KR20220068692A - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to a novel organic light-emitting compound represented by chemical formula I and can realize light-emitting properties such as low voltage driving and excellent light-emitting efficiency of a device by being employed as a material such as a light-emitting layer, a hole transport layer, an electron transport layer, and an electron blocking layer in an organic light-emitting device and a material for an organic layer such as a light efficiency improvement layer provided in the organic light-emitting device and the organic light-emitting device comprising the same.

Description

An organic light emitting compound and an organic light emitting device comprising the same {An electroluminescent compound and an electroluminescent device comprising the same}

The present invention relates to an organic light emitting compound, and more particularly, to an organic light emitting compound, characterized in that it is employed as a material for a light efficiency improvement layer (Capping layer) provided in an organic light emitting device, and low voltage driving and excellent luminous efficiency of the device by employing the same It relates to an organic light emitting device having significantly improved light emitting characteristics, such as.

The organic light emitting device can be formed on a transparent substrate as well as being able to drive at a low voltage of 10 V or less compared to a plasma display panel or an inorganic electroluminescent (EL) display, and consume relatively little power. , has the advantage of excellent color, and can represent three colors of green, blue, and red.

However, in order for such an organic light emitting device to exhibit the above characteristics, the material constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, is supported by stable and efficient materials. However, the development of a stable and efficient organic material layer material for an organic light emitting device has not yet been sufficiently developed.

Therefore, in order to realize a more stable organic light emitting device, and to achieve high efficiency, long lifespan, and large size of the device, additional improvements are required in terms of efficiency and lifespan characteristics. It is desperately needed.

In addition, in recent years, research on improving the characteristics of an organic light emitting device by giving a change in the performance of each organic material layer material, as well as a technology to improve color purity and increase luminous efficiency by optimized optical thickness between the anode and the cathode It has been focused on one of the important factors for improving the performance, and as an example of this method, an increase in luminous efficiency and excellent color purity are achieved by using a capping layer on an electrode.

Accordingly, the present invention is to provide a novel organic light emitting compound capable of implementing excellent light emitting characteristics such as low voltage driving and improved light emitting efficiency of the device by being employed in the light efficiency improving layer provided in the organic light emitting device and an organic light emitting device including the same. .

In order to solve the above problems, the present invention provides any one organic light emitting compound selected from the compounds represented by the following [Formula I].

[Formula Ⅰ]

Characteristic structures of the [Formula I] and R ₁ to L ₄ and X will be described later.

When the organic light-emitting compound according to the present invention is employed as a material for the light efficiency improvement layer provided in the organic light-emitting device, it is possible to realize light-emitting characteristics such as low voltage driving and excellent light-emitting efficiency of the device, so that it can be usefully used in various display devices.

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

The present invention relates to an organic light emitting compound represented by the following [Formula I] that can achieve light emitting characteristics such as low voltage driving and excellent luminous efficiency of the device of an organic light emitting device, and structurally includes an adamantyl group It is characterized in that it is a skeletal structure condensed by further bonding the following [Structural Formula A1] or [Structural Formula A2] to the skeleton of ].

[Formula Ⅰ]

In the [Formula I],

Adjacent two selected from a plurality of X are connected to the following [Structural Formula A1] or [Structural Formula A2] to form a condensed ring, and the remaining Xs are each independently CH.

[Structural formula A1] [Structural formula A2]

In the [Structural Formula A1] to [Structural Formula A2],

Y is any one selected from O, S, NR ₁₁ and CR ₁₂ R ₁₃ .

wherein R ₁ to R ₁₃ are each independently hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 1 to C 20 alkoxy group, a substituted or unsubstituted A halogenated alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted halogenated alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 3 to 30 carbon atoms , a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 3 to C 30 heteroaryl group, a substituted or unsubstituted C 1 to C 30 alkylamine group, a substituted or unsubstituted C 5 to Any one selected from a 30 arylamine group, a substituted or unsubstituted C1-C30 alkylsilyl group, and a substituted or unsubstituted C5-C30 arylsilyl group.

Each of R ₁₂ and R ₁₃ may be connected to each other to form an alicyclic or aromatic monocyclic or polycyclic ring, and the carbon atom of the formed alicyclic or aromatic monocyclic or polycyclic ring is selected from N, S and O It may be substituted with any one or more heteroatoms.

Meanwhile, in the definitions of R ₁ to R ₁₃ , 'substituted or unsubstituted' means deuterium, a halogen group, a cyano group, a nitro group, a hydroxy group, a silyl group, an alkyl group, a halogenated alkyl group, a cycloalkyl group, or a heterocycloalkyl group. , a heterocycloalkenyl group, an alkoxy group, an aryl group, a heteroaryl group, an alkylamine group, an arylamine group and substituted with one or more substituents selected from the group consisting of a silyl group, or substituted with a substituent to which two or more of the substituents are connected Or, it means that it does not have any substituents.

For specific examples, the substituted aryl group means that a phenyl group, a biphenyl group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group, a tetracenyl group, an anthracenyl group, etc. are substituted with other substituents do.

In addition, the substituted heteroaryl group refers to a pyridyl group, a thiophenyl group, a triazine group, a quinoline group, a phenanthroline group, an imidazole group, a thiazole group, an oxazole group, a carbazole group and a condensed heterocyclic group thereof, such as a benzquinoline group. , a benzimidazole group, a benzoxazole group, a benzthiazole group, a benzcarbazole group, a dibenzothiophenyl group, a dibenzofuran group, and the like are substituted with other substituents.

In the present invention, examples of the substituents will be described in detail below, but the present invention is not limited thereto.

In the present invention, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 20. Specific examples include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1- Ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl- 2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert -Octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group , isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, and the like, but is not limited thereto.

In the present invention, the alkoxy group may be straight-chain or branched. Although the number of carbon atoms of the alkoxy group is not particularly limited, it is preferably 1 to 20 in a range that does not cause steric hindrance. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, i-propyloxy group, n-butoxy group, isobutoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group , neopentyloxy group, isopentyloxy group, n-hexyloxy group, 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group , a benzyloxy group, a p-methylbenzyloxy group, etc., but is not limited thereto.

In the present invention, the aryl group may be monocyclic or polycyclic, and the number of carbon atoms is not particularly limited, but is preferably 6 to 30. Examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group, and a stilbene group. Examples of the polycyclic aryl group include a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, and a tetracenyl group. , chrysenyl group, fluorenyl group, acenaphthacenyl group, triphenylene group, fluoranthrene group, etc., but the scope of the present invention is not limited to these examples.

,

,

등이 있다.In the present invention, the fluorenyl group is a structure in which two ring organic compounds are connected through one atom, for example,

,

,

etc.

,

등이 있다.In the present invention, the fluorenyl group includes a structure of an open fluorenyl group, wherein the open fluorenyl group is a structure in which one ring compound is disconnected in a structure in which two ring organic compounds are connected through one atom. , for example

,

etc.

,

,

,

등이 있다.In addition, the carbon atom of the ring may be substituted with any one or more heteroatoms selected from N, S and O, for example,

,

,

,

etc.

In the present invention, the heteroaryl group is a heterocyclic group containing O, N, or S as a heteroatom, and the number of carbon atoms is not particularly limited, but preferably has 2 to 30 carbon atoms, and for a specific example thereof in the present invention, a thiophene group , furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, acridyl group, pyridazine group, pyra Zinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, carbazole group, benzoxa Zol group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, dibenzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group, oxadia and a zolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, a phenoxazine group, a phenothiazine group, and the like, but are not limited thereto.

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

Specific examples of the halogen group as a substituent used in the present invention include fluorine (F), chlorine (Cl), bromine (Br), and the like.

In the present invention, the cycloalkyl group refers to, and includes, monocyclic, polycyclic and spiro alkyl radicals, and preferably contains 3 to 20 ring carbon atoms, cyclopropyl, cyclopentyl, cyclohexyl, bicyclo heptyl, spirodecyl, spirodecyl, adamantyl, and the like, wherein the cycloalkyl group may be optionally substituted.

In the present invention, heterocycloalkyl groups refer to and include aromatic and non-aromatic cyclic radicals containing one or more heteroatoms, wherein one or more heteroatoms are O, S, N, P, B, Si, and Se , Preferably it is selected from O, N or S, and specifically, when N is included, it may be aziridine, pyrrolidine, piperidine, azepane, azocan, and the like.

In the present invention, an alkenyl group refers to and includes both straight-chain and branched-chain alkene radicals, and an alkenyl group is essentially an alkyl group comprising at least one carbon-carbon double bond in the alkyl chain. A cycloalkenyl group is essentially a cycloalkyl group comprising one or more carbon-carbon double bonds within the cycloalkyl ring.

Also, heteroalkenyl group as used herein refers to an alkenyl radical having one or more carbon atoms substituted by a heteroatom, and one or more heteroatoms are O, S, N, P, B, Si, and Se; Preferably, it is selected from O, N or S.

In the present invention, preferred alkenyl, cycloalkenyl, or heteroalkenyl groups contain 2 to 20 carbon atoms.

Also, in the present invention, an alkynyl group refers to and includes both straight-chain and branched-chain alkene radicals, and a preferred alkenyl group contains 2 to 20 carbon atoms.

The organic light emitting compound according to the present invention represented by the above [Formula I] can be used as various organic material layers in the organic light emitting device due to its structural specificity, and more specifically, it can be used as a light efficiency improving layer material provided in the organic light emitting device.

Preferred examples of the organic light emitting compound represented by [Formula I] according to the present invention include the following compounds, but is not limited thereto.

As such, the organic light emitting compound according to the present invention can synthesize an organic light emitting compound having various characteristics using a characteristic skeleton exhibiting unique properties and a moiety having intrinsic properties introduced thereto, As a result, when the organic light emitting compound according to the present invention is applied to various organic material layers such as a light emitting layer, a light efficiency improving layer, a hole transport layer, an electron transport layer, an electron blocking layer, a hole blocking layer, etc. can

In addition, the compound of the present invention can be applied to a device according to a general method for manufacturing an organic light emitting device.

The organic light emitting device according to an embodiment of the present invention may have a structure including a first electrode and a second electrode and an organic material layer disposed therebetween, and the organic light emitting compound according to the present invention is used in the organic material layer of the device Except that, it may be manufactured using a conventional device manufacturing method and material.

The organic material layer of the organic light emitting device according to the present invention may have a single-layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, it may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an electron blocking layer, a hole blocking layer, a light efficiency improving layer (Capping layer), and the like. However, the present invention is not limited thereto and may include a smaller number or a larger number of organic material layers.

In addition, the organic electroluminescent device according to an embodiment of the present invention includes a substrate, a first electrode (anode), an organic material layer, a second electrode (cathode), and a light efficiency improving layer, wherein the light efficiency improving layer is a lower portion of the first electrode ( Bottom emission) or on the second electrode top (Top emission).

In the method of forming the second electrode upper (Top emission), the light formed in the light emitting layer is emitted toward the cathode, and the light emitted toward the cathode passes through the light efficiency improvement layer (CPL) formed of the compound according to the present invention having a relatively high refractive index. The wavelength of is amplified and thus the light efficiency is increased .

The organic material layer structure of the preferred organic light emitting device according to the present invention will be described in more detail in the following Examples.

In addition, the organic light emitting device according to the present invention uses a PVD (physical vapor deposition) method, such as sputtering or e-beam evaporation, to form a metal or a conductive metal oxide or an alloy thereof on a substrate. It can be prepared by depositing an anode, forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon.

In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer, but is not limited thereto and may have a single layer structure. In addition, the organic layer is formed using a variety of polymer materials by a solvent process rather than a vapor deposition method, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be made in layers.

As the anode material, a material having a large work function is generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc. Metal oxides, combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT) , a conductive polymer such as polypyrrole and polyaniline, but is not limited thereto.

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

The hole injection material is a material capable of well injecting holes from the anode at a low voltage, and it is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene, quinacridone-based organic material, perylene-based organic material, Anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

As the hole transport material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer is suitable, and a material having high hole mobility is suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together. can be further improved.

The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ), carbazole-based compounds, dimerized styryl compounds, BAlq, 10-hydroxybenzoquinoline-metal compounds, benzoxazole, benzthiazole and There are benzimidazole-based compounds, poly(p-phenylenevinylene) (PPV)-based polymers, spiro compounds, polyfluorene, rubrene, and the like, but is not limited thereto.

As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high electron mobility is suitable. Specific examples include, but are not limited to, an Al complex of 8-hydroxyquinoline, a complex including Alq ₃ , an organic radical compound, and a hydroxyflavone-metal complex.

The organic light emitting diode according to the present invention may be a top emission type, a back emission type, or a double side emission type depending on the material used.

In addition, the organic light emitting compound according to the present invention can act on a principle similar to that applied to the organic light emitting device in organic electronic devices including organic solar cells, organic photoreceptors, organic transistors, and the like.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are for explaining the present invention in more detail, the scope of the present invention is not limited thereby, and it is common in the art that various changes and modifications are possible within the scope and spirit of the present invention. It will be obvious to those with knowledge.

Synthesis example 1: Synthesis of compound 1

(One) production example 1: Synthesis of Intermediate 1-1

9-tricyclo[3.3.1.13,7]dec-1-yl-9H-carbazole (10.0 g, 0.033 mol), N-bromosuccinimide (7.1 g, 0.040 mol) was added to 200 mL of DMF and stirred at room temperature for 5 hours. reacted. After completion of the reaction, the mixture was extracted and concentrated, and then columned to obtain 7.4 g (yield 58.7%) of <Intermediate 1-1>.

(2) production example 2: Synthesis of intermediate 1-2

Intermediate 1-1 (10.0 g, 0.026 mol), bis(pinacolato)diboron (8.0 g, 0.032 mol), KOAc (5.2 g, 0.053 mol), dioxane 200 in Pd(dppf)Cl ₂ (0.6 g, 0.001 mol) mL and stirred at 100 °C for 12 hours to react. After completion of the reaction, extraction and concentration were performed, followed by column to obtain 7.2 g (yield 64.1%) of <Intermediate 1-2>.

(3) production example 3: Synthesis of Intermediate 1-3

Intermediate 1-2 (10.0 g, 0.023 mol), 1-iodo-2-nitrobenzene (6.9 g, 0.028 mol), K ₂ CO ₃ (9.7 g, 0.070 mol), Pd(PPh ₃ ) ₄ (0.5 g, 0.001) mol), toluene 200 mL, ethanol 50 mL, H ₂ O 50 mL were added, and the reaction was stirred under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column to obtain 6.7 g (yield: 67.8%) of <Intermediate 1-3>.

(4) production example 4: Synthesis of Intermediate 1-4

Intermediate 1-3 (10.0 g, 0.024 mol), PPh ₃ (15.5 g, 0.059 mol), DCB were added, and the reaction was stirred under reflux at 180° C. for 3 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 4.2 g (yield 45.4%) of <Intermediate 1-4>.

(5) production example 5: Synthesis of compound 1

Intermediate 1-4 (10.0 g, 0.026 mol), fluorobenzene (3.0 g, 0.031 mol), Cs ₂ CO ₃ (5.3 g, 0.038 mol) was added with 500 mL of DMF, followed by stirring under reflux at 150 ° C for 12 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 8.4 g (yield 70.3%) of <Compound 1>.

LC/MS: m/z=466[(M+1) ⁺ ]

Synthesis example 2: Synthesis of compound 20

(One) production example 1: Synthesis of Intermediate 20-1

Intermediate 1-2 (10.0 g, 0.023 mol), 4-bromo-2-iodonitrobenzene (9.2 g, 0.028 mol) K ₂ CO ₃ (9.7 g, 0.070 mol), Pd(PPh ₃ ) ₄ (0.5 g, 0.001 mol) ), toluene 200 mL, ethanol 50 mL, H ₂ O 50 mL were added, and the reaction was stirred under reflux at 100 °C for 6 hours. After completion of the reaction, the mixture was extracted and concentrated, and then columned to obtain 6.7 g (yield: 57.1%) of <Intermediate 20-1>.

(2) production example 2: Synthesis of Intermediate 20-2

Intermediate 20-1 (10.0 g, 0.020 mol), PPh ₃ (13.1 g, 0.050 mol), DCB were added, and the reaction was stirred under reflux at 180° C. for 3 hours. After completion of the reaction, the mixture was extracted, concentrated, and columned to obtain 4.5 g (yield: 48.1%) of <Intermediate 20-2>.

(3) production example 3: Synthesis of Intermediate 20-3

Intermediate 20-2 (10.0 g, 0.021 mol), 1-(tert-butyl)-2-fluorobenzene (3.9 g, 0.026 mol), Cs ₂ CO ₃ (4.4 g, 0.032 mol) Add 500 mL of DMF to 150 ℃ The reaction was stirred at reflux for 12 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 8.8 g (yield 68.7%) of <Intermediate 20-3>.

(4) production example 4: Synthesis of compound 20

Intermediate 20-3 (10.0 g, 0.017 mol), 3,5-di-tert-butylphenylboronic acid (4.7 g, 0.020 mol), K ₂ CO ₃ (6.9 g, 0.050 mol), Pd(PPh ₃ ) ₄ (0.4 g, 0.0003 mol), toluene 200 mL, ethanol 50 mL, H ₂ O 50 mL were added, and the reaction was stirred under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 8.2 g (yield 69.4%) of <Compound 20>.

LC/MS: m/z=710[(M+1) ⁺ ]

Synthesis example 3: Synthesis of compound 57

(One) production example 1: Synthesis of intermediate 57-1

Add 500 mL of DMF to Intermediate 1-4 (10.0 g, 0.026 mol), 1-bromo-2-fluorobenzene (5.4 g, 0.031 mol), and Cs ₂ CO ₃ (5.3 g, 0.038 mol) at 150 ° C for 12 hours. The reaction was stirred under reflux. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 9.4 g (yield 67.3%) of <Intermediate 57-1>.

(2) production example 2: Synthesis of compound 57

Intermediate 57-1 (10.0 g, 0.018 mol), 3,5-bis(trifluoromethyl)phenylboronic acid (5.7 g, 0.022 mol), K ₂ CO ₃ (7.6 g, 0.055 mol), Pd(PPh ₃ ) ₄ (0.4 g, 0.0004 mol), toluene 200 mL, ethanol 50 mL, H ₂ O 50 mL were added, and the reaction was stirred under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 8.3 g (yield 66.7%) of <Compound 57>.

LC/MS: m/z=678 [(M+1) ⁺ ]

Synthesis example 4: Synthesis of compound 67

(One) production example 1: Synthesis of Intermediate 67-1

Intermediate 20-2 (10.0 g, 0.021 mol), fluorobenzene (2.5 g, 0.026 mol), Cs ₂ CO ₃ (4.4 g, 0.032 mol) was added with 500 mL of DMF, followed by stirring under reflux at 150 ° C for 12 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 8.5 g (yield 73.1%) of <Intermediate 67-1>.

(2) production example 2: Synthesis of compound 67

Intermediate 67-1 (10.0 g, 0.018 mol), (2-tert-butylphenyl)boronic acid (3.9 g, 0.022 mol) K ₂ CO ₃ (7.6 g, 0.055 mol), Pd(PPh ₃ ) ₄ (0.4 g, 0.0004 mol), toluene 200 mL, ethanol 50 mL, H ₂ O 50 mL were added, and the reaction was stirred under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 7.4 g (yield 67.4%) of <Compound 67>.

LC/MS: m/z=598[(M+1) ⁺ ]

Synthesis example 5: Synthesis of compound 75

(One) production example 1: Synthesis of intermediate 75-1

Add 500 mL of DMF to Intermediate 1-4 (10.0 g, 0.026 mol), 1-Bromo-4-fluorobenzene (5.4 g, 0.031 mol), and Cs ₂ CO ₃ (5.3 g, 0.038 mol) at 150 ° C for 12 hours. The reaction was stirred under reflux. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 8.9 g (yield 63.7%) of <Intermediate 75-1>.

(2) production example 2: Synthesis of compound 75

Intermediate 75-1 (10.0 g, 0.018 mol), 2-(4-Biphenylyl)amino-9,9-dimethylfluorene (9.9 g, 0.028 mol), NaOC(CH ₃ ) ₃ (3.5 g, 0.037 mol), catalyst Pd 170 mL of toluene was added to (dba) ₂ (0.5 g, 0.001 mol), P(t-Bu) ₃ (0.4 g, 0.002 mol), and the reaction was stirred at 100 °C for 5 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 11.2 g (yield 74.0%) of <Compound 75>.

LC/MS: m/z=825[(M+1) ⁺ ]

Synthesis example 6: Synthesis of compound 80

(One) production example 1: Synthesis of Intermediate 80-1

Intermediate 1-1 (10 g, 0.026 mol), 2-chloroaniline (5.03 g, 0.039 mol), NaOC(CH ₃ ) ₃ (5.1 g, 0.053 mol), catalyst Pd(dba) ₂ (0.7 g, 0.001 mol) , P(t-Bu) ₃ (0.53 g, 0.003 mol) was added to toluene and stirred at 100° C. for 5 hours to react. After completion of the reaction, the mixture was extracted, concentrated, and columned to obtain 8.2 g (yield 73.0%) of <Intermediate 80-1>.

(2) production example 2: Synthesis of Intermediate 80-2

NaOC(CH ₃ ) ₃ (12.3 g, 0.128 mol), Pd(OAc) ₂ (0.3 g, 0.001 mol) and [[(CH ₃ ) ₃ C] ₃ PH]BF ₄ (1.9 g, 0.006 mol) dioxane dissolved in Then, the intermediate 80-1 (in dioxane, 10 g, 0.026 mol) was added, and the reaction was stirred under reflux at 110° C. for 18 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 4.2 g (yield 45.9%) of <Intermediate 80-2>.

(3) production example 3: Synthesis of compound 80

Add 500 mL of DMF to Intermediate 80-2 (10.0 g, 0.026 mol), 1,3-Di-tert-butyl-5-fluorobenzene (6.4 g, 0.031 mol), Cs ₂ CO ₃ (5.3 g, 0.038 mol) The reaction was stirred under reflux at 150 °C for 12 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 9.3 g (yield 62.7%) of <Compound 80>.

LC/MS: m/z=578 [(M+1) ⁺ ]

Synthesis example 7: Synthesis of compound 189

(One) production example 1: Synthesis of intermediate 189-1

Intermediate 1-2 (10.0 g, 0.023 mol), methyl-5-bromo-2-iodobenzoate (9.6 g, 0.028 mol), K ₂ CO ₃ (9.7 g, 0.070 mol), Pd(PPh ₃ ) ₄ (0.5 g , 0.001 mol), toluene 200 mL, ethanol 50 mL, H ₂ O 50 mL, and reacted by stirring under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed to obtain 7.1 g (yield 58.9%) of <Intermediate 189-1>.

(2) production example 2: Synthesis of intermediate 189-2

Intermediate 189-1 (10.0 g, 0.019 mol) was dissolved in 50 mL of Anhydrous DCM, and then BBr ₃ (in DCM, 6.1 g, 0.024 mol) was added dropwise while maintaining 0 °C. Then, the reaction was stirred at 25 °C for 16 hours. After completion of the reaction, extraction and concentration were performed, followed by column to obtain 5.8 g (yield 58.0%) of <Intermediate 189-2>.

(3) production example 3: Synthesis of intermediate 189-3

Intermediate 189-2 (10.0 g, 0.019 mol) was placed in AcOH and stirred at 0 °C for 30 minutes, then H ₂ SO ₄ was slowly added dropwise and stirred again at room temperature for 1 hour to react. After the reaction was completed, the mixture was extracted with ethyl acetate, concentrated, and columnar to obtain 5.3 g (yield 54.9%) of <Intermediate 189-3>.

(4) production example 4: Synthesis of intermediate 189-4

Intermediate 189-3 (10.0 g, 0.020 mol), bis(pinacolato)diboron (6.1 g, 0.024 mol), KOAc (4.0 g, 0.040 mol), dioxane 200 in Pd(dppf)Cl ₂ (0.4 g, 0.001 mol) mL and stirred at 100 °C for 12 hours to react. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 7.5 g (yield 68.5%) of <Intermediate 189-4>.

(5) production example 5: Synthesis of compound 189

Intermediate 189-4 (10.0 g, 0.018 mol), 2'-bromo-3,5-bistrifluoromethylbiphenyl (8.2 g, 0.022 mol), K ₂ CO ₃ (7.6 g, 0.055 mol), Pd(PPh ₃ ) ₄ (0.4 g, 0.0004 mol), toluene 200 mL, ethanol 50 mL, H ₂ O 50 mL were added, and the reaction was stirred under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 7.8 g (yield: 60.1%) of <Compound 189>.

LC/MS: m/z=705[(M+1) ⁺ ]

Device embodiment (capping layer)

In an embodiment according to the present invention, the ITO transparent electrode was cleaned using an ITO glass substrate containing 25 mm × 25 mm × 0.7 mm Ag, after patterning so that the emission area was 2 mm × 2 mm in size. After the substrate was mounted in a vacuum chamber, the base pressure was 1 × 10 ^-6 torr or more, and an organic material and a metal were deposited in the following structure on the ITO glass substrate containing Ag.

Device Examples 1 to 20

By employing the compound implemented according to the present invention in the light efficiency improving layer, a blue organic light emitting device having the following device structure was manufactured, and light emission characteristics including light emission efficiency were measured.

Ag/ITO / hole injection layer (HAT-CN, 5 nm) / hole transport layer (α-NPB, 100 nm) / electron blocking layer (TCTA, 10 nm) / light emitting layer (20 nm) / electron transport layer (201: Liq, 30 nm) / LiF (1 nm) / Mg:Ag (15 nm) / Light efficiency improvement layer (70 nm)

HAT-CN was formed to a thickness of 5 nm to form a hole injection layer on an ITO transparent electrode containing Ag on a glass substrate, and then α-NPB was formed into a film of 100 nm for the hole transport layer. The electron blocking layer was formed of TCTA with a thickness of 10 nm. In addition, the light emitting layer was co-deposited at 20 nm using BH1 as a host compound and BD1 as a dopant compound. Further, an electron transport layer (50% doped with [201] compound Liq below) was formed to a thickness of 30 nm and LiF 1 nm. Then, a film of 15 nm was formed of Mg:Ag in a ratio of 1:9. And as the light efficiency improvement layer (capping layer) compound, compounds 1, 3, 20, 37, 57, 58, 60, 61, 67, 75, 80, 127, 189, 219, 237, 240, 243 implemented in the present invention , 244, 261, and 271 were formed to a thickness of 70 nm to fabricate an organic light emitting diode.

Device Comparative Example 1

The organic light emitting device for Device Comparative Example 1 was manufactured in the same manner except that the light efficiency improving layer was not used in the device structures of Examples 1 to 20.

Device Comparative Example 2

The organic light emitting device for Device Comparative Example 2 was prepared in the same manner except that Alq ₃ was used instead of the compound of the present invention as the light efficiency improving layer compound in the device structures of Examples 1 to 20.

Experimental Example 1: Light emitting characteristics of Device Examples 1 to 20

The organic light emitting device manufactured according to the above example was measured using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research) to measure the driving voltage, current efficiency and color coordinates, and the result value based on 1,000 nits is shown in [Table 1] below.

Example Light Efficiency Improvement Layer V cd/A CIEx CIEy One Formula 1 3.6 8.7 0.136 0.057 2 Formula 3 4.0 8.0 0.142 0.049 3 Formula 20 3.8 8.3 0.140 0.052 4 Formula 37 4.1 7.9 0.141 0.050 5 chemical formula 57 3.5 8.8 0.135 0.058 6 Formula 58 3.6 8.6 0.139 0.055 7 Formula 60 3.5 8.7 0.137 0.058 8 Formula 61 3.8 8.4 0.140 0.054 9 Formula 67 4.0 8.0 0.142 0.048 10 Formula 75 3.9 8.0 0.143 0.045 11 Formula 80 4.0 8.0 0.141 0.052 12 Formula 127 3.7 8.6 0.141 0.056 13 Formula 189 3.8 8.4 0.140 0.054 14 Formula 219 3.8 8.3 0.142 0.052 15 Formula 237 3.6 8.5 0.140 0.056 16 Formula 240 3.7 8.4 0.139 0.054 17 Formula 243 3.9 8.6 0.143 0.050 18 Formula 244 3.8 8.5 0.138 0.055 19 Formula 261 4.0 8.7 0.137 0.049 20 Formula 271 3.7 8.3 0.140 0.051 Comparative Example 1 not used 4.5 7.0 0.151 0.140 Comparative Example 2 Alq ₃ 4.3 7.8 0.145 0.063

Looking at the results shown in [Table 1], when the compound according to the present invention is applied to the device as a light efficiency improving layer, compared to the conventional devices (Comparative Examples 1 and 2), it can be confirmed that the driving voltage is reduced and the current efficiency is improved. have.

[HAT-CN] [α-NPB] [BH1] [BD1] [201]

[TCTA]

Claims (7)

An organic light emitting compound represented by the following [Formula I]:
[Formula Ⅰ]

In the [Formula I],
Adjacent two selected from a plurality of X are linked to the following [Structural Formula A1] or [Structural Formula A2] to form a condensed ring, and the remaining Xs are each independently CH,
[Structural formula A1] [Structural formula A2]

In the [Structural Formula A1] to [Structural Formula A2],
Y is any one selected from O, S, NR ₁₁ and CR ₁₂ R ₁₃ ,
R ₁ to R ₁₃ are each independently hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 1 to C 20 alkoxy group, a substituted or unsubstituted C 1 A halogenated alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted halogenated alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 3 to 30 carbon atoms, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, a substituted or unsubstituted C1 to C30 alkylamine group, a substituted or unsubstituted C5 to C30 of an arylamine group, a substituted or unsubstituted C1-C30 alkylsilyl group, or a substituted or unsubstituted C5-C30 arylsilyl group,
Each of R ₁₂ and R ₁₃ may be connected to each other to form an alicyclic or aromatic monocyclic or polycyclic ring, and the carbon atom of the formed alicyclic or aromatic monocyclic or polycyclic ring is selected from N, S and O It may be substituted with any one or more heteroatoms. According to claim 1,
In the definitions of R ₁ to R ₁₃ , 'substituted or unsubstituted' means deuterium, a halogen group, a cyano group, a nitro group, a hydroxy group, a silyl group, an alkyl group, a halogenated alkyl group, a cycloalkyl group, a heterocycloalkyl group, a hetero substituted with one or two or more substituents selected from the group consisting of a cycloalkenyl group, an alkoxy group, an aryl group, a heteroaryl group, an alkylamine group, an arylamine group, and a silyl group Or an organic light emitting compound, characterized in that it does not have any substituents. The method of claim 1,
The [Formula I] is an organic light-emitting compound, characterized in that any one selected from the following [Compound 1] to [Compound 279]:

An organic light emitting device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode,
At least one layer of the organic material layer is an organic light emitting device comprising the organic light emitting compound of [Formula I] according to claim 1. 5. The method of claim 4,
The organic material layer is selected from a hole injection layer, a hole transport layer, a layer that performs both hole injection and hole transport functions, an electron transport layer, an electron injection layer, a layer that performs both electron transport and electron injection functions, an electron blocking layer, a hole blocking layer and a light emitting layer including one or more floors that become
At least one of the layers comprises an organic light emitting compound represented by the [Formula I]. 5. The method of claim 4,
Further comprising a light efficiency improvement layer (Capping layer) formed on at least one side opposite to the organic material layer among the upper or lower portions of the first electrode and the second electrode,
The light efficiency improving layer is an organic light emitting device, characterized in that it comprises an organic light emitting compound represented by the [Formula I]. 7. The method of claim 6,
The light efficiency improving layer is an organic light emitting device, characterized in that formed on at least one of a lower portion of the first electrode or an upper portion of the second electrode.