KR20220106372A - 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 employed as a material for an organic layer such as a hole transporting layer in an organic light-emitting device or a light efficiency improvement layer provided in an organic light-emitting device to realize luminous properties such as improved low-voltage driving properties and excellent luminous efficiency and an organic light-emitting device comprising the same.

Description

An organic light emitting compound and an organic light emitting device comprising the same

The present invention relates to an organic light emitting compound, and more particularly, an organic light emitting compound, which is employed as a material for various organic layers in an organic light emitting device and a light efficiency improving layer (Capping layer) provided in the organic light emitting device, and a device using the same It relates to an organic light-emitting device with significantly improved low-voltage driving and luminous efficiency characteristics.

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 electroluminescence (EL) display, and consume relatively little power. , has the advantage of excellent color, and can represent three colors of green, blue, and red, and has recently become a subject of much interest as a next-generation display device.

However, in order for such an organic light emitting device to exhibit the above characteristics, a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc. However, the development of a stable and efficient organic 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 this regard, recently, with respect to the material of the hole transport layer in the structure of the organic light emitting device, research for improving the conductivity of the existing organic material has been actively conducted.

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 layer material, as well as a technology for improving color purity and increasing luminous efficiency by an optical thickness optimized between an anode and a cathode has been developed. It has been focused on one of the important factors for improving the performance, and as an example of this method, an increase in light efficiency and excellent color purity are achieved by using a capping layer on an electrode.

Accordingly, the present invention is a novel organic light emitting compound capable of implementing various hole transport layers in an organic light emitting device and a light efficiency improving layer provided in the organic light emitting device to realize improved low voltage driving and excellent light emitting efficiency characteristics of the device, and organic light emitting including the same We want to provide a device.

In order to solve the above problems, the present invention introduces various substituents, including the following [Formula 1] to [Structural Formula 2], at positions A ₁ and A ₂ in the skeleton represented by the following [Formula I], A ₁ and It provides an organic light emitting compound, characterized in that the following [Structural Formula 2] is introduced into at least one of the positions of A ₂ .

[Formula Ⅰ]

[Structural Formula 1]

[Structural Formula 2]

Characteristic structures of the [Formula I], [Structural Formula 1] to [Structural Formula 2], specific compounds implemented thereby, and definitions of each substituent will be described later.

When the compound according to the present invention is employed as a material for an organic layer such as a hole transport layer in an organic light emitting device and a light efficiency improvement layer provided in an organic light emitting device, it is possible to realize improved low voltage driving characteristics and excellent luminous efficiency of the device. It can be useful.

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], which can achieve improved low voltage driving characteristics and excellent luminous efficiency of an organic light emitting diode.

The organic light emitting compound represented by [Formula I] according to the present invention is dibenzofuran (dibenzothiophene) or benzoxazole (benzothiazole) at a specific position of the fluorene skeleton, as represented by the following [Formula I] ) a derivative is introduced, various substituents are introduced including the following [Structural Formula 1] to [Structural Formula 2] at positions A ₁ and A ₂ , and the following [Structural Formula 2] is introduced at at least one of positions A ₁ and A ₂ . An organic light emitting device having improved low voltage driving and excellent luminous efficiency can be realized by employing the compound according to the present invention in a hole transport layer or a light efficiency improving layer due to these skeleton and substituent characteristics.

[Formula Ⅰ]

In the above [Formula I],

X ₁ is O, S, NR or CRR'.

Wherein R and R' are the same or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, and a substituted or unsubstituted C number It is selected from 3 to 30 heteroaryl groups.

In addition, R and R' may be connected to each other to form an alicyclic or aromatic monocyclic or polycyclic ring.

X ₂ is O or S.

R ₁ to R ₄ are the same as or different from each other, and each independently hydrogen, deuterium, cyano group, halogen group, hydroxy group, nitro group, substituted or unsubstituted C 1 to C 20 alkyl group, substituted or unsubstituted C 1 bet 20 alkoxy group, substituted or unsubstituted C 1 to C 20 halogenated alkyl group, substituted or unsubstituted C 1 to C 20 halogenated alkoxy group, substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or unsubstituted A cyclic alkylsilyl group having 1 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms selected from among

A ₁ and A ₂ are the same as or different from each other, and each independently hydrogen, deuterium, cyano group, halogen group, hydroxy group, nitro group, substituted or unsubstituted C 1 to C 20 alkyl group, substituted or unsubstituted C 1 bet 20 alkoxy group, substituted or unsubstituted C 1 to C 20 halogenated alkyl group, substituted or unsubstituted C 1 to C 20 halogenated alkoxy group, substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or unsubstituted A cyclic alkylsilyl group having 1 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and any one selected from the following [Structural Formula 1] and [Structural Formula 2].

At least one of A ₁ and A ₂ is characterized in that it is represented by the following [Structural Formula 2].

[Structural Formula 1]

In the [Structural Formula 1],

X ₃ is O or S,

R ₅ to R ₈ are the same as or different from each other, and each independently hydrogen, deuterium, cyano group, halogen group, hydroxy group, nitro group, substituted or unsubstituted C 1 to C 20 alkyl group, substituted or unsubstituted C 1 bet 20 alkoxy group, substituted or unsubstituted C 1 to C 20 halogenated alkyl group, substituted or unsubstituted C 1 to C 20 halogenated alkoxy group, substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or unsubstituted A cyclic alkylsilyl group having 1 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms selected from among

[Structural Formula 2]

In the above [Structural Formula 2],

L ₁ to L ₃ are the same or different from each other, and each independently a single bond or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted carbazolylene group, and It is selected from a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms.

n, m, and l are each an integer of 0 to 3, and when n, m, and l are each 2 or more, a plurality of L ₁ to L ₃ are the same as or different from each other, respectively.

Ar ₁ To Ar ₂ are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 6 to C 30 It is selected from an aryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazolyl group, and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms.

o and p are each an integer of 1 to 3, and when o and p are each 2 or more, a plurality of Ar ₁ to Ar ₂ are the same as or different from each other, respectively.

In addition, according to an embodiment of the present invention, when L ₁ to L ₃ and Ar ₁ to Ar ₂ are each a heteroaryl group, it may have a structure represented by [Structural Formula 1].

On the other hand, in the definitions of R, R', R ₁ to R ₈ , A ₁ , A ₂ , L ₁ to L ₃ and Ar ₁ to Ar ₂ , 'substituted or unsubstituted' means deuterium, a halogen group, Substituted with one or two or more substituents selected from the group consisting of a cyano group, a nitro group, a hydroxyl group, an amine group, a silyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, a fluorenyl group, an aryl group, a carbazolyl group and a heteroaryl group Or, it means that two or more of the substituents are substituted with a connected substituent, or do not have any substituents.

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

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, and can be clearly identified in the specific compound according to the present invention.

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 cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, cyclohex Sil group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2,3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclo Octyl group, spirodecyl, spirodecyl, adamantyl, 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, which is 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, and examples of the polycyclic aryl group include a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, 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 may have a spiro structure in which two ring organic compounds are connected through one atom, for example,

,

,

etc.

,

등이 있다.In addition, 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 two ring organic compounds are connected through one atom in a state in which the connection of one ring compound is broken structure, such as

,

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 addition, the fluorenyl structure as described above may be a form in which an alicyclic ring or an aromatic ring is further condensed.

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 a specific example thereof in the present invention is 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.

The organic light emitting compound according to the present invention represented by the [Formula I] may be used as a material for an organic layer such as a hole transport layer of an organic light emitting device, and a light efficiency improving layer material provided in the organic light emitting device due to its structural specificity.

Preferred examples of the organic light emitting compound represented by [Formula I] according to the present invention include the following compounds, but are 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 by using a characteristic skeleton exhibiting intrinsic properties and a moiety having intrinsic properties introduced thereto, As a result, the organic light emitting compound according to the present invention can be applied to various organic layer materials such as a light emitting layer, a light efficiency improving layer, a hole transport layer, an electron transport layer, an electron blocking layer, and a hole blocking layer, and according to a preferred embodiment of the present invention, an organic light emitting device It is possible to further improve light-emitting characteristics such as the light-emitting efficiency of the device by applying it to the hole transport layer or the light efficiency improving layer provided in the organic light-emitting device.

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 layer disposed therebetween. Except that, it may be manufactured using conventional device manufacturing methods and materials.

The organic layer of the organic light emitting diode according to the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic 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 layers.

In addition, the organic electroluminescent device according to an embodiment of the present invention includes a substrate, a first electrode (anode), an organic 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 formed on the second electrode top (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 improving 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 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 diode according to the present invention is a metal or conductive metal oxide or an alloy thereof on a substrate by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation. It can be prepared by depositing an anode, forming an organic 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 diode may be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate. The organic 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 can be formed in a smaller number by a solvent process rather than a deposition method using various polymer materials, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer method. 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 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 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 multilayers 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 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 well injecting electrons from the cathode and transferring them to the light emitting layer, 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 may 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 self-evident to those with knowledge.

Synthesis example 1: Synthesis of compound 84

(One) production example 1: Synthesis of Intermediate 84-1

4,6-Dibromodibenzofuran (10.0 g, 0.031 mol), Benzoxazole (5.5 g, 0.046 mol), K ₂ CO ₃ (8.5 g, 0.061 mol), PPh ₃ (4.0 g, 0.015 mol), Cu(OAc) ₂ ( Toluene was added to 0.1 g, 0.001 mol) and Pd(OAc) ₂ (0.1 g, 0.0003 mol), and the reaction was stirred under reflux at 110° C. for 4 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 7.2 g (yield 64.5%) of <Intermediate 84-1>.

(2) production example 2: Synthesis of compound 84

Intermediate 84-1 (10.0 g, 0.028 mol), 4-(2-Naphthyl)-N-[4-(2-naphthyl)phenyl]aniline (17.4 g, 0.041 mol), NaO ^t Bu (5.3 g, 0.055 mol) ), t-Bu ₃ P (0.6 g, 0.003 mol), Pd(dba) ₂ (0.8 g, 0.001 mol) was added with 150 mL of toluene and stirred at 70 °C for 4 hours to react. After completion of the reaction, 13.4 g (yield 69.2%) of <Compound 84> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=704[(M+1) ⁺ ]

Synthesis example 2: Synthesis of compound 96

(One) production example 1: Synthesis of compound 96

Intermediate 84-1 (10.0 g, 0.028 mol), N-([1,1'-biphenyl]-4-yl)dibenzo[b,d]thiophen-4-amine (14.5 g, 0.041 mol), NaO ^t Bu (5.3 g, 0.055 mol), t-Bu ₃ P (0.6 g, 0.003 mol), Pd(dba) ₂ (0.8 g, 0.001 mol) was added to 150 mL of Toluene and stirred at 70 °C for 4 hours to react. After completion of the reaction, 12.7 g (yield 72.9%) of <Compound 96> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=634 [(M+1) ⁺ ]

Synthesis example 3: Synthesis of compound 116

(One) production example 1: Synthesis of intermediate 116-1

6-Bromo-2-chlorodibenzo[b,d]furan (10.0 g, 0.036 mol), Benzoxazole (6.4 g, 0.053 mol), K ₂ CO ₃ (9.8 g, 0.071 mol), PPh ₃ (4.7 g, 0.078 mol) ), Cu(OAc) ₂ (0.1 g, 0.001 mol), Pd(OAc) ₂ (0.1 g, 0.0004 mol) was added to Toluene, and the reaction was stirred under reflux at 110° C. for 4 hours. After completion of the reaction, 8.3 g (yield 73.1%) of <Intermediate 116-1> was obtained by extraction, concentration, and column.

(2) production example 2: Synthesis of intermediate 116-2

2-Bromo-9,9'-spirobi[9H-fluorene] (10.0 g, 0.025 mol), 4-Aminobiphenyl (6.4 g, 0.038 mol), NaO ^t Bu (4.9 g, 0.051 mol), t-Bu ₃ P (0.5 g, 0.003 mol), 150 mL of toluene was added to Pd(dba) ₂ (0.7 g, 0.001 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 8.1 g (yield 66.2%) of <Intermediate 116-2> was obtained by extraction and concentration by column.

(3) production example 3: Synthesis of intermediate 116-3

1-Bromo-4-iodobenzene (10.0 g, 0.035 mol), Intermediate 116-2 (25.6 g, 0.053 mol), NaO ^t Bu (6.8 g, 0.071 mol), t-Bu ₃ P (0.7 g, 0.004 mol) , 150 mL of Toluene was added to Pd(dba) ₂ (1.0 g, 0.002 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 14.3 g (yield 63.4%) of <Intermediate 116-3> was obtained by extraction, concentration, and column.

(4) production example 4: Synthesis of intermediate 116-4

Dioxane 100 in Intermediate 116-3 (10.0 g, 0.016 mol), Bis(pinacolato)diboron (4.8 g, 0.019 mol), KOAc (3.1 g, 0.031 mol), Pd(dppf)Cl ₂ (0.3 g, 0.001 mol) mL and stirred at 100 °C for 12 hours to react. After completion of the reaction, 8.2 g (yield 76.4%) of <Intermediate 116-4> was obtained by extraction and concentration, followed by column and recrystallization.

(5) production example 5: Synthesis of compound 116

Intermediate 116-1 (10.0 g, 0.031 mol), Intermediate 116-4 (25.7 g, 0.038 mol), K ₂ CO ₃ (13.0 g, 0.094 mol), Catalyst Pd(OAc) ₂ (1.8 g, 0.002 mol), Ligand X-Phos (1.5 g, 0.003 mol), 200 mL of THF, 50 mL of H ₂ O, and 50 mL of ethanol were added, and the reaction was stirred at 90 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 17.6 g (yield 66.8%) of <Compound 116>.

LC/MS: m/z=842[(M+1) ⁺ ]

Synthesis example 4: Synthesis of compound 122

(One) production example 1: Synthesis of intermediate 122-1

4,6-Dibromodibenzofuran (10.0 g, 0.031 mol), Benzoxazole (11.0 g, 0.092 mol), K ₂ CO ₃ (17.0 g, 0.123 mol), PPh ₃ (8.1 g, 0.031 mol), Cu(OAc) ₂ ( 0.2 g, 0.001 mol), Pd(OAc) ₂ (0.1 g, 0.001 mol) was added to Toluene, and the reaction was stirred under reflux at 110° C. for 4 hours. After completion of the reaction, 9.5 g (yield 77.0%) of <Intermediate 122-1> was obtained by extraction, concentration, and column.

(2) production example 2: Synthesis of intermediate 122-2

Intermediate 122-1 (10.0 g, 0.025 mol) was dissolved in CHCl ₃ 100 mL, Bromine (in CHCl ₃ , 9.9 g, 0.062 mol) was slowly added dropwise, followed by stirring at room temperature for 12 hours to react. After completion of the reaction, 6.1 g (yield 51.0%) of <Intermediate 122-2> was obtained by extraction and concentration, followed by column and recrystallization.

(3) production example 3: Synthesis of compound 122

Intermediate 122-2 (10.0 g, 0.021 mol), (4-Biphenyl)-(9,9-dimethylfluoren-2-yl)amine (11.3 g, 0.031 mol), NaO ^t Bu (4.0 g, 0.042 mol), t 150 mL of Toluene was added to -Bu ₃ P (0.4 g, 0.002 mol), Pd(dba) ₂ (0.6 g, 0.001 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 10.4 g (yield 65.7%) of <Compound 122> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=761 [(M+1) ⁺ ]

Synthesis example 5: Synthesis of compound 146

(One) production example 1: Synthesis of intermediate 146-1

4,6-Dibromodibenzothiophene (10.0 g, 0.029 mol), Benzoxazole (5.2 g, 0.044 mol), K ₂ CO ₃ (8.1 g, 0.059 mol), PPh ₃ (3.8 g, 0.015 mol), Cu(OAc) ₂ ( Toluene was added to 0.1 g, 0.001 mol) and Pd(OAc) ₂ (0.1 g, 0.3 mmol), and the reaction was stirred under reflux at 110° C. for 4 hours. After completion of the reaction, 7.3 g (yield 65.7%) of <Intermediate 146-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) production example 2: Synthesis of compound 146

Intermediate 146-1 (10.0 g, 0.026 mol), 1,1′ (10.6 g, 0.039 mol), NaO ^t Bu (5.1 g, 0.053 mol), t-Bu ₃ P (0.5 g, 0.003 mol), Pd ( dba) ₂ (0.8 g, 0.001 mol) was added with 150 mL of Toluene and stirred at 70 °C for 4 hours to react. After completion of the reaction, 9.5 g (yield 63.5%) of <Compound 146> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=568 (M+1) ⁺ ]

Synthesis example 6: Synthesis of compound 149

(One) production example 1: Synthesis of Intermediate 149-1

9-(4-Bromo-phenyl)-9H-carbazole (10.0 g, 0.031 mol), 2-Amino-9,9-dimethylfluorene (9.7 g, 0.047 mol), NaO ^t Bu (6.0 g, 0.062 mol), t 150 mL of Toluene was added to -Bu ₃ P (0.6 g, 0.003 mol), Pd(dba) ₂ (0.9 g, 0.002 mol), and the reaction was stirred at 70° C. for 4 hours. After completion of the reaction, 9.7 g (yield 69.4%) of <Intermediate 149-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) production example 2: Synthesis of compound 149

Intermediate 146-1 (10.0 g, 0.026 mol), Intermediate 149-1 (17.8 g, 0.039 mol), NaO ^t Bu (5.1 g, 0.053 mol), t-Bu ₃ P (0.5 g, 0.003 mol), Pd ( dba) ₂ (0.8 g, 0.001 mol) was added with 150 mL of Toluene and stirred at 70 °C for 4 hours to react. After completion of the reaction, 10.8 g (yield 54.8%) of <Compound 149> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=749[(M+1) ⁺ ]

Synthesis example 7: Synthesis of compound 279

(One) production example 1: Synthesis of intermediate 279-1

4,6-Dibromodibenzofuran (10.0 g, 0.031 mol), Benzothiazole (6.2 g, 0.046 mol), K ₂ CO ₃ (8.5 g, 0.061 mol), PPh ₃ (4.0 g, 0.015 mol), Cu(OAc) ₂ ( Toluene was added to 0.1 g, 0.001 mol) and Pd(OAc) ₂ (0.1 g, 0.0003 mol), and the reaction was stirred under reflux at 110° C. for 4 hours. After completion of the reaction, 6.9 g (yield 59.2%) of <Intermediate 279-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) production example 2: Synthesis of compound 279

Intermediate 279-1 (10.0 g, 0.026 mol), Bis(4-biphenylyl)amine (12.7 g, 0.039 mol), NaO ^t Bu (5.1 g, 0.053 mol), t-Bu ₃ P (0.5 g, 0.003 mol) , 150 mL of Toluene was added to Pd(dba) ₂ (0.8 g, 0.001 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 10.3 g (yield 63.1%) of <Compound 279> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=620[(M+1) ⁺ ]

Synthesis example 8: Synthesis of compound 306

(One) production example 1: Synthesis of intermediate 306-1

(4-Bromophenyl)benzoxazole (10.0 g, 0.037 mol), 4-(1,3-benzoxazol-2-yl)aniline (11.5 g, 0.055 mol), NaO ^t Bu (7.0 g, 0.073 mol), t-Bu 150 mL of Toluene was added to ₃ P (0.7 g, 0.004 mol), Pd(dba) ₂ (1.1 g, 0.002 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 10.1 g (yield 68.6%) of <Intermediate 306-1> was obtained by extraction, concentration, and column.

(2) production example 2: Synthesis of intermediate 306-2

1-Bromo-4-iodobenzene (10.0 g, 0.035 mol), Intermediate 306-1 (21.4 g, 0.053 mol), NaO ^t Bu (6.8 g, 0.071 mol), t-Bu ₃ P (0.7 g, 0.004 mol) , 150 mL of Toluene was added to Pd(dba) ₂ (1.0 g, 0.002 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 13.9 g (yield 70.4%) of <Intermediate 306-2> was obtained by extraction, concentration, and column.

(3) production example 3: Synthesis of intermediate 306-3

Intermediate 306-2 (10.0 g, 0.018 mol), Bis(pinacolato)diboron (5.5 g, 0.022 mol), KOAc (3.5 g, 0.036 mol), Dioxane 100 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, 8.4 g (yield 77.5%) of <Intermediate 306-3> was obtained by extraction and concentration, followed by column and recrystallization.

(4) production example 4: Synthesis of compound 306

Intermediate 279-1 (10.0 g, 0.026 mol), Intermediate 306-3 (19.1 g, 0.032 mol), K ₂ CO ₃ (10.9 g, 0.079 mol), Pd(PPh ₃ ) ₄ (0.6 g, 0.001 mol) Toluene 200 mL, Ethanol 50 mL, H ₂ O 50 mL were added, and the reaction was stirred at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 15.1 g (yield 73.7%) of <Compound 306>.

LC/MS: m/z=778 [(M+1) ⁺ ]

Synthesis example 9: Synthesis of compound 321

(One) production example 1: Synthesis of intermediate 321-1

4,6-Dibromodibenzofuran (10.0 g, 0.031 mol), Benzothiazole (12.4 g, 0.092 mol), K ₂ CO ₃ (17.0 g, 0.123 mol), PPh ₃ (8.1 g, 0.031 mol), Cu(OAc) ₂ ( 0.2 g, 0.001 mol), Pd(OAc) ₂ (0.1 g, 0.001 mol) was added to Toluene, and the reaction was stirred under reflux at 110° C. for 4 hours. After completion of the reaction, 10.7 g (yield 80.3%) of <Intermediate 321-1> was obtained by extraction, concentration, and column.

(2) production example 2: Synthesis of intermediate 321-2

Intermediate 321-1 (10.0 g, 0.023 mol) was dissolved in 100 mL of CHCl ₃ , Bromine (in CHCl ₃ , 9.2 g, 0.058 mol) was slowly added dropwise, followed by stirring at room temperature for 12 hours to react. After completion of the reaction, 6.6 g (yield 55.9%) of <Intermediate 321-2> was obtained by extraction and concentration, followed by column and recrystallization.

(3) production example 3: Synthesis of compound 321

Intermediate 321-2 (10.0 g, 0.020 mol), N-[1,1'-biphenyl]-2-yl-[1,1'-Biphenyl]-2-amine (9.4 g, 0.029 mol), NaO ^t Bu (3.7 g, 0.039 mol), t-Bu ₃ P (0.4 g, 0.002 mol), Pd(dba) ₂ (0.6 g, 0.001 mol) was added to 150 mL of Toluene, followed by stirring at 70 °C for 4 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 6.4 g (yield 43.6%) of <Compound 321>.

LC/MS: m/z=753 [(M+1) ⁺ ]

Synthesis example 10: Synthesis of compound 327

(One) production example 1: Synthesis of compound 327

Intermediate 321-2 (10.0 g, 0.020 mol), Bis(dibenzo[b,d]furan-3-yl)amine (10.2 g, 0.029 mol), NaO ^t Bu (3.7 g, 0.039 mol), t-Bu ₃ 150 mL of Toluene was added to P (0.4 g, 0.002 mol), Pd(dba) ₂ (0.6 g, 0.001 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 10.2 g (yield 67.0%) of <Compound 327> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=781[(M+1) ⁺ ]

Synthesis example 11: Synthesis of compound 356

(One) production example 1: Synthesis of intermediate 356-1

4,6-Dibromodibenzothiophene (10.0 g, 0.029 mol), Benzothiazole (5.9 g, 0.044 mol), K ₂ CO ₃ (8.1 g, 0.059 mol), PPh ₃ (3.8 g, 0.015 mol), Cu(OAc) ₂ ( Toluene was added to 0.1 g, 0.001 mol) and Pd(OAc) ₂ (0.1 g, 0.0003 mol), and the reaction was stirred under reflux at 110° C. for 4 hours. After completion of the reaction, the mixture was extracted, concentrated, and columned to obtain 5.5 g (yield: 47.5%) of <Intermediate 356-1>.

(2) production example 2: Synthesis of intermediate 356-2

2-Bromo-9,9'-spirobi[9H-fluorene] (10.0 g, 0.025 mol), 2-Amino-9,9-dimethylfluorene (7.9 g, 0.038 mol), NaO ^t Bu (4.9 g, 0.051 mol) , t-Bu ₃ P (0.5 g, 0.003 mol), Pd(dba) ₂ (0.7 g, 0.001 mol) was added to 150 mL of toluene and stirred at 70 °C for 4 hours to react. After completion of the reaction, 8.1 g (yield 61.1%) of <Intermediate 356-2> was obtained by extraction and concentration by column.

(3) production example 3: Synthesis of intermediate 356-3

1-Bromo-4-iodobenzene (10.0 g, 0.035 mol), Intermediate 356-2 (27.8 g, 0.53 mol), NaO ^t Bu (6.8 g, 0.071 mol), t-Bu ₃ P (0.7 g, 0.004 mol) , 150 mL of Toluene was added to Pd(dba) ₂ (1.0 g, 0.002 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 16.1 g (yield 67.1%) of <Intermediate 356-3> was obtained by extraction, concentration, and column.

(4) production example 4: Synthesis of intermediate 356-4

Intermediate 356-3 (10.0 g, 0.015 mol), Bis(pinacolato)diboron (4.5 g, 0.018 mol), KOAc (2.9 g, 0.030 mol), Pd(dppf)Cl ₂ (0.3 g, 0.4 mmol) in Dioxane 100 mL and stirred at 100 °C for 12 hours to react. After completion of the reaction, 8.1 g (yield 75.8%) of <Intermediate 356-4> was obtained by extraction and concentration, followed by column and recrystallization.

(5) production example 5: Synthesis of compound 356

Intermediate 356-1 (10.0 g, 0.025 mol), Intermediate 356-4 (22.0 g, 0.030 mol), K ₂ CO ₃ (10.5 g, 0.076 mol), Pd(PPh ₃ ) ₄ (0.6 g, 0.001 mol) Toluene 200 mL, Ethanol 50 mL, H ₂ O 50 mL were added, and the reaction was stirred at 100 °C for 6 hours. After completion of the reaction, 14.8 g (yield 64.1%) of <Compound 356> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=915 [(M+1) ⁺ ]

Synthesis example 12: Synthesis of compound 380

(One) production example 1: Synthesis of intermediate 380-1

4,6-Dibromodibenzothiophene (10.0 g, 0.029 mol), Benzothiazole (11.9 g, 0.088 mol), K ₂ CO ₃ (16.2 g, 0.117 mol), PPh ₃ (7.7 g, 0.029 mol), Cu(OAc) ₂ ( 0.2 g, 0.001 mol), Pd(OAc) ₂ (0.1 g, 0.001 mol) was added to Toluene, and the reaction was stirred under reflux at 110° C. for 4 hours. After completion of the reaction, 9.7 g (yield 73.6%) of <Intermediate 380-1> was obtained by extraction, concentration, and column.

(2) production example 2: Synthesis of intermediate 380-2

Intermediate 380-1 (10.0 g, 0.022 mol) was dissolved in 100 mL of CHCl ₃ , Bromine (in CHCl ₃ , 8.9 g, 0.056 mol) was slowly added dropwise, followed by stirring at room temperature for 12 hours to react. After completion of the reaction, 5.8 g (yield 49.4%) of <Intermediate 380-2> was obtained by extraction, concentration, and column.

(3) production example 3: Synthesis of intermediate 380-3

2-Bromo-11,11-dimethyl-11H-benzo[b]fluorene (10.0 g, 0.031 mol), 4-Aminobiphenyl (7.9 g, 0.046 mol), NaO ^t Bu (6.0 g, 0.062 mol), t-Bu 150 mL of Toluene was added to ₃ P (0.6 g, 0.003 mol), Pd(dba) ₂ (0.9 g, 0.002 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 8.8 g (yield 69.1%) of <Intermediate 380-3> was obtained by extraction and concentration, followed by column and recrystallization.

(4) production example 4: Synthesis of compound 380

Intermediate 380-2 (10.0 g, 0.019 mol), Intermediate 380-3 (11.7 g, 0.028 mol), NaO ^t Bu (3.6 g, 0.038 mol), t-Bu ₃ P (0.4 g, 0.002 mol), Pd ( dba) ₂ (0.5 g, 0.001 mol) was added with 150 mL of Toluene and stirred at 70 °C for 4 hours to react. After completion of the reaction, 10.2 g (yield 62.8%) of <Compound 380> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=589 [(M+1) ⁺ ]

Synthesis example 13: Synthesis of compound 381

(One) production example 1: Synthesis of intermediate 381-1

4-Bromo-9,9-diphenyl-9H-fluorene (10.0 g, 0.025 mol), 4-Aminobiphenyl (6.4 g, 0.038 mol), NaO ^t Bu (4.8 g, 0.050 mol), t-Bu ₃ P (0.5 g, 0.003 mol), Pd(dba) ₂ (0.7 g, 0.001 mol) was added with 150 mL of toluene and stirred at 70° C. for 4 hours to react. After completion of the reaction, 7.7 g (yield 63.0%) of <Intermediate 381-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) production example 2: Synthesis of compound 381

Intermediate 380-2 (10.0 g, 0.019 mol), Intermediate 381-1 (13.8 g, 0.028 mol), NaO ^t Bu (3.6 g, 0.038 mol), t-Bu ₃ P (0.4 g, 0.002 mol), Pd ( dba) ₂ (0.5 g, 0.001 mol) was added with 150 mL of Toluene and stirred at 70 °C for 4 hours to react. After completion of the reaction, 10.6 g (yield 60.1%) of <Compound 381> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=933 [(M+1) ⁺ ]

Synthesis example 14: Synthesis of compound 392

(One) production example 1: Synthesis of intermediate 392-1

1,8-Dibromo-9h-carbazole (10.0 g, 0.031 mol), Iodobenzene (7.5 g, 0.037 mol), K ₂ CO ₃ (12.8 g, 0.092 mol), dibenzo-18-crown-6 (0.6 g, 0.002) mol), Cu (2.0 g, 0.031 mol) was added with 160 mL of DMF, and the mixture was reacted by stirring under reflux at 150 °C for 7 hours. After completion of the reaction, the mixture was extracted, concentrated, and then columned to obtain 7.8 g (yield: 63.2%) of <Intermediate 392-1>.

(2) production example 2: Synthesis of intermediate 392-2

Intermediate 392-1 (10.0 g, 0.025 mol), 1,3-Benzothiazole-6-carbonitrile (6.0 g, 0.037 mol), K ₂ CO ₃ (6.9 g, 0.050 mol), PPh ₃ (3.3 g, 0.013 mol) , Cu(OAc) ₂ (0.1 g, 0.001 mol), Pd(OAc) ₂ (0.1 g, 0.0002 mol) was added to Toluene and reacted by stirring under reflux at 110 °C for 4 hours. After completion of the reaction, 6.5 g (yield 54.3%) of <Intermediate 392-2> was obtained by extraction and concentration, followed by column and recrystallization.

(3) production example 3: Synthesis of compound 392

Intermediate 392-2 (10.0 g, 0.021 mol), Diphenylamine (5.3 g, 0.031 mol), NaO ^t Bu (4.0 g, 0.042 mol), t-Bu ₃ P (0.4 g, 0.002 mol), Pd(dba) ₂ 150 mL of Toluene was added to (0.6 g, 0.001 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 5.9 g (yield 49.8%) of <Compound 392> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=568[(M+1) ⁺ ]

Device Example (CPL)

In the embodiment according to the present invention, the anode was cleaned using an ITO glass substrate containing 25 mm × 25 mm × 0.7 mm Ag, after patterning so that the light emitting area has a size of 2 mm × 2 mm. After mounting the patterned ITO substrate in a vacuum chamber, organic materials and metals were deposited on the substrate in the following structure at a process pressure of 1 × 10 ^-6 torr or more.

Device Examples 1 to 50

By employing the compound implemented according to the present invention in the light efficiency improving layer, an organic light emitting device having the following device structure was manufactured, and then light emission and driving characteristics according to the compound implemented according to the present invention 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 on a glass substrate to a thickness of 5 nm on an ITO transparent electrode containing Ag to form a hole injection layer, and then, [α-NPB] was formed to a film of 100 nm to form a hole transport layer. , [TCTA] was deposited to a thickness of 10 nm to form an electron blocking layer. Then, using [BH1] as a host compound and [BD1] as a dopant compound, it was co-deposited at 20 nm to form a light emitting layer. Thereafter, after depositing an electron transport layer (50% doping of [201] compound Liq below) at 30 nm, LiF was deposited to a thickness of 1 nm to form an electron injection layer. After that, Mg:Ag was formed into a film to a thickness of 15 nm in a ratio of 1:9 to form a cathode. And as the light efficiency improvement layer (capping layer) compound according to the present invention compounds 4, 9, 16, 22, 31, 57, 70, 75, 84, 86, 96, 97, 99, 104, 109, 116, 122, 146, 149, 154, 158, 164, 165, 167, 175, 182, 192, 200, 203, 213, 218, 221, 232, 251, 259, 268, 279, 290, 292, 306, 312, 321, 325, 327, 330, 350, 356, 380, 381, and 392 were formed into a film 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 50.

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 according to the present invention as the light efficiency improving layer compound in the device structures of Examples 1 to 50.

Device Comparative Example 3

The organic light emitting device for Device Comparative Example 3 was manufactured in the same manner except that CP 1 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 50.

Experimental Example 1: Light emitting characteristics of Device Examples 1 to 50

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 4 3.6 8.8 0.135 0.050 2 Formula 9 3.9 8.0 0.139 0.047 3 Formula 16 3.8 8.4 0.132 0.053 4 Formula 22 3.5 8.8 0.131 0.057 5 Formula 31 3.7 8.5 0.138 0.055 6 chemical formula 57 3.5 8.8 0.131 0.059 7 Formula 70 3.8 8.3 0.133 0.055 8 Formula 75 3.6 8.8 0.137 0.052 9 Formula 84 3.9 8.0 0.139 0.046 10 Formula 86 3.8 8.4 0.130 0.053 11 Formula 96 3.6 8.8 0.131 0.063 12 Formula 97 3.4 8.9 0.133 0.056 13 Formula 99 3.9 8.0 0.135 0.049 14 Formula 104 3.7 8.7 0.132 0.058 15 Formula 109 3.8 8.3 0.130 0.055 16 Formula 116 3.7 8.5 0.131 0.054 17 Formula 122 3.8 8.2 0.135 0.053 18 Formula 146 3.8 8.4 0.130 0.060 19 Formula 149 3.9 8.1 0.135 0.051 20 Formula 154 3.6 8.7 0.137 0.049 21 Formula 158 3.9 8.0 0.139 0.046 22 Formula 164 3.8 8.4 0.130 0.053 23 Formula 165 3.5 8.8 0.132 0.058 24 Formula 167 3.8 8.3 0.135 0.055 25 Formula 175 3.9 8.0 0.136 0.049 26 Formula 182 3.8 8.4 0.132 0.057 27 Formula 192 3.5 8.8 0.135 0.055 28 Formula 200 3.9 8.0 0.137 0.049 29 Formula 203 4.0 8.0 0.138 0.050 30 Formula 213 3.8 8.4 0.131 0.055 31 Formula 218 3.5 8.8 0.132 0.058 32 Formula 221 3.8 8.3 0.134 0.056 33 Formula 232 3.9 8.0 0.135 0.049 34 Formula 251 3.7 8.5 0.131 0.057 35 Formula 259 3.8 8.3 0.130 0.055 36 Formula 268 3.7 8.5 0.133 0.059 37 Formula 279 3.8 8.2 0.136 0.050 38 Formula 290 3.8 8.2 0.132 0.056 39 Formula 292 3.9 8.1 0.139 0.048 40 Formula 306 3.6 8.7 0.138 0.047 41 Formula 312 3.7 8.5 0.133 0.052 42 Formula 321 3.7 8.6 0.132 0.056 43 Formula 325 3.8 8.3 0.131 0.057 44 Formula 327 3.8 8.0 0.138 0.049 45 Formula 330 3.7 8.8 0.135 0.050 46 Formula 350 4.0 8.4 0.131 0.049 47 Formula 356 3.5 8.2 0.133 0.057 48 Formula 390 3.9 8.0 0.132 0.055 49 Formula 381 3.8 8.3 0.134 0.049 50 Formula 392 3.5 8.1 0.135 0.048 Comparative Example 1 not used 4.6 7.0 0.150 0.141 Comparative Example 2 Alq ₃ 4.3 7.8 0.147 0.058 Comparative Example 3 CP 1 4.4 7.5 0.137 0.073

Looking at the results shown in [Table 1], when the compound according to the present invention is employed in the light efficiency improving layer provided in the organic light emitting device, the device without the light efficiency improving layer, the compound used as the conventional light efficiency improving layer material It can be seen that the driving voltage is reduced and the current efficiency is improved as compared to the device employing the device and the device employing the compound contrasting with the characteristic structure of the compound according to the present invention (Comparative Examples 1 to 3).

[HAT-CN] [α-NPB] [BH1] [BD1] [201]

[TCTA] [CP 1]

Device Example (HTL)

In the embodiment according to the present invention, the anode was cleaned using a glass substrate having an ITO transparent electrode of 25 mm × 25 mm × 0.7 mm attached to it, and then patterned so that the light emitting area had a size of 2 mm × 2 mm. After mounting the patterned ITO substrate in a vacuum chamber, organic materials and metals were deposited on the substrate in the following structure at a process pressure of 1 × 10 ^-6 torr or more.

Device Examples 51 to 79

The compound implemented according to the present invention was employed in the hole transport layer in the device. After manufacturing an organic light emitting device having the device structure as follows, light emission and driving characteristics according to the compound implemented according to the present invention were measured.

ITO / hole injection layer (HAT-CN, 5 nm) / hole transport layer (100 nm) / electron blocking layer (EBL1, 10 nm) / light emitting layer (20 nm) / electron transport layer (201:Liq, 30 nm) / LiF ( 1 nm) / Al (100 nm)

[HAT-CN] was formed on the ITO transparent electrode to a thickness of 5 nm to form a hole injection layer, after which compounds 1, 8, 12, 28, 37, 42, 51, 66, 83, 96, 111, 120, 122, 149, 224, 246, 237, 248, 262, 270, 283, 300, 316, 321, 347, 356, 361, 381, and 398 were deposited at 100 nm to form a hole transport layer. Then, using [BH1] as a host compound and [BD1] as a dopant compound, 20 nm co-deposition was performed to form a light emitting layer. Then, an electron transport layer (50% doped with [201] compound Liq below) was deposited at 30 nm. Thereafter, LiF 1 nm and Al were deposited to a thickness of 100 nm to fabricate an organic light emitting diode.

Device Comparative Example 4

The organic light emitting device for Device Comparative Example 4 was manufactured in the same manner except that the following α-NPB was used instead of the compound according to the present invention as the hole transport layer material in the device structures of Examples 51 to 79.

Experimental Example 2: Light emitting properties of Device Examples 51 to 79

The organic light emitting device manufactured according to the above example was measured for voltage, current and luminous efficiency using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research), and the result value based on 1000 nit was It is shown in [Table 2] below.

Example hole transport layer V cd/A CIEx CIEy 51 Formula 1 4.0 7.3 0.134 0.150 52 Formula 8 3.9 7.7 0.134 0.151 53 Formula 12 4.2 7.0 0.134 0.151 54 Formula 28 4.0 7.3 0.134 0.151 55 Formula 37 3.9 7.3 0.131 0.156 56 Formula 42 3.9 7.3 0.132 0.153 57 Formula 51 3.8 7.3 0.135 0.148 58 Formula 66 3.8 7.2 0.133 0.152 59 Formula 83 4.3 7.2 0.136 0.148 60 Formula 96 4.0 7.3 0.135 0.149 61 Formula 111 4.1 7.3 0.134 0.150 62 Formula 120 4.1 7.5 0.133 0.153 63 Formula 122 4.2 7.5 0.134 0.151 64 Formula 149 3.9 7.0 0.135 0.148 65 Formula 224 4.3 7.1 0.135 0.153 66 Formula 246 4.3 7.5 0.135 0.149 67 Formula 237 4.2 7.5 0.135 0.149 68 Formula 248 4.2 7.0 0.133 0.152 69 Formula 262 4.1 7.3 0.134 0.151 70 Formula 270 4.1 7.3 0.134 0.151 71 Formula 283 4.1 7.1 0.134 0.151 72 Formula 300 4.1 7.1 0.133 0.150 73 Formula 316 4.2 7.3 0.133 0.153 74 Formula 321 4.3 7.5 0.132 0.153 75 Formula 347 4.2 7.2 0.134 0.151 76 Formula 356 4.2 7.1 0.133 0.151 77 Formula 361 4.1 7.3 0.136 0.152 78 Formula 381 3.9 7.1 0.135 0.148 79 Formula 398 4.1 7.6 0.134 0.151 Comparative Example 4 α-NPB 4.7 6.6 0.135 0.151

Looking at the results shown in [Table 2], when the compound according to the present invention is employed in the hole transport layer provided in the organic light emitting device, driving compared to the device (Comparative Example 4) employing the conventional hole transport layer material α-NPB It can be seen that the voltage is decreased and characteristics such as luminous efficiency are improved.

[HAT_CN] [α-NPB] [BH1] [BD1] [201]

[EBL1]

Claims (8)

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

In the [Formula I],
X ₁ is O, S, NR or CRR',
Wherein R and R' are the same or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, and a substituted or unsubstituted C number It is selected from 3 to 30 heteroaryl groups,
Wherein R and R' may be connected to each other to form an alicyclic or aromatic monocyclic or polycyclic ring,
X ₂ is O or S,
R ₁ to R ₄ are the same as or different from each other, and each independently hydrogen, deuterium, cyano group, halogen group, hydroxy group, nitro group, substituted or unsubstituted C 1 to C 20 alkyl group, substituted or unsubstituted C 1 bet 20 alkoxy group, substituted or unsubstituted C 1 to C 20 halogenated alkyl group, substituted or unsubstituted C 1 to C 20 halogenated alkoxy group, substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or unsubstituted A cyclic alkylsilyl group having 1 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms selected from among
A ₁ and A ₂ are the same as or different from each other, and each independently hydrogen, deuterium, cyano group, halogen group, hydroxy group, nitro group, substituted or unsubstituted C 1 to C 20 alkyl group, substituted or unsubstituted C 1 bet 20 alkoxy group, substituted or unsubstituted C 1 to C 20 halogenated alkyl group, substituted or unsubstituted C 1 to C 20 halogenated alkoxy group, substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or unsubstituted a cyclic alkylsilyl group having 1 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, any one selected from the following [Structural Formula 1] and [Structural Formula 2],
At least one of A ₁ and A ₂ is characterized in that it is represented by the following [Structural Formula 2],
[Structural Formula 1]

In the [Structural Formula 1],
X ₃ is O or S,
R ₅ to R ₈ are the same as or different from each other, and each independently hydrogen, deuterium, cyano group, halogen group, hydroxy group, nitro group, substituted or unsubstituted C 1 to C 20 alkyl group, substituted or unsubstituted C 1 bet 20 alkoxy group, substituted or unsubstituted C 1 to C 20 halogenated alkyl group, substituted or unsubstituted C 1 to C 20 halogenated alkoxy group, substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or unsubstituted A cyclic alkylsilyl group having 1 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms selected from among
[Structural Formula 2]

In the [Structural Formula 2],
L ₁ to L ₃ are the same or different from each other, and each independently a single bond or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted carbazolylene group, and It is selected from a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms,
n, m and l are each an integer of 0 to 3, and when n, m and l are each 2 or more, a plurality of L ₁ to L ₃ are the same as or different from each other,
Ar ₁ To Ar ₂ are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 6 to C 30 It is selected from an aryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazolyl group, and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms,
o and p are each an integer of 1 to 3, and when o and p are each 2 or more, a plurality of Ar ₁ to Ar ₂ are the same as or different from each other, respectively. According to claim 1,
In the definitions of R, R', R ₁ to R ₈ , A ₁ , A ₂ , L ₁ to L ₃ and Ar ₁ to Ar ₂ above, 'substituted or unsubstituted' means deuterium, a halogen group, or a cyano group. , a nitro group, a hydroxyl group, an amine group, a silyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, a fluorenyl group, an aryl group, a carbazolyl group and a heteroaryl group substituted with one or two or more substituents selected from the group consisting of, 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. According to claim 1,
The [Formula I] is an organic light emitting compound, characterized in that selected from the following [Compound 1] to [Compound 405]:

An organic light emitting device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode,
At least one of the organic layers 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 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]. 6. The method of claim 5,
An organic light emitting device comprising an organic light emitting compound represented by the [Formula I] in the hole transport layer or a layer that performs both hole injection and hole transport functions. 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 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]. 8. The method of claim 7,
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.