
8. The method of claim 7, wherein

   The organic material layer may include a light emitting layer, and the light emitting layer includes two or more host materials.
9. The method of claim 8,

   The two or more host materials include a compound represented by Formula 1, an organic light emitting device.

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