KR20210146628A - 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 an organic matter layer material such as a light emitting layer, a hole transport layer, an electron transport layer, an electron blocking layer, and a light efficiency improving layer in an organic light emitting device to realize light emitting characteristics such as low voltage driving and excellent luminous efficiency of the device; and an organic light emitting device comprising the same.

Description

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

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

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

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

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

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

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

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

[Formula Ⅰ]

Characteristic structures of the [Formula I] and Y, L ₁ to L ₄ and A ₁ to A ₄ will be described later.

When the organic light emitting compound according to the present invention is employed as an organic material layer material such as a light emitting layer, a hole transport layer, an electron transport layer, an electron blocking layer, and a light efficiency improvement layer in an organic light emitting device, low voltage driving of the device and excellent luminous efficiency, etc. Therefore, it can be usefully used for various display devices.

1 is a representative view showing the structure of an organic light emitting compound according to the present invention.

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 light-emitting characteristics such as low voltage driving of the organic light-emitting device and excellent light-emitting efficiency.

[Formula Ⅰ]

In the [Formula I],

Y is any one selected from O, S, NR ₁ , C=O and CR ₂ R _{3 .}

The R ₁ is represented by the following [Structural Formula 1].

[Structural Formula 1]

wherein R ₂ and R ₃ are the same as or different from each other, and each independently 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 3 to C 30 is selected from the heteroaryl group of, wherein R ₂ and R ₃ are connected to each other to form at least one alicyclic, aromatic monocyclic or polycyclic ring, and the formed alicyclic, aromatic monocyclic or polycyclic ring The carbon atom may be substituted with any one or more heteroatoms selected from a nitrogen atom (N), a sulfur atom (S) and an oxygen atom (O).

In addition, in [Formula I] and [Structural Formula 1],

L ₁ to L ₅ are the same or different from each other, and each independently is a single bond, or any one selected from a substituted or unsubstituted arylene group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms; , n, m, o, p and q are each an integer of 0 to 2, and a plurality of L ₁ to L ₅ are the same as or different from each other, respectively.

A ₁ to A ₂ and A ₅ are the same as or different from each other, and each independently 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 3 to 30 heteroaryl groups.

A ₃ and A ₄ are the same as or different from each other, and are each independently represented by the following [Structural Formula 2].

[Structural Formula 2]

In the above [Structural Formula 2],

X is O or S.

R ₁₁ to R ₁₅ are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 2 to C 20 alkenyl group, A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 halogenated alkyl group, a substituted or unsubstituted C1 to C20 a halogenated alkoxy group, a substituted or unsubstituted C 6 to C 30 aryl group, and a substituted or unsubstituted C 3 to C 30 heteroaryl group, wherein any one of _{R 11} to R _{15 is A 3} to A ₄ is a part connected in [Formula I], respectively.

Wherein R ₁₁ to R ₁₄ may be bonded to each other or connected to adjacent substituents to form at least one alicyclic or aromatic monocyclic or polycyclic ring, and the carbon atom of the formed alicyclic, aromatic monocyclic or polycyclic ring is nitrogen It may be substituted with any one or more heteroatoms selected from an atom (N), a sulfur atom (S), and an oxygen atom (O).

According to an embodiment of the present invention, in the [Formula I], A ₃ and A ₄ are each represented by the [Structural Formula 2], and the A ₁ to A ₂ and A _{5 are} also, if necessary, the [Structural Formula 2] can be displayed as

According to an embodiment of the present invention, the [Structural Formula 2] may be any one selected from among those represented by the following [Structural Formula 3] to [Structural Formula 7].

[Structural Formula 3] [Structural Formula 4] [Structural Formula 5]

[Structural Formula 6] [Structural Formula 7]

In the [Structural Formula 3] to [Structural Formula 7],

X is O or S.

Y ₁ to Y ₄ are the same as or different from each other, each independently represent N or CR ₄ , and a plurality of R ₄ are the same as or different from each other.

R ₁₁ to R ₁₅ and the plurality of R ₄ are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 2 to 20 alkenyl group, substituted or unsubstituted C 3 to C 20 cycloalkyl group, substituted or unsubstituted C 1 to C 20 alkoxy group, substituted or unsubstituted C 1 to C 20 halogenated alkyl group, substituted or unsubstituted selected from a halogenated alkoxy group having 1 to 20 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, wherein R ₁ to R ₅ and the plurality of Of R ₄ , any one of A ₁ to A ₅ is a moiety connected to each of the above [Formula I].

Meanwhile, in the _{definitions of L 1} to L ₅ , A ₁ to A ₅ , R ₁ to R ₄ and R ₁₁ to R ₁₅ , substituted or unsubstituted means hydrogen, deuterium, halogen group, cyano group, nitro group, hydroxyl group, silyl substituted with 1 or 2 or more substituents selected from the group consisting of a group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an aryl group, and a heterocyclic group means not

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

In addition, the substituted heteroarylene 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 benzquinoline. It means that the group, benzimidazole group, benzoxazole group, benzthiazole group, benzcarbazole group, dibenzothiophenyl group, dibenzofuran group, etc. are substituted with other substituents.

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

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

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

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

,

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

,

etc.

,

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

,

etc.

In the present invention, the heteroaryl group and the heterocyclic group are heterocyclic groups including O, N or S as heteroatoms, and the number of carbon atoms is not particularly limited, but preferably has 2 to 30 carbon atoms, and in the present invention, specific examples thereof include , thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, acridyl group, pyridyl group Chopped group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, carba Zol group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, dibenzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, phenoxazine group, phenothiazine group, and the like, but is 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 above [Formula I] can be used as various organic material layers in an organic light emitting device due to its structural specificity, and more specifically, it can be used as a material for a light emitting layer, a hole transport layer or a light efficiency improving layer in the organic material layer. have.

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

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

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

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

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

In addition, the organic electroluminescent device according to an embodiment of the present invention includes a substrate, a first electrode (anode), an organic material layer, a second electrode (cathode) and a light efficiency improving layer, wherein the light efficiency improving layer is a lower portion of the first electrode ( Bottom emission) or it may be formed on top of the second electrode (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 improvement layer (CPL) formed of the compound according to the present invention having a relatively high refractive index. The wavelength of is amplified and thus the light efficiency is increased .

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

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

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

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

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

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

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

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

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

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

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

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

Synthesis example 1: Synthesis of compound 1

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

4,6-Dibromodibenzofuran (10 g, 0.031 mol, TCI), Phenylboronic acid (8.98 g, 0.074 mol, sigma aldrich) potassium carbonate (21.2 g, 0.153 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (1.77 g, 0.002 mol, sigma aldrich), toluene 200 mL, ethanol 50 mL, and H ₂ O 50 mL were added, and the reaction was stirred under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and column purification were performed to obtain 6.9 g (yield 70.2%) of <Intermediate 1-1>.

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

Intermediate 1-1 (10 g, 0.031 mol) and N-Bromosuccinimide (13.3 g, 0.075 mol, sigma aldrich) were added to 200 mL of DMF and reacted by stirring at room temperature for 5 hours. After completion of the reaction, extraction was performed and column purification was performed to obtain 9.2 g (yield 61.6%) of <Intermediate 1-2>.

(3) production example 3: Synthesis of compound 1

Intermediate 1-2 (10 g, 0.021 mol), benzo[d]oxazol-2-ylboronic acid (8.18 g, 0.050 mol, mascot) potassium carbonate (14.5 g, 0.105 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (1.21 g, 0.001 mol, sigma aldrich), 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added, and the reaction was stirred under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and column purification were performed to obtain 7.5 g (yield 64.7%) of <Compound 1>.

H-NMR (200MHz, CDCl3): δ ppm, 2H (7.67/s, 7.63/s, 7.41/m) 4H (7.74/m, 7.52/d, 7.51/m, 7.39/d)

LC/MS: m/z=554 [(M+1) ⁺ ]

Synthesis example 2: Synthesis of compound 8

(One) production example 1: Synthesis of Intermediate 8-1

dibenzo[b,d]furan-4,6-diyldiboronic acid (10 g, 0.039 mol, mascot), 1-bromo-4-fluorobenzene (16.4 g, 0.094 mol, sigma aldrich) potassium carbonate (27 g, 0.195 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (2.26 g, 0.002 mol, sigma aldrich), toluene 200 mL, ethanol 50 mL, H ₂ O 50 mL, and reacted by stirring under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and column purification were performed to obtain 10.3 g (yield 73.9%) of <Intermediate 8-1>.

(2) production example 2: Synthesis of Intermediate 8-2

Intermediate 8-1 (10 g, 0.028 mol) and N-Bromosuccinimide (12 g, 0.067 mol, sigma aldrich) were added to 200 mL of DMF and reacted by stirring at room temperature for 5 hours. After completion of the reaction, extraction was performed and column purification was performed to obtain 8.7 g (yield 60.3%) of <Intermediate 8-2>.

(3) production example 3: Synthesis of Intermediate 8-3

Intermediate 8-2 (10 g, 0.019 mol), 5-ethylbenzo[d]oxazol-2-ylboronic acid (8.92 g, 0.047 mol, mascot) potassium carbonate (13.4 g, 0.097 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (1.12 g, 0.001 mol, sigma aldrich), 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added, and the reaction was stirred under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and column purification were performed to obtain 8.2 g (yield 65.2%) of <Intermediate 8-3>.

(4) production example 4: Synthesis of compound 8

Intermediate 8-3 (10 g, 0.016 mol), carbazole (6.2 g, 0.038 mol, sigma aldrich), cesium carbonate (6.41 g, 0.046 mol, sigma aldrich) was added with 500 mL of DMF and stirred under reflux at 150 °C for 12 hours. and reacted. After completion of the reaction, extraction was performed and column purification was performed to obtain 10.3 g (yield 70.8%) of <Compound 8>.

H-NMR (200 MHz, CDCl3): δ ppm, 2H (8.55/d, 8.12/d, 7.94/d, 7.74/d, 7.67/s, 7.62/s, 7.50/m, 7.33/m, 7.25/m) 4H (7.79/d, 7.68/d, 7.63/s, 7.29/d, 2.60/s) 6H (1.25/s)

LC/MS: m/z=940[(M+1) ⁺ ]

Synthesis example 3: Synthesis of compound 13

(One) production example 1: Synthesis of compound 13

2,4,6,8-tetrabromodibenzofuran (10 g, 0.021 mol, mascot), benzo[d]oxazol-2-ylboronic acid (16.2 g, 0.099 mol, mascot), potassium carbonate (25.7 g, 0.186 mol, sigma aldrich) ), Pd(PPh ₃ ) ₄ (1.19 g, 0.001 mol, sigma aldrich), toluene 200 mL, ethanol 50 mL, H ₂ O 50 mL, and H 2 O 50 mL were added, and the reaction was stirred under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and column purification were performed to obtain 9.2 g (yield 69.9%) of <Compound 13>.

H-NMR (200MHz, CDCl3): δ ppm, 2H (7.67/s, 7.63/s) 8H (7.74/m, 7.39/d)

LC/MS: m/z=636[(M+1) ⁺ ]

Synthesis example 4: Synthesis of compound 50

(One) production example 1: Synthesis of compound 50

2,4,6,8-tetrabromodibenzofuran (10 g, 0.021 mol, mascot), 2-phenylbenzo[d]oxazol-5-ylboronic acid (23.7 g, 0.099 mol, mascot) potassium carbonate (25.7 g, 0.186 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (1.19 g, 0.001 mol, sigma aldrich), toluene 200 mL, ethanol 50 mL, H ₂ O 50 mL, and reacted by stirring under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and column purification were performed to obtain 12.9 g of <Compound 50> (yield 66.3%).

H-NMR (200MHz, CDCl3): δ ppm, 2H (7.67/s, 7.63/s) 4H (8.09/s, 7.85/d, 7.79/d, 7.41/m) 8H (8.05/d, 7.51/m)

LC/MS: m/z=940[(M+1) ⁺ ]

Synthesis example 5: Synthesis of compound 89

(One) production example 1: Synthesis of Intermediate 89-1

4,6-dibromodibenzo[b,d]thiophene (10 g, 0.029 mol, mascot), benzo[d]oxazol-2-ylboronic acid (11.5 g, 0.070 mol, mascot) potassium carbonate (20.2 g, 0.146 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (1.69 g, 0.002 mol, sigma aldrich), toluene 200 mL, ethanol 50 mL, H ₂ O 50 mL, and reacted by stirring under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and column purification were performed to obtain 8.3 g (yield: 67.8%) of <Intermediate 89-1>.

(2) production example 2: Synthesis of Intermediate 89-2

Intermediate 89-1 (10 g, 0.024 mol) and N-Bromosuccinimide (10.5 g, 0.057 mol, sigma aldrich) were added to 200 mL of DMF and reacted by stirring at room temperature for 5 hours. After completion of the reaction, extraction was performed and column forward wp to obtain 8.9 g (yield 64.1%) of <Intermediate 89-2>.

(3) production example 3: Synthesis of compound 89

Intermediate 89-2 (10 g, 0.017 mol), benzo[d]oxazol-2-ylboronic acid (6.79 g, 0.042 mol, mascot) potassium carbonate (12 g, 0.087 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (2.01 g, 0.002 mol, sigma aldrich), 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added, and the reaction was stirred under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and column purification were performed to obtain 7.9 g (yield 69.8%) of <Compound 89>.

H-NMR (200MHz, CDCl3): δ ppm, 2H (7.96/s, 7.75/s) 8H (7.74/m, 7.39/d)

LC/MS: m/z=837 [(M+1) ⁺ ]

Synthesis example 6: Synthesis of compound 133

(One) production example 1: Synthesis of Intermediate 133-1

4,6-dibromodibenzothiophene (10 g, 0.029 mol, mascot), 2-Naphthylboronic acid (12.1 g, 0.070 mol, sigma aldrich) potassium carbonate (20.2 g, 0.146 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (1.69 g, 0.002 mol, sigma aldrich), toluene 200 mL, ethanol 50 mL, H ₂ O 50 mL, and reacted by stirring under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and column purification were performed to obtain 9.1 g (yield 71.3%) of <Intermediate 133-1>.

(2) production example 2: Synthesis of intermediate 133-2

Intermediate 133-1 (10 g, 0.023 mol) and N-Bromosuccinimide (9.8 g, 0.055 mol, sigma aldrich) were added to 200 mL of DMF and reacted by stirring at room temperature for 5 hours. After completion of the reaction, extraction was performed and column purification was performed to obtain 8.8 g (yield 63.9%) of <Intermediate 133-2>.

(3) production example 3: Synthesis of intermediate 133-3

2-bromothiazolo[4,5-b]pyridine (10 g, 0.047 mol, mascot), bis(pinacolato)diboron (14.2 g, 0.056 mol, sigma aldrich), potassium acetate (9.13 g, 0.093 mol, sigma aldrich), 200 mL of dioxane was added to Pd(dppf)Cl ₂ (1.02 g, 0.001 mol, sigma aldrich), and the reaction was stirred at 100 °C for 12 hours. After completion of the reaction, extraction was performed and column purification was performed to obtain 9.3 g (yield 76.3%) of <Intermediate 133-3>.

(4) production example 4: Synthesis of compound 133

Intermediate 133-2 (10 g, 0.017 mol), Intermediate 133-3 (10.6 g, 0.040 mol) potassium carbonate (11.6 g, 0.084 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (1.97 g, 0.001 mol, sigma aldrich), toluene 200 mL, ethanol 50 mL, H ₂ O 50 mL, and reacted by stirring under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and column purification were performed to obtain 7.9 g (yield 66.6%) of <Compound 133>.

H-NMR (200 MHz, CDCl3): δ ppm, 2H (8.43/d, 7.96/s, 7.92/d, 7.73/d, 7.58/s, 7.36/m) 4H (8.00/d, 7.75/s, 7.59/m) )

LC/MS: m/z=704[(M+1) ⁺ ]

Synthesis example 7: Synthesis of compound 146

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

Add 500 mL of DMF to 1,3,6,8-tetrabromocarbazole (10 g, 0.021 mol, TCI), fluorobenzene (2.4 g, 0.025 mol, sigma aldrich), cesium carbonate (4.29 g, 0.031 mol, sigma aldrich) 150 The reaction was stirred under reflux at ℃ for 12 hours. After completion of the reaction, extraction was performed and column purification was performed to obtain 8.4 g (yield 72.6%) of <Intermediate 146-1>.

(2) production example 2: Synthesis of compound 146

Add 500 mL of DMF to Intermediate 146-1 (10 g, 0.031 mol), benzo[d]oxazol-2-ylboronic acid (14 g, 0.086 mol, mascot), and cesium carbonate (14.8 g, 0.107 mol, sigma aldrich) The reaction was stirred under reflux at 150 °C for 12 hours. After completion of the reaction, extraction was performed and column purification was performed to obtain 8.7 g (yield 68.3%) of <Compound 146>.

H-NMR (200 MHz, CDCl3): δ ppm, 1H (7.45/m) 2H (7.73/s, 7.58/m, 7.52/s, 7.50/d) 8H (7.74/m, 7.39/d)

LC/MS: m/z=711 [(M+1) ⁺ ]

Device embodiment (capping layer)

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

Device Examples 1 to 11

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

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

HAT-CN was formed to a thickness of 5 nm to form a hole injection layer on an ITO transparent electrode containing Ag on a glass substrate, and then α-NPB was formed as a film of 100 nm for the hole transport layer. The electron blocking layer was formed of TCTA with a thickness of 10 nm. In addition, the light emitting layer was co-deposited at 20 nm using BH1 as a host compound and BD1 as a dopant compound. In addition, an electron transport layer (the following [201] compound doped with 50% Liq) was formed to a thickness of 30 nm and LiF 1 nm. Then, a film of 15 nm was formed of Mg:Ag in a ratio of 1:9. And as a light efficiency improving layer (capping layer) compound, compounds 1, 8, 13, 31, 50, 66, 89, 114, 133, 146, 206 implemented in the present invention were formed into a film to a thickness of 70 nm to form an organic light emitting device. produced.

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 11.

Device Comparative Example 2

The organic light emitting device for Device Comparative Example 2 was manufactured in the same manner except that _{Alq 3} was used instead of the compound of the present invention as the light efficiency improving layer compound in the device structures of Examples 1 to 11.

Experimental Example 1: Light emitting characteristics of Device Examples 1 to 11

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

Example Light Efficiency Improvement Layer V cd/A CIEx CIEy One Formula 1 3.6 8.6 0.140 0.052 2 Formula 8 3.7 8.8 0.141 0.052 3 Formula 13 3.7 9.0 0.142 0.049 4 Formula 31 3.6 8.7 0.142 0.050 5 Formula 50 3.7 8.6 0.140 0.050 6 Formula 66 3.7 8.5 0.142 0.051 7 Formula 89 3.6 8.5 0.141 0.049 8 Formula 114 3.7 8.5 0.142 0.051 9 Formula 133 3.6 8.4 0.141 0.051 10 Formula 146 3.8 8.8 0.140 0.050 11 Formula 206 3.7 8.7 0.142 0.049 Comparative Example 1 not used 4.5 7.0 0.151 0.140 Comparative Example 2 Alq ₃ 4.3 7.8 0.149 0.057

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

[HAT-CN] [α-NPB] [BH1] [BD1] [201]

[TCTA]

Claims (11)

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

In the [Formula I],
Y is any one selected from O, S, NR ₁ , C=O and CR ₂ R _{3 ,}
Wherein R ₁ is represented by the following [Structural Formula 1],
[Structural Formula 1]

wherein R ₂ and R ₃ are the same as or different from each other, and each independently 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 3 to C 30 It is selected from the heteroaryl group of
R ₂ and R ₃ may be connected to each other to form at least one alicyclic or aromatic monocyclic or polycyclic ring, and the carbon atom of the formed alicyclic, aromatic monocyclic or polycyclic ring is a nitrogen atom (N), may be substituted with any one or more heteroatoms selected from a sulfur atom (S) and an oxygen atom (O),
L ₁ to L ₅ are the same or different from each other, and each independently is a single bond, or any one selected from a substituted or unsubstituted arylene group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms; (n, m, o, p and q are each an integer from 0 to 2),
A ₁ to A ₂ and A ₅ are the same as or different from each other, and each independently 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 3 to 30 heteroaryl groups,
A ₃ and A ₄ are the same as or different from each other, and are each independently represented by the following [Structural Formula 2],
[Structural Formula 2]

In the above [Structural Formula 2],
X is O or S;
R ₁₁ to R ₁₅ are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 2 to C 20 alkenyl group, A substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C1 to C20 halogenated alkyl group, a substituted or unsubstituted C1 to C20 It is selected from a halogenated alkoxy group, 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,
Any one of R ₁₁ to R _{15 is a moiety in which A 3} to A ₄ are each connected in [Formula I],
Wherein R ₁₁ to R ₁₄ may be bonded to each other or connected to adjacent substituents to form at least one alicyclic or aromatic monocyclic or polycyclic ring, and the carbon atom of the formed alicyclic, aromatic monocyclic or polycyclic ring is nitrogen It may be substituted with any one or more heteroatoms selected from an atom (N), a sulfur atom (S), and an oxygen atom (O). According to claim 1,
A ₁ to A ₂ and A ₅ are each independently represented by the [Structural Formula 2], and in [Structural Formula 2], any one of _{R 11} to R _{15 is A 1} to A ₂ and A ₅ Each of the [ An organic light emitting compound that is a moiety connected in Formula I]. According to claim 1,
The [Structural Formula 2] is an organic light-emitting compound, characterized in that any one selected from the following [Structural Formula 3] to [Structural Formula 7]:
[Structural formula 3] [Structural formula 4] [Structural formula 5]

[Structural formula 6] [Structural formula 7]

In the [Structural Formula 3] to [Structural Formula 7],
X is O or S;
Y _{1 To} Y _{4 Are} the same as or different from each other, and each independently N or CR ₄ (The plurality of R _{4 Are} the same or different from each other),
R ₁₁ to R ₁₅ and the plurality of R ₄ are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 2 to 20 alkenyl group, substituted or unsubstituted C 3 to C 20 cycloalkyl group, substituted or unsubstituted C 1 to C 20 alkoxy group, substituted or unsubstituted C 1 to C 20 halogenated alkyl group, substituted or unsubstituted selected from a halogenated alkoxy group having 1 to 20 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,
Any one of R ₁ to R ₅ and the plurality of R _{4 is a moiety to which A 1} to A ₅ are each connected in [Formula I]. 4. The method according to any one of claims 1 to 3,
In the _{definitions of L 1} to L ₅ , A ₁ to A ₅ , R ₁ to R ₄ and R ₁₁ to R ₁₅ , 'substituted or unsubstituted' means deuterium, a halogen group, a cyano group, a nitro group, a hydroxyl group, It is substituted with one or more substituents selected from the group consisting of a silyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, an aryl group and a heterocyclic group, or is substituted with a substituent to which two or more of the substituents are connected, or any substituent An organic light emitting compound, characterized in that it does not have one. According to claim 1,
The [Formula I] is an organic light emitting compound, characterized in that selected from the following [Compound 1] to [Compound 219]:

An organic light emitting device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode,
At least one layer of the organic material layer is an organic light emitting device comprising the organic light emitting compound of [Formula I] according to claim 1. 7. The method of claim 6,
The organic material layer is selected from a hole injection layer, a hole transport layer, a layer that performs both hole injection and hole transport functions, an electron transport layer, an electron injection layer, a layer that performs both electron transport and electron injection functions, an electron blocking layer, a hole blocking layer and a light emitting layer including one or more floors that become
At least one of the layers comprises an organic light emitting compound represented by the [Formula I]. 8. The method of claim 7,
The electron transport layer or the layer that performs both electron transport and electron injection functions 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 hole transport layer or the layer that performs both hole injection and hole transport functions at the same time is an organic light emitting device, characterized in that it comprises an organic light emitting compound represented by the [Formula I]. 7. The method of claim 6,
Further comprising a light efficiency improvement layer (Capping layer) formed on at least one side opposite to the organic material layer among the upper or lower portions of the first electrode and the second electrode,
The light efficiency improving layer is an organic light emitting device, characterized in that it comprises an organic light emitting compound represented by the [Formula I]. 11. The method of claim 10,
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.

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