KR20220073135A - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention is a novel organic light emitting compound represented by [Formula I] that can implement light emitting characteristics such as low voltage driving and excellent luminous efficiency of the device by being employed as a light efficiency improving layer material provided in an organic light emitting device, and organic light emitting containing the same It's about the little ones.
[Formula Ⅰ]

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 an organic light emitting compound represented by the following [Formula I].

[Formula Ⅰ]

Characteristic structures of the [Formula I] and R ₁ , L, X and Ar ₁ to Ar ₂ 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 a skeleton structure represented by the following [Formula I] and a characteristic substituent is introduced at the R ₁ (ortho) position, and a characteristic moiety is introduced through the linking group L.

[Formula Ⅰ]

In the [Formula I],

R ₁ is deuterium, a halogen group, a cyano group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C1-C20 halogenated alkyl group, A substituted or unsubstituted halogenated alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted deuterated alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted deuterated alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted A cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, Any one selected from a substituted or unsubstituted C1-C30 alkylsilyl group and a substituted or unsubstituted C5-C30 arylsilyl group.

L is a single bond as a divalent linking group, or any one selected from the following [Structural Formula 1] (* represents a site to be connected, n is an integer from 0 to 2, and L is the same or different from each other when plural).

[Structural Formula 1]

Each X is independently CH or N, and at least one of the plurality of Xs is N.

Ar ₁ to Ar ₂ are the same as or different from each other, and each independently represents a deuterium, a halogen group, a cyano group, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkyl group, a substituted or An unsubstituted C 3 to C 30 heterocycloalkyl group, 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 alkyl Any one selected from an amine group, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, and a substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms.

Meanwhile, in the definitions of R ₁ and Ar ₁ to Ar ₂ , 'substituted or unsubstituted' means deuterium, deuterium, halogen group, cyano group, nitro group, hydroxyl group, silyl group, alkyl group, halogenated alkyl group, heavy water One or two or more selected from the group consisting of a digested alkyl group, a cycloalkyl group, a heterocycloalkyl group, an alkoxy group, a halogenated alkoxy group, a deuterated alkoxy group, an aryl group, a heteroaryl group, an alkylamine group, an arylamine group, and a silyl group It means that it is substituted with a substituent, or is substituted with a substituent to which two or more of the substituents are connected, or 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, a deuterated alkyl group or alkoxy group, halogenated alkyl group or alkoxy group means an alkyl group or alkoxy group in which the alkyl group or alkoxy group is substituted with deuterium or a halogen group.

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 an unsubstituted silyl group or a silyl group substituted with an alkyl group, an aryl group, etc., and specific examples of the silyl group include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxy phenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, dimethylfurylsilyl, and the like, but is not limited thereto.

In the present invention, the amine group may be -NH ₂ , an alkylamine group, an arylamine group, etc., the arylamine group means an amine substituted with aryl, and the alkylamine group means an amine substituted with an alkyl, an arylamine group Examples of these include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group, and the aryl group in the arylamine group is the same as the definition of the aryl group, , The alkyl group of the alkylamine group is also the same as the definition of the alkyl group.

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.

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 compound, dimerized styryl compound, BAlq, 10-hydroxybenzoquinoline-metal compound, 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 2

(One) production example 1: Synthesis of Intermediate 2-1

Add 500 mL of DMF to 4-Bromocarbazole (10.0 g, 0.041 mol), 1-(tert-butyl)-2-fluorobenzene (7.4 g, 0.049 mol), and Cs ₂ CO ₃ (8.4 g, 0.061 mol) at 150 °C. The reaction was stirred under reflux for 12 hours. After completion of the reaction, 11.2 g (yield 72.9%) of <Intermediate 2-1> was obtained by extraction and concentration by column.

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

Intermediate 2-1 (10.0 g, 0.026 mol), bis(pinacolato)diboron (8.1 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 was performed, recrystallization and column purification were performed to obtain 7.4 g (yield 65.8%) of <Intermediate 2-2>.

(3) production example 3: Synthesis of compound 2

Intermediate 2-2 (10.0 g, 0.024 mol), 4-Bromo-2,6-diphenylpyridine (8.8 g, 0.028 mol), K ₂ CO ₃ (9.8 g, 0.071 mol), Pd(PPh ₃ ) ₄ (0.5 g , 0.001 mol) was added 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O, followed by stirring 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 66.0%) of <Compound 2>.

LC/MS: m/z=528[(M+1) ⁺ ]

Synthesis example 2: Synthesis of compound 49

(One) production example 1: Synthesis of intermediate 49-1

Add 500 mL of DMF to 4-Bromocarbazole (10.0 g, 0.041 mol), 1-Fluoro-2-iodobenzene (10.8 g, 0.049 mol), Cs ₂ CO ₃ (8.4 g, 0.061 mol) and reflux at 150 ° C for 12 hours. The reaction was stirred. After completion of the reaction, 13.6 g (yield 74.7%) of <Intermediate 49-1> was obtained by extraction, concentration, and column.

(2) production example 2: Synthesis of intermediate 49-2

Intermediate 49-1 (10.0 g, 0.022 mol), 3,5-Di-tert-butylphenylboronic acid (6.3 g, 0.027 mol), K ₂ CO ₃ (9.3 g, 0.067 mol), Pd(PPh ₃ ) ₄ (0.5 g, 0.0004 mol) was added 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O, followed by stirring under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed to obtain 7.6 g (yield 66.7%) of <Intermediate 49-2>.

(3) production example 3: Synthesis of intermediate 49-3

Intermediate 49-2 (10.0 g, 0.020 mol), bis(pinacolato)diboron (6.0 g, 0.024 mol), KOAc (3.8 g, 0.039 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, recrystallization and column purification were performed to obtain 7.8 g (yield 71.4%) of <Intermediate 49-3>.

(4) production example 4: Synthesis of compound 49

Intermediate 49-3 (10.0 g, 0.018 mol), 4-[1,1'-Biphenyl]-4-yl-6-bromo-2-phenylpyrimidine (8.3 g, 0.022 mol), K ₂ CO ₃ (7.4 g, 0.054 mol), Pd(PPh ₃ ) ₄ (0.4 g, 0.0004 mol) was added to 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O, followed by reaction under reflux stirring at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 8.7 g (yield 65.7%) of <Compound 49>.

LC/MS: m/z=737[(M+1) ⁺ ]

Synthesis example 3: Synthesis of compound 125

(One) production example 1: Synthesis of Intermediate 125-1

Intermediate 49-1 (10.0 g, 0.022 mol), (2-Tert-butylphenyl)boronic acid (4.8 g, 0.027 mol), K ₂ CO ₃ (9.3 g, 0.067 mol), Pd(PPh ₃ ) ₄ (0.5 g , 0.0004 mol) was added 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O, followed by stirring under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column to obtain 6.8 g (yield: 67.1%) of <Intermediate 125-1>.

(2) production example 2: Synthesis of intermediate 125-2

Intermediate 125-1 (10.0 g, 0.022 mol), bis(pinacolato)diboron (6.7 g, 0.026 mol), KOAc (4.3 g, 0.044 mol), dioxane 200 in Pd(dppf)Cl ₂ (0.5 g, 0.001 mol) mL and stirred at 100 °C for 12 hours to react. After completion of the reaction, extraction was performed, recrystallization and column purification were performed to obtain 8.2 g (yield 74.3%) of <Intermediate 125-2>.

(3) production example 3: Synthesis of compound 125

Intermediate 125-2 (10.0 g, 0.020 mol), 4-(2-Bromophenyl)-2,6-diphenylpyrimidine (9.3 g, 0.024 mol), K ₂ CO ₃ (8.3 g, 0.060 mol), Pd(PPh ₃ ) ₄ (0.5 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 8.5 g (yield: 62.5%) of <Compound 125>.

LC/MS: m/z=681 [(M+1) ⁺ ]

Synthesis example 4: Synthesis of compound 156

(One) production example 1: Synthesis of Intermediate 156-1

Intermediate 49-1 (10.0 g, 0.022 mol), 3,5-Bis(trifluoromethyl)phenylboronic acid (6.9 g, 0.027 mol), K ₂ CO ₃ (9.3 g, 0.067 mol), Pd(PPh ₃ ) ₄ (0.5 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 to obtain 6.8 g (yield: 57.0%) of <Intermediate 156-1>.

(2) production example 2: Synthesis of Intermediate 156-2

Intermediate 156-1 (10.0 g, 0.019 mol), bis(pinacolato)diboron (5.7 g, 0.023 mol), KOAc (3.7 g, 0.037 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 was performed, recrystallization and column purification were performed to obtain 7.3 g (yield 67.1%) of <Intermediate 156-2>.

(3) production example 3: Synthesis of compound 156

Intermediate 156-2 (10.0 g, 0.017 mol), 2-(2-Bromophenyl)-4,6-diphenyl-1,3,5-triazine (8.0 g, 0.021 mol), K ₂ CO ₃ (7.1 g, 0.052) mol), Pd(PPh ₃ ) ₄ (0.4 g, 0.0003 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, followed by column and recrystallization to obtain 8.4 g (yield 64.0%) of <Compound 156>.

LC/MS: m/z=762 [(M+1) ⁺ ]

Synthesis example 5: Synthesis of compound 227

(One) production example 1: Synthesis of intermediate 227-1

Intermediate 49-1 (10.0 g, 0.022 mol), Phenylboronic acid (3.3 g, 0.027 mol), K ₂ CO ₃ (9.3 g, 0.067 mol), Pd(PPh ₃ ) ₄ (0.5 g, 0.0004 mol), toluene 200 mL, 50 mL of ethanol, and 50 mL of H ₂ O 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 to obtain 6.2 g (yield 69.8%) of <Intermediate 227-1>.

(2) production example 2: Synthesis of intermediate 227-2

Intermediate 227-1 (10.0 g, 0.025 mol), bis(pinacolato)diboron (7.7 g, 0.030 mol), KOAc (4.9 g, 0.050 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 to obtain 8.2 g (yield 73.3%) of <Intermediate 227-2>.

(3) production example 3: Synthesis of intermediate 227-3

DMF was added to 1-Bromo-2-naphthaldehyde (10.0 g, 0.043 mol), Benzamidine hydrochloride (13.3 g, 0.085 mol), K ₂ CO ₃ (11.8 g, 0.085 mol), and the reaction was stirred at 120 ° C. for 18 hours. . After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 12.4 g (yield 66.5%) of <Intermediate 227-3>.

(4) production example 4: Synthesis of compound 227

Intermediate 227-2 (10.0 g, 0.023 mol), Intermediate 227-3 (11.8 g, 0.027 mol), K ₂ CO ₃ (9.3 g, 0.067 mol), Pd(PPh ₃ ) ₄ (0.5 g, 0.0004 mol), 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O 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 10.4 g (yield 68.4%) of <Compound 227>.

LC/MS: m/z=676[(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 on the Ag-containing ITO glass substrate in the following structure.

Device Examples 1 to 13

By employing the compound implemented according to the present invention in the light efficiency improvement 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 as 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. In addition, an electron transport layer (the following [201] compound doped with 50% Liq) 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 a light efficiency improving layer (capping layer) compound, compounds 2, 28, 38, 49, 87, 99, 125, 137, 152, 156, 171, 227, 245 implemented in the present invention were formed into a film to a thickness of 70 nm. An organic light emitting device was manufactured.

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 13.

Device Comparative Example 2

The organic light emitting device for Device Comparative Example 2 was manufactured 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 13.

Experimental Example 1: Light emitting characteristics of Device Examples 1 to 13

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 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 2 3.9 8.3 0.139 0.054 2 Formula 28 3.7 8.4 0.142 0.055 3 Formula 38 3.5 8.8 0.146 0.054 4 Formula 49 3.7 8.5 0.141 0.059 5 Formula 87 3.6 8.6 0.143 0.055 6 Formula 99 3.6 8.6 0.142 0.058 7 Formula 125 3.9 8.1 0.140 0.051 8 Formula 137 3.9 8.0 0.140 0.047 9 Formula 152 3.7 8.2 0.140 0.050 10 Formula 156 4.1 8.0 0.141 0.052 11 Formula 171 3.8 8.1 0.143 0.052 12 Formula 227 3.8 8.3 0.141 0.053 13 Formula 245 3.7 8.2 0.142 0.049 Comparative Example 1 not used 4.5 7.0 0.151 0.140 Comparative Example 2 Alq ₃ 4.3 7.8 0.149 0.057

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],
R ₁ is deuterium, a halogen group, a cyano group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C1-C20 halogenated alkyl group, A substituted or unsubstituted halogenated alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted deuterated alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted deuterated alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted A cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, Any one selected from a substituted or unsubstituted C1-C30 alkylsilyl group and a substituted or unsubstituted C5-C30 arylsilyl group,
L is a single bond as a divalent linking group, or any one selected from the following [Structural Formula 1] (* represents a linked site, n is an integer of 0 to 2),
[Structural Formula 1]

X is each independently CH or N, at least one of the plurality of X is N,
Ar ₁ to Ar ₂ are the same as or different from each other, and each independently represents a deuterium, a halogen group, a cyano group, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkyl group, a substituted or An unsubstituted C 3 to C 30 heterocycloalkyl group, 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 alkyl Any one selected from an amine group, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, and a substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms. The method of claim 1,
In the definitions of R ₁ and Ar ₁ to Ar ₂ , '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 deuterated alkyl group, substituted with one or more substituents selected from the group consisting of a cycloalkyl group, a heterocycloalkyl group, an alkoxy group, a halogenated alkoxy group, a deuterated alkoxy group, an aryl group, a heteroaryl group, an alkylamine group, an arylamine group, and a silyl group; , An organic light-emitting compound, characterized in that it is substituted with a substituent to which two or more of the substituents are connected, or 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 381]:

An organic light emitting device comprising a first electrode, a second electrode, and one or more organic material layers 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.