KR20220101829A - 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 which is employed as a material for an organic layer such as an electron transport layer in an organic light-emitting device and a light efficiency improving 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, characterized in that it is employed as an organic layer in an organic light emitting device, or a light efficiency improvement layer (Capping layer) material provided in an 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 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 that can implement low voltage driving and excellent light emitting efficiency characteristics of an improved device by being employed in an organic layer such as an electron transport layer in an organic light emitting device, or a light efficiency improving layer provided in an organic light emitting device, and including the same An object of the present invention is to provide an organic light emitting device.

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

[Formula Ⅰ]

The characteristic structure of the [Formula I] and specific compounds implemented thereby, and X, A, and B will be described later.

When the compound according to the present invention is employed as an electron transport layer in an organic light emitting device or as a material for 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, which is useful for various display devices. can be used

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 introduces a phenyl group substituted with A and B at a specific position of the dibenzofuran (thiophene) or fluorene skeleton, as represented by the following [Formula I] 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 an electron transport layer or a light efficiency improving layer due to these skeleton and substituent characteristics.

[Formula Ⅰ]

In the above [Formula I],

X is O, S or CRR', wherein R and R' are the same as 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 an aryl group and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

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

A is characterized in that it is represented by the following [Structural Formula 1]. That is, [Formula I] according to the present invention is characterized in that a benzofuran (thiophene) derivative as shown in the following [Structural Formula 1] is bonded to the A position.

[Structural Formula 1]

In the [Structural Formula 1],

X is O or S.

R ₁ to R ₅ 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

Any one of R ₁ to R ₅ is bonded at the A position in [Formula I].

B is characterized in that it is represented by the following [Structural Formula 2] or [Structural Formula 3].

[Structural Formula 2]

[Structural Formula 3]

In the [Structural Formula 2] and [Structural Formula 3],

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

In addition, according to an embodiment of the present invention, Ar ₁ to Ar ₃ may each have a structure represented by the [Structural Formula 1].

Meanwhile, in the definitions of R, R', R ₁ to R ₅ , L ₁ to L ₃ , Ar ₁ to Ar ₃ , 'substituted or unsubstituted' means deuterium, a halogen group, a cyano group, a nitro group, or a hydroxyl group. , a silyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, a fluorenyl group, substituted with one or two or more substituents selected from the group consisting of an aryl group and a heteroaryl group, or two or more of the substituents are substituted with a connected substituent, or , or means not having 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 alkoxy group may be straight-chain or branched. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is 1-20 which is a range which does not give 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 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.

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 electron transport layer in an organic light emitting device or a light efficiency improving layer provided in an 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 By applying to the electron transport layer and the light efficiency improvement layer provided in the organic light emitting device, it is possible to further improve the light emitting characteristics such as the light emitting efficiency of the 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 of forming the second electrode on 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 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 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 1

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

1-Bromo-9,9-dimethyl-9H-fluorene (10.0 g, 0.042 mol), 3,5-Dichlorophenylboronic Acid (9.7 g, 0.051 mol), K ₂ CO ₃ (17.5 g, 0.127 mol), Pd(PPh) ₃ ) 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added to ₄ (0.97 g, 0.0008 mol) and stirred at 100 °C for 6 hours to react. After completion of the reaction, 10.5 g (yield 73.4%) of <Intermediate 1-1> was obtained by extraction and concentration by column.

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

Intermediate 1-1 (10.0 g, 0.030 mol), Benzoxazole (5.3 g, 0.044 mol), Pd(OAc) ₂ (0.07 g, 0.0003 mol), Cu(OAc) ₂ (0.1 g, 0.0006 mol), K ₂ CO Toluene was added to ₃ (8.2 g, 0.059 mol), PPh ₃ (3.9 g, 0.015 mol), and X-Phos (0.28 g, 0.0006 mol) and stirred at 110° C. for 4 hours to react. After completion of the reaction, 6.8 g (yield 54.7%) of <Intermediate 1-2> was obtained by extraction and concentration, followed by column and recrystallization.

(3) production example 3: Synthesis of compound 1

Intermediate 1-2 (10.0 g, 0.024 mol), Diphenylamine (6.0 g, 0.036 mol), NaO ^t Bu (4.5 g, 0.047 mol), Pd(dba) ₂ (0.7 g, 0.001 mol), t-Bu ₃ P 150 mL of Toluene was added to (0.5 g, 0.002 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 9.4 g (yield 71.5%) of <Compound 1> was obtained by extraction, concentration, and column.

LC/MS: m/z=554 [(M+1) ⁺ ]

Synthesis example 2: Synthesis of compound 17

(One) production example 1: Synthesis of intermediate 17-1

9-Bromobenzo[b]naphtho[1,2-d]furan (10.0 g, 0.034 mol), 4-Aminobiphenyl (8.5 g, 0.051 mol), NaO ^t Bu (6.5 g, 0.067 mol), Pd(dba) ₂ (1.0 g, 0.002 mol), 150 mL of Toluene was added to t-Bu ₃ P (0.7 g, 0.003 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 7.1 g (yield 54.7%) of <Intermediate 17-1> was obtained by extraction, concentration, and column.

(2) production example 2: Synthesis of compound 17

Intermediate 1-2 (10.0 g, 0.024 mol), Intermediate 17-1 (13.7 g, 0.036 mol), NaO ^t Bu (4.5 g, 0.047 mol), Pd(dba) ₂ (0.7 g, 0.001 mol), t- 150 mL of Toluene was added to Bu ₃ P (0.5 g, 0.002 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 12.5 g (yield 68.4%) of <Compound 17> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=770[(M+1) ⁺ ]

Synthesis example 3: Synthesis of compound 20

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

2-Bromo-9-spirobifluorene (10.0 g, 0.025 mol), 4-Aminobiphenyl (6.4 g, 0.038 mol), NaO ^t Bu (4.9 g, 0.051 mol), Pd(dba) ₂ (0.7 g, 0.001 mol), 150 mL of Toluene was added to t-Bu ₃ P (0.5 g, 0.003 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 6.5 g (yield 53.1%) of <Intermediate 20-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) production example 2: Synthesis of compound 20

Intermediate 1-2 (10.0 g, 0.024 mol), Intermediate 20-1 (17.2 g, 0.036 mol), NaO ^t Bu (4.6 g, 0.047 mol), Pd(dba) ₂ (0.7 g, 0.001 mol), t- 150 ml of Toluene was added to Bu ₃ P (0.5 g, 0.003 mol), and the reaction was stirred at 70° C. for 4 hours. After completion of the reaction, 14.2 g (yield 68.9%) of <Compound 20> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=868[(M+1) ⁺ ]

Synthesis example 4: Synthesis of compound 79

(One) production example 1: Synthesis of Intermediate 79-1

1-Bromo-9,9'-spirobi[9H-fluorene] (10.0 g, 0.025 mol), 3,5-Dichlorophenylboronic Acid (5.8 g, 0.030 mol), K ₂ CO ₃ (10.5 g, 0.076 mol), Pd 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added to (PPh ₃ ) ₄ (0.6 g, 0.0005 mol), and the reaction was stirred at 100 °C for 6 hours. After completion of the reaction, the mixture was extracted, concentrated, and columned to obtain 6.7 g (yield: 57.4%) of <Intermediate 79-1>.

(2) production example 2: Synthesis of intermediate 79-2

Intermediate 79-1 (10.0 g, 0.022 mol), Benzoxazole (3.9 g, 0.033 mol), Pd(OAc) ₂ (0.05 g, 0.0002 mol), Cu(OAc) ₂ (0.08 g, 0.0004 mol), K ₂ CO Toluene was added to ₃ (5.9 g, 0.043 mol), PPh ₃ (2.8 g, 0.011 mol), and X-Phos (0.21 g, 0.0004 mol), and the reaction was stirred at 110° C. for 4 hours. After completion of the reaction, 6.1 g (yield 51.7%) of <Intermediate 79-2> was obtained by extraction and concentration, followed by column and recrystallization.

(3) production example 3: Synthesis of compound 79

Intermediate 79-2 (10.0 g, 0.018 mol), 2-(4-Biphenylyl)amino-9,9-dimethylfluorene (9.9 g, 0.028 mol), NaO ^t Bu (3.5 g, 0.037 mol), Pd(dba) ₂ (0.5 g, 0.001 mol), 150 mL of Toluene was added to t-Bu ₃ P (0.4 g, 0.002 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 12.5 g (yield 78.3%) of <Compound 79> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=868[(M+1) ⁺ ]

Synthesis example 5: Synthesis of compound 111

(One) production example 1: Synthesis of intermediate 111-1

4-Bromodibenzofuran (10.0 g, 0.041 mol), 3,5-Dichlorophenylboronic Acid (9.3 g, 0.049 mol), K ₂ CO ₃ (16.8 g, 0.121 mol), Pd(PPh ₃ ) ₄ (0.9 g, 0.0008 mol) 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added thereto, and the reaction was stirred at 100 °C for 6 hours. After completion of the reaction, the mixture was extracted and concentrated, and then columned to obtain 9.1 g (yield 71.8%) of <Intermediate 111-1>.

(2) production example 2: Synthesis of intermediate 111-2

Intermediate 111-1 (10.0 g, 0.032 mol), Benzoxazole (5.7 g, 0.048 mol), Pd(OAc) ₂ (0.07 g, 0.0003 mol), Cu(OAc) ₂ (0.1 g, 0.0006 mol), K ₂ CO Toluene was added to ₃ (8.8 g, 0.064 mol), PPh ₃ (4.2 g, 0.016 mol), and X-Phos (0.30 g, 0.0006 mol), and the reaction was stirred at 110 °C for 4 hours. After completion of the reaction, 5.8 g (yield 45.9%) of <Intermediate 111-2> was obtained by extraction and concentration, followed by column and recrystallization.

(3) production example 3: Synthesis of compound 111

Intermediate 111-2 (10.0 g, 0.025 mol), N-(9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazol-2-amine (17.1 g, 0.038 mol), NaO Add 150 mL of Toluene to ^t Bu (4.9 g, 0.051 mol), Pd(dba) ₂ (0.7 g, 0.001 mol), and t-Bu ₃ P (0.5 g, 0.003 mol) and react by stirring at 70 °C for 4 hours. did it After completion of the reaction, 13.3 g (yield 65.0%) of <Compound 111> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=809 (M+1) ⁺ ]

Synthesis example 6: Synthesis of compound 129

(One) production example 1: Synthesis of Intermediate 129-1

Intermediate 111-1 (10.0 g, 0.032 mol), Benzothiazole (6.5 g, 0.048 mol), Pd(OAc) ₂ (0.07 g, 0.0003 mol), Cu(OAc) ₂ (0.1 g, 0.0006 mol), K ₂ CO Toluene was added to ₃ (8.8 g, 0.064 mol), PPh ₃ (4.2 g, 0.016 mol), and X-Phos (0.30 g, 0.0006 mol), and the reaction was stirred at 110 °C for 4 hours. After completion of the reaction, 5.2 g (yield 39.5%) of <Intermediate 129-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) production example 2: Synthesis of compound 129

Intermediate 129-1 (10.0 g, 0.024 mol), N-(biphenyl-4-yl)dibenzo[b,d]furan-1-amine (12.2 g, 0.036 mol), NaO ^t Bu (4.7 g, 0.049 mol) , Pd(dba) ₂ (0.7 g, 0.001 mol), t-Bu ₃ P (0.5 g, 0.002 mol) was added with 150 mL of Toluene and stirred at 70 °C for 4 hours to react. After completion of the reaction, 12.5 g (yield 72.4%) of <Compound 129> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=710[(M+1) ⁺ ]

Synthesis example 7: Synthesis of compound 135

(One) production example 1: Synthesis of Intermediate 135-1

2-(4-Aminophenyl)benzoxazole (10.0 g, 0.048 mol), 2-(4-Bromophenyl)benzoxazole (19.6 g, 0.071 mol), NaO ^t Bu (9.1 g, 0.095 mol), t-Bu ₃ P (1.4 g, 0.002 mol), Pd(dba) ₂ (0.9 g, 0.005 mol) was added with 150 ml of Toluene and stirred at 70° C. for 4 hours to react. After completion of the reaction, 11.2 g (yield 58.4%) of <Intermediate 135-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) production example 2: Synthesis of compound 135

Intermediate 129-1 (10.0 g, 0.024 mol), Intermediate 135-1 (14.7 g, 0.036 mol), NaO ^t Bu (4.7 g, 0.049 mol), Pd(dba) ₂ (0.7 g, 0.001 mol), t- 150 mL of Toluene was added to Bu ₃ P (0.5 g, 0.002 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 13.2 g (yield 69.8%) of <Compound 135> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=778 [(M+1) ⁺ ]

Synthesis example 8: Synthesis of compound 147

(One) production example 1: Synthesis of intermediate 147-1

4-Bromodibenzothiophene (10.0 g, 0.038 mol), 3,5-Dichlorobromobenzene (8.7 g, 0.046 mol), K ₂ CO ₃ (15.8 g, 0.114 mol), Pd(PPh ₃ ) ₄ (0.9 g, 0.001 mol) 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added, and the reaction was stirred at 100 °C for 6 hours. After completion of the reaction, the mixture was extracted and concentrated, and then columned to obtain 9.3 g (yield 74.3%) of <Intermediate 147-1>.

(2) production example 2: Synthesis of intermediate 147-2

Intermediate 147-1 (10.0 g, 0.030 mol), Benzoxazole (5.4 g, 0.046 mol), Pd(OAc) ₂ (0.07 g, 0.0003 mol), Cu(OAc) ₂ (0.1 g, 0.0006 mol), K ₂ CO Toluene was added to ₃ (8.4 g, 0.061 mol), PPh ₃ (3.9 g, 0.015 mol), and X-Phos (0.29 g, 0.0006 mol), and the reaction was stirred at 110° C. for 4 hours. After completion of the reaction, 7.1 g (yield 56.8%) of <Intermediate 147-2> was obtained by extraction and concentration, followed by column and recrystallization.

(3) production example 3: Synthesis of compound 147

Intermediate 147-2 (10.0 g, 0.024 mol), 4-(2-Naphthalenyl)-N-[4-(2-naphthalenyl)phenyl]-benzeneamine (15.3.g, 0.036 mol), NaO ^t Bu (4.7 g, 0.049 mol), Pd(dba) ₂ (0.7 g, 0.001 mol), and t-Bu ₃ P (0.5 g, 0.002 mol) were added with 150 mL of Toluene and stirred at 70 °C for 4 hours to react. After completion of the reaction, 12.6 g (yield 65.1%) of <Compound 147> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=796[(M+1) ⁺ ]

Synthesis example 9: Synthesis of compound 152

(One) production example 1: Synthesis of intermediate 152-1

2-Bromo-9,9'-spirobi[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), Pd (dba) ₂ (0.7 g, 0.001 mol), t-Bu ₃ P (0.5 g, 0.002 mol) was added to 150 mL of Toluene to react by stirring at 70 ℃ for 4 hours. After completion of the reaction, 7.2 g (yield 54.4%) of <Intermediate 152-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) production example 2: Synthesis of compound 152

Intermediate 147-2 (10.0 g, 0.024 mol), Intermediate 152-1 (19.1 g, 0.036 mol), NaO ^t Bu (4.7 g, 0.049 mol), Pd(dba) ₂ (0.7 g, 0.001 mol), t- 150 mL of Toluene was added to Bu ₃ P (0.5 g, 0.002 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 15.3 g (yield 70.1%) of <Compound 152> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=898[(M+1) ⁺ ]

Synthesis example 10: Synthesis of compound 172

(One) production example 1: Synthesis of intermediate 172-1

4-Amino-4'-cyanobiphenyl (10.0 g, 0.052 mol), 4'-Bromo-4-cyano-biphenyl (19.9 g, 0.077 mol), NaO ^t Bu (9.9 g, 0.103 mol), Pd(dba) ₂ (1.5 g, 0.003 mol), 150 mL of Toluene was added to t-Bu ₃ P (1.0 g, 0.005 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 10.9 g (yield 57.0%) of <Intermediate 172-1> was obtained by extraction, concentration, and column.

(2) production example 2: Synthesis of intermediate 172-2

Intermediate 147-1 (10.0 g, 0.030 mol), Benzothiazole (6.2 g, 0.046 mol), Pd(OAc) ₂ (0.07 g, 0.0003 mol), Cu(OAc) ₂ (0.1 g, 0.0006 mol), K ₂ CO Toluene was added to ₃ (8.4 g, 0.061 mol), PPh ₃ (4.0 g, 0.015 mol), and X-Phos (0.29 g, 0.0006 mol), and the reaction was stirred at 110° C. for 4 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 5.2 g (yield 39.5%) of <Intermediate 172-2>.

(3) production example 3: Synthesis of compound 172

Intermediate 172-2 (10.0 g, 0.024 mol), Intermediate 172-1 (19.1 g, 0.036 mol), NaO ^t Bu (4.7 g, 0.049 mol), Pd(dba) ₂ (0.7 g, 0.001 mol), t- 150 mL of Toluene was added to Bu ₃ P (0.5 g, 0.002 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 15.3 g (yield 70.1%) of <Compound 172> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=762[(M+1) ⁺ ]

Synthesis example 11: Synthesis of compound 254

(One) production example 1: Synthesis of Intermediate 254-1

Intermediate 111-2 (10.0 g, 0.025 mol), Bis(pinacolato)diboron (6.7 g, 0.027 mol), CH ₃ COOK (12.4 g, 0.126 mol), Pd(dba) ₂ (0.3 g, 0.0005 mol), X -Phos (0.2 g, 0.0005 mol) was put in THF and reacted by stirring at 100 °C for 12 hours under nitrogen gas. After completion of the reaction, 9.5 g (yield 77.2%) of <Intermediate 254-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) production example 2: Synthesis of compound 254

Intermediate 254-1 (10.0 g, 0.021 mol), 2-Chloro-4,6-bis(4-phenylphenyl)-1,3,5-triazine (10.3 g, 0.025 mol), K ₂ CO ₃ (8.5 g, 0.062 mol), Pd(PPh ₃ ) ₄ (0.5 g, 0.0004 mol) was added with 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O, followed by stirring at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 11.2 g (yield 73.3%) of <Compound 254>.

LC/MS: m/z=744[(M+1) ⁺ ]

Synthesis example 12: Synthesis of compound 256

(One) production example 1: Synthesis of Intermediate 256-1

2,4-Dichloro-6-(4-phenylphenyl)-1,3,5-triazine (10.0 g, 0.033 mol), 9,9-Dimethyl-2-fluoreneboronic acid (9.5 g, 0.040 mol), K ₂ CO ₃ (13.7 g, 0.099 mol), Pd(PPh ₃ ) ₄ (0.8 g, 0.0007 mol) was added to 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O, followed by stirring at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 8.4 g (yield 55.2%) of <Intermediate 256-1>.

(2) production example 2: Synthesis of compound 256

Intermediate 254-1 (10.0 g, 0.021 mol), Intermediate 256-1 (11.3 g, 0.025 mol), K ₂ CO ₃ (8.5 g, 0.062 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 at 100 °C for 6 hours. After completion of the reaction, 11.8 g (yield 73.3%) of <Compound 256> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=784 [(M+1) ⁺ ]

Synthesis example 13: Synthesis of compound 258

(One) production example 1: Synthesis of intermediate 258-1

2,4-Dichloro-6-(4-phenylphenyl)-1,3,5-triazine (10.0 g, 0.033 mol), 3-Dibenzofuranboronic acid (8.4 g, 0.040 mol), K ₂ CO ₃ (13.7 g, 0.099) mol), Pd(PPh ₃ ) ₄ (0.8 g, 0.0007 mol) was added to 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O, followed by stirring at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 7.6 g (yield 52.9%) of <Intermediate 258-1>.

(2) production example 2: Synthesis of compound 258

Intermediate 254-1 (10.0 g, 0.021 mol), Intermediate 258-1 (10.7 g, 0.025 mol), K ₂ CO ₃ (8.5 g, 0.062 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 at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 11.4 g (yield 73.2%) of <Compound 258>.

LC/MS: m/z=758 [(M+1) ⁺ ]

Synthesis example 14: Synthesis of compound 291

(One) production example 1: Synthesis of intermediate 291-1

2,4-Dichloro-6-(4-phenylphenyl)-1,3,5-triazine (10.0 g, 0.033 mol), 9,9'-Spirobi(9H-fluorene)-2-boronic acid (14.3 g, 0.040) mol), K ₂ CO ₃ (13.7 g, 0.099 mol), Pd(PPh ₃ ) ₄ (0.8 g, 0.0007 mol) to 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added and heated at 100 °C for 6 hours. The reaction was stirred. After completion of the reaction, the mixture was extracted, concentrated, and then columned to obtain 9.9 g (yield: 51.4%) of <Intermediate 291-1>.

(2) production example 2: Synthesis of intermediate 291-2

Intermediate 147-2 (10.0 g, 0.024 mol), Bis(pinacolato)diboron (6.5 g, 0.026 mol), CH ₃ COOK (11.9 g, 0.121 mol), Pd(dba) ₂ (0.3 g, 0.0005 mol), X -Phos (0.2 g, 0.0005 mol) was put in THF and reacted by stirring at 100 °C for 12 hours under nitrogen gas. After completion of the reaction, 9.2 g (yield 75.3%) of <Intermediate 291-2> was obtained by extraction and concentration, followed by column and recrystallization.

(3) production example 3: Synthesis of compound 291

Intermediate 291-2 (10.0 g, 0.020 mol), Intermediate 291-1 (13.9 g, 0.024 mol), K ₂ CO ₃ (8.2 g, 0.060 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 at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 13.3 g (yield 72.5%) of <Compound 291>.

LC/MS: m/z=923 [(M+1) ⁺ ]

Synthesis example 15: Synthesis of compound 320

(One) production example 1: Synthesis of compound 320

Intermediate 254-1 (10.0 g, 0.021 mol), 2-(4'-Bromophenyl)-4,6-diphenyl-1,3,5-triazine (9.6 g, 0.025 mol), K ₂ CO ₃ (8.5 g, 0.062 mol), Pd(PPh ₃ ) ₄ (0.5 g, 0.0004 mol) was added with 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O, followed by stirring at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 10.5 g (yield 76.5%) of <Compound 320>.

LC/MS: m/z=668[(M+1) ⁺ ]

Synthesis example 16: Synthesis of compound 324

(One) production example 1: Synthesis of intermediate 324-1

Intermediate 254-1 (10.0 g, 0.021 mol), 1-Bromo-4-iodobenzene (7.0 g, 0.025 mol), K ₂ CO ₃ (8.5 g, 0.062 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, and stirred at 100 °C for 6 hours to react. After completion of the reaction, extraction and concentration were performed, followed by column to obtain 8.1 g (yield 76.5%) of <Intermediate 324-1>.

(2) production example 2: Synthesis of intermediate 324-2

Intermediate 324-1 (10.0 g, 0.019 mol), Bis(pinacolato)diboron (5.9 g, 0.023 mol), KOAc (3.8 g, 0.039 mol), Pd(dppf)Cl ₂ (0.4 g, 0.0006 mol) in dioxane 200 mL and stirred at 100 °C for 12 hours to react. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 8.3 g (yield 76.1%) of <Intermediate 324-2>.

(3) production example 3: Synthesis of compound 324

Intermediate 324-2 (10.0 g, 0.018 mol), 2-Chloro-4,6-bis(3-dibenzofuranyl)-1,3,5-triazine (9.5 g, 0.021 mol), K ₂ CO ₃ (7.4 g, 0.053 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 stirring at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 10.2 g (yield 67.7%) of <Compound 324>.

LC/MS: m/z=848[(M+1) ⁺ ]

Synthesis example 17: Synthesis of compound 327

(One) production example 1: Synthesis of compound 327

Intermediate 254-1 (10.0 g, 0.021 mol), 2-(4-Bromo-1-naphthalenyl)-4,6-diphenyl-1,3,5-triazine (10.8 g, 0.025 mol), K ₂ CO ₃ ( 8.5 g, 0.062 mol), Pd(PPh ₃ ) ₄ (0.5 g, 0.0004 mol) was added to 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O, followed by stirring at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 10.7 g (yield 72.6%) of <Compound 327>.

LC/MS: m/z=718 [(M+1) ⁺ ]

device embodiment

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 the patterned ITO substrate was mounted in a vacuum chamber, organic materials and metals were deposited in the following structure on the substrate at a process pressure of 1 × 10 ^-6 torr or more.

Device Examples 1 to 43

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. Then, [α-NPB] was formed to a film of 100 nm to form a hole transport layer. did. After that, [TCTA] was formed into a film to a thickness of 10 nm to form an electron blocking layer. Thereafter, 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, an electron transport layer (50% doped with [201] compound Liq below) was deposited at 30 nm, and then LiF was deposited to a thickness of 1 nm to form an electron injection layer. Thereafter, 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 a light efficiency improvement layer (capping layer) compound, compounds 1, 3, 10, 11, 13, 14, 16, 17, 20, 21, 22, 25, 30, 35, 37, 42, 45 implemented in the present invention , 46, 72, 78, 79, 93, 95, 96, 98, 100, 101, 103, 109, 111, 116, 117, 123, 129, 135, 141, 144, 147, 152, 158, 172, 185 , 189 to a thickness of 70 nm to prepare an organic light emitting device.

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 43.

Device Comparative Example 2

The organic light emitting device for Device Comparative Example 2 was prepared in the same manner as in Examples 1 to 43, except that the following Alq ₃ was used instead of the compound according to the present invention as the light efficiency improving layer compound in the device structure.

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 according to the present invention as the light efficiency improving layer compound in the device structures of Examples 1 to 43.

Experimental Example 1: Light emitting properties of Device Examples 1 to 43

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 1 3.6 8.8 0.135 0.050 2 Formula 3 3.9 8.0 0.139 0.047 3 Formula 10 3.8 8.4 0.132 0.053 4 Formula 11 3.5 8.8 0.131 0.057 5 Formula 13 3.7 8.5 0.138 0.055 6 Formula 14 3.5 8.8 0.131 0.059 7 Formula 16 3.8 8.3 0.133 0.055 8 Formula 17 3.6 8.8 0.137 0.052 9 Formula 20 3.9 8.0 0.139 0.046 10 Formula 21 3.8 8.4 0.130 0.053 11 Formula 22 3.6 8.8 0.131 0.063 12 Formula 25 3.4 8.9 0.133 0.056 13 Formula 30 3.9 8.0 0.135 0.049 14 Formula 35 3.7 8.7 0.132 0.058 15 Formula 37 3.8 8.3 0.130 0.055 16 Formula 42 3.7 8.5 0.131 0.054 17 Formula 45 3.8 8.2 0.135 0.053 18 Formula 46 3.8 8.4 0.130 0.060 19 Formula 72 3.9 8.1 0.135 0.051 20 Formula 78 3.6 8.7 0.137 0.049 21 Formula 79 3.9 8.0 0.139 0.046 22 Formula 93 3.8 8.4 0.130 0.053 23 Formula 95 3.5 8.8 0.132 0.058 24 Formula 96 3.8 8.3 0.135 0.055 25 Formula 98 3.9 8.0 0.136 0.049 26 Formula 100 3.8 8.4 0.132 0.057 27 Formula 101 3.5 8.8 0.135 0.055 28 Formula 103 3.9 8.0 0.137 0.049 29 Formula 109 4.0 8.0 0.138 0.050 30 Formula 111 3.8 8.4 0.131 0.055 31 Formula 116 3.5 8.8 0.132 0.058 32 Formula 117 3.8 8.3 0.134 0.056 33 Formula 123 3.9 8.0 0.135 0.049 34 Formula 129 3.7 8.5 0.131 0.057 35 Formula 135 3.8 8.3 0.130 0.055 36 Formula 141 3.7 8.5 0.133 0.059 37 Formula 144 3.8 8.2 0.136 0.050 38 Formula 147 3.8 8.2 0.132 0.056 39 Formula 152 3.9 8.1 0.139 0.048 40 Formula 158 3.6 8.7 0.138 0.047 41 Formula 172 3.7 8.5 0.133 0.052 42 Formula 185 3.7 8.6 0.132 0.056 43 Formula 189 3.8 8.3 0.131 0.057 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 conventional light efficiency improving layer, the compound used as the conventional light efficiency improving layer It can be seen that the driving voltage is reduced and the current efficiency is improved as compared to the device employing the ?

[HAT-CN] [α-NPB] [BH1] [BD1] [201]

[TCTA] [CP 1]

Device Example (ETL)

In an embodiment according to the present invention, the ITO transparent electrode is patterned so that the light emitting area is 2 mm × 2 mm in size using an ITO glass substrate to which an ITO transparent electrode is attached, on a glass substrate of 25 mm × 25 mm × 0.7 mm and then washed. After the substrate was mounted in a vacuum chamber and the base pressure was set to 1 × 10 ^-6 torr or more, the organic material and the metal were deposited on the ITO in the following structure.

Device Examples 44 to 77

The compound implemented according to the present invention was used as the electron transport layer. An organic light emitting device having the following device structure was manufactured, and light emitting characteristics including current efficiency were measured.

ITO / hole injection layer (HAT-CN, 5 nm) / hole transport layer (α-NPB, 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)

To form a hole injection layer on the ITO transparent electrode, [HAT-CN] was used to deposit at 5 nm, and then the hole transport layer was deposited at 100 nm using α-NPB. The electron blocking layer was deposited to a thickness of 10 nm using [EBL1]. In addition, [BH1] was used as a host compound for the emission layer, and [BD1] was used as a dopant compound to be co-deposited to a thickness of 20 nm. In addition, the electron transport layer is a chemical formula 197, 204, 207, 218, 227, 235, 250, 254, 255, 256, 257, 258, 261, 267, 269, 270, 271, 272, 273, 274 implemented according to the present invention. , 275, 286, 291, 299, 307, 308, 309, 312, 320, 321, 324, 325, 327, 328 were used to form a film to a thickness of 30 nm (Liq doping). An organic light emitting diode was manufactured by forming a film of 1 nm LiF and 100 nm of Al.

Device Comparative Example 4

The organic light emitting device for Device Comparative Example 4 was manufactured in the same manner except that the following 201 was used instead of the compound embodied in the present invention for the electron transport layer in the device structure.

Experimental Example 2: Light emitting properties of Device Examples 44 to 77

The organic electroluminescent 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 is shown in [Table 2] below.

Example electron transport layer V cd/A CIEx CIEy 44 Formula 197 3.9 7.4 0.133 0.153 45 Formula 204 4.1 7.3 0.134 0.151 46 Formula 207 4.0 7.3 0.137 0.148 47 Formula 218 4.2 7.5 0.135 0.151 48 Formula 227 3.9 7.3 0.133 0.152 49 Formula 235 4.0 7.3 0.132 0.153 50 Formula 250 4.2 7.2 0.133 0.152 51 Formula 254 4.1 7.1 0.135 0.148 52 Formula 255 4.0 7.3 0.136 0.154 53 Formula 256 3.8 7.4 0.135 0.149 54 Formula 257 4.1 7.3 0.135 0.150 55 Formula 258 3.9 7.3 0.133 0.155 56 Formula 261 4.0 7.2 0.134 0.147 57 Formula 267 4.1 7.3 0.134 0.151 58 Formula 269 4.2 7.3 0.135 0.146 59 Formula 270 4.0 7.5 0.134 0.150 60 Formula 271 4.1 7.0 0.135 0.148 61 Formula 272 4.1 6.9 0.136 0.147 62 Formula 273 3.9 7.4 0.136 0.157 63 Formula 274 4.0 7.5 0.134 0.151 64 Formula 275 4.2 7.1 0.133 0.153. 65 Formula 286 4.2 7.5 0.134 0.151 66 Formula 291 4.2 7.5 0.135 0.148 67 Formula 299 4.1 7.2 0.133 0.153 68 Formula 307 4.1 7.5 0.133 0.153 69 Formula 308 3.9 7.3 0.135 0.148 70 Formula 309 4.1 7.0 0.134 0.157 71 Formula 312 4.0 7.5 0.135 0.148 72 Formula 320 4.1 7.5 0.134 0.151 73 Formula 321 4.2 7.3 0.135 0.150 74 Formula 324 4.2 7.3 0.134 0.151 75 Formula 325 4.0 7.3 0.132 0.151 76 Formula 327 4.1 7.4 0.133 0.151 77 Formula 328 3.9 7.6 0.132 0.149 Comparative Example 4 201 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 electron transport layer in the organic light emitting device, the luminous efficiency and quantum efficiency compared to the device employing the conventionally used electron transport material compound (Comparative Example 4) It can be seen that the light emission characteristics are remarkably excellent.

[HAT_CN] [α-NPB] [BH1] [BD1] [EBL1]

[201]

Claims (8)

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

In the [Formula I],
X is O, S or CRR';
R and R' are the same as 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,

A is represented by the following [Structural Formula 1],
[Structural Formula 1]

In the [Structural Formula 1],
X is O or S;
R ₁ to R ₅ 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
Any one of R ₁ to R ₅ is bonded at the A position in [Formula I],

B is represented by the following [Structural Formula 2] or [Structural Formula 3],
[Structural Formula 2]

[Structural Formula 3]

In the [Structural Formula 2] and [Structural Formula 3],
L ₁ to L ₃ are the same as 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 ₃ 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, and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms,
o, p, and q are each an integer of 1 to 3, and when o, p, and q are each 2 or more, a plurality of Ar ₁ to Ar ₃ are the same or different from each other, respectively. According to claim 1,
In the definitions of R, R', R ₁ to R ₅ , L ₁ and L ₂ , 'substituted or unsubstituted' means deuterium, a halogen group, a cyano group, a nitro group, a hydroxyl group, a silyl group, an alkyl group, a cyclo Substituted with 1 or 2 or more substituents selected from the group consisting of an alkyl group, an alkoxy group, an alkenyl group, a fluorenyl group, an aryl group, and a heteroaryl group An organic light emitting compound, characterized in that it means that. According to claim 1,
The [Formula I] is an organic light emitting compound, characterized in that selected from the following [Compound 1] to [Compound 374]:

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 above [Formula I] in the electron transport layer or a layer that performs both electron transport and electron injection 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.