KR20160051210A - Hetero-cyclic compound and organic light emitting device using the same - Google Patents

Abstract

The present invention provides: a heterocyclic compound capable of greatly improving lifespan, efficiency, electrochemical stability and thermal stability of an organic light emitting device; and an organic light emitting device where the heterocyclic compound is contained in an organic compound layer. In addition, the heterocyclic compound is represented by chemical formula 1.

Description

HETERO-CYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE USING THE SAME [0002]

The present invention relates to a heterocyclic compound and an organic light emitting device using the same.

An electroluminescent device is one type of self-luminous display device, and has advantages of wide viewing angle, excellent contrast, and high response speed.

The organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to the organic light emitting device having such a structure, electrons and holes injected from the two electrodes couple to each other in the organic thin film and form a pair, which then extinguishes and emits light. The organic thin film may be composed of a single layer or a multilayer, if necessary.

The material of the organic thin film may have a light emitting function as needed. For example, as the organic thin film material, a compound capable of forming a light emitting layer by itself may be used, or a compound capable of serving as a host or a dopant of a host-dopant light emitting layer may be used. In addition, as the material of the organic thin film, a compound capable of performing a role such as hole injection, hole transport, electron blocking, hole blocking, electron transport, electron injection, etc. may be used.

In order to improve the performance, life or efficiency of an organic light emitting device, development of materials for organic thin films is continuously required.

U.S. Patent No. 4,356,429

A compound having a chemical structure capable of satisfying the conditions required for a material usable in an organic light emitting device, for example, an appropriate energy level, electrochemical stability and thermal stability, The organic light-emitting device is required to be studied.

An embodiment of the present application provides a heterocyclic compound represented by the following formula (1): < EMI ID =

[Chemical Formula 1]

In Formula 1,

X is NR13, S, O, SiR14R15 or CR16R17,

R13 to R17 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; -CN; A substituted or unsubstituted C ₁ to C ₆₀ straight or branched alkyl group; A substituted or unsubstituted C ₂ to C ₆₀ linear or branched alkenyl group; A substituted or unsubstituted C ₂ to C ₆₀ linear or branched alkynyl group; A substituted or unsubstituted C ₁ to C ₆₀ straight or branched chain alkoxy group; A substituted or unsubstituted C ₃ to C ₆₀ monocyclic or polycyclic cycloalkyl group; A substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heterocycloalkyl group; A substituted or unsubstituted C ₆ to C ₆₀ monocyclic or polycyclic aryl group; A substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group; -SiRR'R "; -P (= O) RR '; and C ₁ to C ₂₀ alkyl group, a substituted or unsubstituted C ₆ to C ₆₀ monocyclic or polycyclic aryl groups, or substituted or unsubstituted C ₂ And an amine group substituted or unsubstituted with a monocyclic or polycyclic heteroaryl group having a carbon number of 1 to ₆₀ ,

L1 and L2 are each independently a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylene group; A substituted or unsubstituted naphthalene group; A substituted or unsubstituted anthracene group; And a substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroarylene group, provided that when L 1 and L 2 are simultaneously a direct bond,

R1 to R12 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; -CN; A substituted or unsubstituted C ₁ to C ₆₀ straight or branched alkyl group; A substituted or unsubstituted C ₂ to C ₆₀ linear or branched alkenyl group; A substituted or unsubstituted C ₂ to C ₆₀ linear or branched alkynyl group; A substituted or unsubstituted C ₁ to C ₆₀ straight or branched chain alkoxy group; A substituted or unsubstituted C ₃ to C ₆₀ monocyclic or polycyclic cycloalkyl group; A substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heterocycloalkyl group; A substituted or unsubstituted C ₆ to C ₆₀ monocyclic or polycyclic aryl group; A substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group; -SiRR'R "; -P (= O) RR '; and C ₁ to C ₂₀ alkyl group, a substituted or unsubstituted C ₆ to C ₆₀ monocyclic or polycyclic aryl groups, or substituted or unsubstituted C ₂ Or an amine group substituted or unsubstituted with a monocyclic or polycyclic heteroaryl group having a carbon number of 1 to ₆₀ , or two or more adjacent groups of R 1 to R 12 are bonded to each other to form a substituted or unsubstituted monocyclic or polycyclic aliphatic or aromatic hydrocarbon ring Lt; / RTI >

A substituted or unsubstituted C ₁ to C ₆₀ linear or branched alkyl group, a substituted or unsubstituted C ₃ to C ₆₀ linear or branched alkyl group, a substituted or unsubstituted C ₃ to C alkenyl group, for C ₆₀ monocyclic or polycyclic cycloalkyl group; or a substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group; a substituted or unsubstituted monocyclic ring of C ₆ to C ₆₀ aryl or polycyclic group.

Another embodiment of the present application is an organic light emitting device comprising a cathode, a cathode, and at least one organic layer provided between the anode and the cathode, wherein at least one of the organic layers is a heterocyclic compound Emitting layer.

The heterocyclic compound according to one embodiment of the present application can be used as an organic material layer material of an organic light emitting device. The heterocyclic compound can be used as a material for a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer in an organic light emitting device. In particular, the heterocyclic compound represented by Formula 1 can be used as an electron transporting layer, a hole transporting layer, or a material of a light emitting layer of an organic light emitting device. In addition, when the compound is used in an organic light emitting device represented by Formula 1, the driving voltage of the device can be lowered, the light efficiency can be improved, and the lifetime characteristics of the device can be improved by thermal stability of the compound.

FIGS. 1 to 3 schematically show a stacked structure of organic light emitting devices according to one embodiment of the present application.
Fig. 4 shows a graph of LTPL measurement at 334 nm wavelength of Compound 1. Fig.
5 is a graph showing the UV value of Compound 1. Fig.
6 shows a PL measurement graph of Compound 1 at a wavelength of 242 nm.
7 shows a PL measurement graph of Compound 1 at a wavelength of 291 nm.
8 shows a PL measurement graph of Compound 1 at a wavelength of 334 nm.
9 is a graph showing the LTPL measurement of Compound 2 at a wavelength of 324 nm.
10 is a graph showing the UV value of Compound 2. Fig.
11 shows the PL measurement graph of Compound 2 at a wavelength of 240 nm.
Fig. 12 shows a PL measurement graph of Compound 2 at a wavelength of 293 nm.
FIG. 13 shows a PL measurement graph of Compound 2 at a wavelength of 324 nm.
14 is a graph showing the LTPL measurement of Compound 3 at a wavelength of 324 nm.
15 is a graph showing the UV value of Compound 3. Fig.
16 shows the PL measurement graph of Compound 3 at a wavelength of 240 nm.
17 shows the PL measurement graph of Compound 3 at a wavelength of 292 nm.
18 shows the PL measurement graph of Compound 3 at a wavelength of 324 nm.
19 is a graph showing the LTPL measurement at a wavelength of 292 nm of Compound 33. Fig.
20 is a graph showing UV values of Compound 33. Fig.
21 shows the PL measurement graph of Compound 33 at a wavelength of 241 nm.
22 shows the PL measurement graph of Compound 33 at a wavelength of 287 nm.
23 shows the PL measurement graph of Compound 33 at a wavelength of 292 nm.
DESCRIPTION OF THE REFERENCE NUMERALS
100: substrate
200: anode
300: organic layer
301: Hole injection layer
302: hole transport layer
303: light emitting layer
304: hole blocking layer
305: electron transport layer
306: electron injection layer
400: cathode

The present application will be described in detail below.

The heterocyclic compound according to one embodiment of the present application is characterized by being represented by the above formula (1). More specifically, the heterocyclic compound represented by the formula (1) can be used as an organic material layer material of the organic light emitting device according to the structural features of the core structure and the substituent.

According to one embodiment of the present application, the formula (1) may be represented by any one of the following formulas (2) to (5).

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In Formulas 2 to 5, X, L 1, L 2, R 3, and R 11 have the same definitions as in Formula 1.

In one embodiment of the present application, at least one of L1 and L2 in Formula 1 of Formula 1 is a direct bond and the other is a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylene group; A substituted or unsubstituted naphthalene group; A substituted or unsubstituted anthracene group; And a substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroarylene group.

In one embodiment of the present application, L 1 and L 2 in Formula 1 are each independently a substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylene group; A substituted or unsubstituted naphthalene group; A substituted or unsubstituted anthracene group; And a substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroarylene group.

In one embodiment of the present application, R 2 in Formula 1 is a substituted or unsubstituted C ₆ to C ₆₀ monocyclic or polycyclic aryl group; And a substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group.

In one embodiment of the present application, R 3 of Formula 1 is a substituted or unsubstituted C ₆ to C ₆₀ monocyclic or polycyclic aryl group; And a substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group.

In one embodiment of the present application, R11 in Formula 1 is a substituted or unsubstituted C ₆ to C ₆₀ monocyclic or polycyclic aryl group; And a substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group.

In one embodiment of the present application, R13 to R17 in Formula 1 are the same or different and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C ₆ to C ₆₀ monocyclic or polycyclic aryl group; And a substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group.

In the present application, the substituents of the formulas (1) to (5) will be described in more detail as follows.

As used herein, the term "substituted or unsubstituted" A halogen group; -CN; A C ₁ to C ₆₀ straight or branched alkyl group; A C ₂ to C ₆₀ straight or branched chain alkenyl group; A C ₂ to C ₆₀ linear or branched alkynyl group; A C ₃ to C ₆₀ monocyclic or polycyclic cycloalkyl group; A C ₂ to C ₆₀ monocyclic or polycyclic heterocycloalkyl group; A C ₆ to C ₆₀ monocyclic or polycyclic aryl group; A C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group; -SiR ' R "; -P (= O) RR '; C ₁ to C ₂₀ alkylamine groups; A C ₆ to C ₆₀ monocyclic or polycyclic arylamine group; And a monocyclic or polycyclic heteroarylamine group having a carbon number of ₂ to ₆₀ , or substituted or unsubstituted with a substituent having two or more of the substituents bonded thereto, or two Quot; means that the above-mentioned substituent is substituted or unsubstituted with a connected substituent. For example, the "substituent group to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected. The additional substituents may be further substituted. A substituted or unsubstituted C ₁ to C ₆₀ linear or branched alkyl group, a substituted or unsubstituted C ₃ to C alkyl group, a substituted or unsubstituted C ₃ to C alkenyl group, a substituted or unsubstituted C ₃ to C alkenyl group, to monocyclic or polycyclic cycloalkyl group of C _60; is a substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group; a substituted or unsubstituted monocyclic the unsubstituted C ₆ to C ₆₀ or polycyclic aryl group.

According to one embodiment of the present application, the "substituted or unsubstituted" refers to a group selected from the group consisting of deuterium, a halogen group, -CN, SiRR'R ", P (= O) RR ', a C ₁ to C ₂₀ linear or branched alkyl group , A monocyclic or polycyclic aryl group having ₆ to ₆₀ carbon atoms, and a monocyclic or polycyclic heteroaryl group having ₂ to ₆₀ carbon atoms,

Wherein R, R 'and R "are the same or different, each independently represent hydrogen, deuterium; -CN; deuterium, halogen, -CN, C ₁ to alkyl groups of linear or branched C _20, C ₆ to C ₆₀ monocyclic or polycyclic aryl groups, and C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group substituted or unsubstituted C ₁ to alkyl groups of straight-chain or branched-chain C ₆₀ of; deuterium, halogen, -CN, C ₁ to alkyl groups of linear or branched C _20, C ₆ to C ₆₀ monocyclic or polycyclic aryl groups, and C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group monocyclic substituted or unsubstituted C ₃ to C ₆₀ ring A straight or branched chain alkyl group having ₁ to ₂₀ carbon atoms, a monocyclic or polycyclic aryl group having ₆ to ₆₀ carbon atoms, and a monocyclic or polycyclic monocyclic or polycyclic hydrocarbon group having ₂ to ₆₀ carbon atoms, monocyclic or polycyclic aryl groups, substituted or unsubstituted groups heteroaryl C ₆ to C _60; It is deuterium, halogen, -CN, C ₁ to C ₂₀ straight or branched chain alkyl group, C ₆ to C ₆₀ monocyclic or polycyclic aryl group, and a C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group substituted or Or an unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group.

The term "substituted" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the substituted position is not limited as long as the substituent is a substitutable position, , Two or more substituents may be the same as or different from each other.

In the present specification, the halogen may be fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group includes a straight chain or a branched chain having 1 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms of the alkyl group may be 1 to 60, specifically 1 to 40, more specifically 1 to 20. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, Ethyl, propyl, isopropyl, n-butyl, isobutyl, isobutyl, isobutyl, An n-pentyl group, a tert-butyl group, a tert-butyl group, a 3-methylbutyl group, a 3-methylbutyl group, a 2-ethylbutyl group, a heptyl group, 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 specification, the alkenyl group includes a straight chain or a branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. The carbon number of the alkenyl group may be 2 to 60, specifically 2 to 40, more specifically, 2 to 20. Specific examples include a vinyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2-yl group, But are not limited to, - (naphthyl-1-yl) vinyl-1-yl group, 2,2-bis (diphenyl-1-yl) vinyl-1-yl group, stilbenyl group, styrenyl group and the like.

In the present specification, the alkynyl group includes a straight chain or a branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. The carbon number of the alkynyl group may be 2 to 60, specifically 2 to 40, more specifically, 2 to 20.

In the present specification, the cycloalkyl group includes monocyclic or polycyclic rings having 3 to 60 carbon atoms, and may be further substituted by other substituents. Herein, the term "polycyclic" means a group in which a cycloalkyl group is directly connected to another ring group or condensed therewith. Here, the other ring group may be a cycloalkyl group, but may be another ring group such as a heterocycloalkyl group, an aryl group, a heteroaryl group and the like. The number of carbon atoms of the cycloalkyl group may be 3 to 60, specifically 3 to 40, more particularly 5 to 20. Specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 3-methylcyclopentyl group, a 2,3-dimethylcyclopentyl group, a cyclohexyl group, a 3-methylcyclohexyl group, , 3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group and the like, but are not limited thereto.

In the present specification, the heterocycloalkyl group includes O, S, Se, N or Si as a heteroatom and includes monocyclic or polycyclic rings having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic ring means a group in which the heterocycloalkyl group is directly connected to another ring group or condensed. Here, the other ring group may be a heterocycloalkyl group, but may be another ring group such as a cycloalkyl group, an aryl group, a heteroaryl group and the like. The number of carbon atoms of the heterocycloalkyl group may be 2 to 60, specifically 2 to 40, more specifically 3 to 20.

In the present specification, the aryl group includes monocyclic or polycyclic rings having 6 to 60 carbon atoms, and may be further substituted by other substituents. Herein, a polycyclic ring means a group in which an aryl group is directly connected to another ring group or condensed with another ring group. Here, the other ring group may be an aryl group, but may be another kind of ring group such as a cycloalkyl group, a heterocycloalkyl group, a heteroaryl group and the like. The aryl group includes a spiro group. The carbon number of the aryl group may be 6 to 60, specifically 6 to 40, more specifically 6 to 25. Specific examples of the aryl group include a phenyl group, a biphenyl group, a triphenyl group, a naphthyl group, an anthryl group, a klychenyl group, a phenanthrenyl group, a perylenyl group, a fluoranthenyl group, a triphenylenyl group, An acenaphthyl group, a benzofluorenyl group, a spirobifluorenyl group, a 2,3-dihydro-1H-indenyl group, a condensed ring group thereof, a thiophenecarbonyl group, , But are not limited thereto.

In the present specification, the spiro group is a group including a spiro structure and may have from 15 to 60 carbon atoms. For example, the spiro group may include a structure in which a 2,3-dihydro-1H-indene group or a cyclohexane group is spiro-bonded to a fluorenyl group. Specifically, the following spiro groups may include any of the groups of the following structural formulas.

In the present specification, the heteroaryl group includes S, O, Se, N or Si as a hetero atom and includes monocyclic or polycyclic rings having 2 to 60 carbon atoms, and may be further substituted by other substituents. Herein, the polycyclic ring means a group in which the heteroaryl group is directly connected to another ring group or condensed therewith. Here, the other ring group may be a heteroaryl group, but may be another ring group such as a cycloalkyl group, a heterocycloalkyl group, an aryl group and the like. The heteroaryl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, more specifically 3 to 25 carbon atoms. Specific examples of the heteroaryl group include a pyridyl group, a pyrrolyl group, a pyrimidyl group, a pyridazinyl group, a furanyl group, a thiophene group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, A thiazolyl group, a thiazolyl group, a furazanyl group, an oxadiazolyl group, a thiadiazolyl group, a dithiazolyl group, a tetrazolyl group, a paranyl group, a thiopyranyl group, a diazinyl group, , A thiazinyl group, a dioxinyl group, a triazinyl group, a tetrazinyl group, a quinolyl group, an isoquinolyl group, a quinazolinyl group, an isoquinazolinyl group, a quinolizolyl group, a naphthyridyl group, An imidazopyridinyl group, a diazanaphthalenyl group, a triazinediyl group, an indolyl group, an indolizinyl group, a benzothiazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiophenyl group, a benzothiophenyl group , A dibenzothiophene group, a dibenzofuran group, a carbazolyl group, a benzocarbazolyl group, (Dibenzosilyl), dihydrophenazinyl, phenoxazinyl, phenanthridyl, imidazopyridinyl, thienyl, indolo [3,3-d] pyrimidinyl, 2,3-a] carbazolyl group, indolo [2,3-b] carbazolyl group, indolinyl group, 10,11-dihydrodibenzo [b, f] azepine group, 9,10-dihydro A phenanthrolinyl group, a phenanthrazinyl group, a phenothiatriazinyl group, a phthalazinyl group, a naphthyridinyl group, a phenanthrolinyl group, a benzo [c] [1,2,5] thiadiazolyl group, 1,5-c] quinazolinyl group, pyrido [l, 2-b] indazolyl group, pyrido [l, 2- a] imidazo [1,2-e] indolinyl group, and 5,11-dihydroindeno [1,2-b] carbazolyl group.

In the present specification, the amine group is a monoalkylamine group; Monoarylamine groups; A monoheteroarylamine group; -NH ₂ ; A dialkylamine group; A diarylamine group; A diheteroarylamine group; Alkylarylamine groups; Alkylheteroarylamine groups; And an arylheteroarylamine group. The number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, a diphenylamine group, an anthracenylamine group, A phenylphenylamine group, a diphenylamine group, a methyl-anthracenylamine group, a diphenylamine group, a phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine group, a triphenylamine group, a biphenylnaphthylamine group, Naphthylamine amine group, phenylnaphthylamine amine group, phenylnaphthylamine amine group, biphenyltriphenylenylamine group, and the like.

In the present specification, an arylene group means a group having two bonding positions in an aryl group, that is, a divalent group. The description of the aryl group described above can be applied except that each of these is 2 groups. Further, the heteroarylene group means that the heteroaryl group has two bonding positions, i.e., divalent. The description of the above-mentioned heteroaryl groups can be applied, except that they are each 2 groups.

According to one embodiment of the present application, the formula 1 may be represented by any one of the following compounds, but is not limited thereto.

Also, by introducing various substituents into the structure of Formula 1, it is possible to synthesize a compound having the intrinsic characteristics of the substituent introduced. For example, by introducing a substituent mainly used in a hole injecting layer material, a hole transporting material, a light emitting layer material, and an electron transporting layer material used in manufacturing an organic light emitting device into the core structure, a material meeting the requirements of each organic layer is synthesized .

In addition, by introducing various substituents into the structure of Formula 1, it is possible to finely control the energy band gap, and the characteristics at the interface between the organic materials can be improved and the use of the materials can be diversified.

On the other hand, the above-mentioned heterocyclic compound has a high glass transition temperature (Tg) and thus is excellent in thermal stability. This increase in thermal stability is an important factor in providing drive stability to the device.

The heterocyclic compound according to one embodiment of the present application can be prepared by a multistage chemical reaction. Some intermediate compounds may be prepared first, and compounds of formula (1) may be prepared from the intermediate compounds. More specifically, the heterocyclic compound according to one embodiment of the present application can be prepared on the basis of the following production example.

Another embodiment of the present application provides an organic light emitting device comprising a heterocyclic compound represented by the above formula (1).

The organic light emitting device according to an embodiment of the present application can be manufactured by a conventional method and material for manufacturing an organic light emitting device, except that one or more organic compound layers are formed using the above-described heterocyclic compound.

The heterocyclic compound may be formed into an organic material layer by a solution coating method as well as a vacuum deposition method in the production of an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

Specifically, the organic light emitting device according to one embodiment of the present application includes a cathode, a cathode, and at least one organic layer provided between the anode and the cathode, and at least one of the organic layers includes a heterocycle ≪ / RTI >

FIGS. 1 to 3 illustrate the stacking process of the electrode and the organic layer of the organic light emitting diode according to one embodiment of the present application. However, it is not intended that the scope of the present application be limited by these drawings, and the structure of the organic light emitting device known in the art can be applied to the present application.

1, an organic light emitting device in which an anode 200, an organic layer 300, and a cathode 400 are sequentially stacked on a substrate 100 is shown. However, the present invention is not limited to such a structure, and an organic light emitting device in which a cathode, an organic material layer, and an anode are sequentially stacked on a substrate may be implemented as shown in FIG.

FIG. 3 illustrates the case where the organic material layer is a multilayer. 3 includes a hole injection layer 301, a hole transport layer 302, a light emitting layer 303, a hole blocking layer 304, an electron transport layer 305, and an electron injection layer 306. However, the scope of the present application is not limited by such a laminated structure, and if necessary, the remaining layers except the light emitting layer may be omitted, and other necessary functional layers may be further added.

The organic light emitting device according to the present invention can be manufactured by materials and methods known in the art, except that at least one of the organic material layers contains the heterocyclic compound represented by the formula (1).

The heterocyclic compound represented by the formula (1) may constitute one or more layers of the organic material layer of the organic light emitting device. However, if necessary, the organic material layer may be formed by mixing with other materials.

The heterocyclic compound represented by Formula 1 may be used as an electron transport layer, a hole blocking layer, a material for a light emitting layer, and the like in an organic light emitting device. For example, the heterocyclic compound represented by Formula 1 may be used as a material for an electron transport layer, a hole transport layer, or a light emitting layer of an organic light emitting device.

The heterocyclic compound represented by Formula 1 may be used as a material of the light emitting layer in an organic light emitting device. For example, the heterocyclic compound represented by Formula 1 may be used as a material of a phosphorescent host of an emission layer in an organic light emitting device.

In particular, the heterocyclic compound represented by Formula 1 may be preferably used as a phosphorescent host of the light emitting layer in the organic light emitting device, and may be more preferably used as the material of the phosphorescent green host of the light emitting layer, but the present invention is not limited thereto.

In the organic light emitting device according to one embodiment of the present application, materials other than the heterocyclic compound of Formula 1 are illustrated below, but these are for illustrative purposes only and are not intended to limit the scope of the present application, , ≪ / RTI >

As the cathode material, materials having a relatively large work function can be used, and a transparent conductive oxide, a metal, or a conductive polymer can be used. Specific examples of the cathode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methyl compounds), poly [3,4- (ethylene-1,2-dioxy) compounds] (PEDT), polypyrrole and polyaniline.

As the cathode material, materials having relatively low work functions can be used, and metals, metal oxides, conductive polymers, and the like can be used. 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; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

As the hole injecting material, a known hole injecting material may be used. For example, a phthalocyanine compound such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429 or a compound described in Advanced Material, 6, p. 677 (1994) Star burst type amine derivatives such as tris (4-carbamoyl-9-phenyl) amine (TCTA), 4,4 ', 4 "-tri [phenyl (m- tolyl) amino] triphenylamine MTDAPA), polyaniline / dodecylbenzenesulfonic acid (poly (vinylidene fluoride)) or poly (vinylidene fluoride), which is a soluble conductive polymer, such as 1,3,5-tris [4- (3,4-ethylenedioxythiophene) / poly (4-styrenesulfonate), polyaniline / camphor sulfonic acid or polyaniline / Poly (4-styrene-sulfonate) and the like can be used.

As the hole transporting material, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, a triphenyldiamine derivative, or the like may be used, and a low molecular weight or a high molecular weight material may be used.

Examples of the electron transporting material include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, Derivatives thereof, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, and the like may be used as well as low molecular weight materials and high molecular weight materials.

As the electron injecting material, for example, LiF is typically used in the art, but the present application is not limited thereto.

As the light emitting material, red, green or blue light emitting materials may be used, and if necessary, two or more light emitting materials may be mixed and used. Further, a fluorescent material may be used as a light emitting material, but it may be used as a phosphorescent material. As the light emitting material, a material which emits light by coupling holes and electrons respectively injected from the anode and the cathode may be used. However, materials in which both the host material and the dopant material participate in light emission may also be used.

The organic light emitting diode according to one embodiment of the present application may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

The heterocyclic compound according to one embodiment of the present application may act on a principle similar to that applied to organic light emitting devices in organic electronic devices including organic solar cells, organic photoconductors, organic transistors and the like.

Hereinafter, the present invention will be described in more detail by way of examples, but these are for the purpose of illustrating the present application and are not intended to limit the scope of the present application.

<Examples>

PREPARATION EXAMPLE 1 Preparation of Compound 1

1) Preparation of compounds 1-4

(9H-carbazole, 0.5 g, 2.99 mmol), CuI (569 mg, 2.99 mmol), trans-1, 2-diaminocyclohexylcarbodiimide (Trans-1,2-diaminocyclohexane, 314 mg, 2.99 mmol) and K ₃ PO ₄ (1.2 g, 6 mmol) were placed in 10 ml of 1,4-dioxane and refluxed for one day. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. And then separated using a short filter to obtain desired product compounds 1-4.

2) Preparation of compound 1-3

2- (dimethylamino) ethanol (0.6 ml, 6 mmol) was dissolved in hexane and then 2.5M n-BuLi (4.3 ml, 12 mmol) was slowly added dropwise to the compound 1-4 at 0 ° C . After stirring for 30 minutes, Compound 1-4 (0.5 g, 2 mmol) was dissolved in 2 ml of hexane and slowly added dropwise. After stirring for 1 hour, it was added CBr ₄ at -78 ℃. After stirring for 1 hour, the mixture was removed from the dry ice bath and stirred at room temperature for one day. After completion of the reaction, H ₂ O was added at 0 ° C, stirred for 30 minutes, and extracted with ether / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. Column chromatography was used to separate the desired product compounds 1-3.

3) Preparation of Compound 1-2

(9-phenyl-9H-carbazol-3-yl) boronic acid (1.1 g, 3.9 mmol), 1-bromo-3-iodobenzene (1-bromo-3-iodobenzene , 1g, 3.5mmol), Pd (PPh 3) was dissolved in _{4 (202mg, 0.175mmol), KOH} (393mg, 7mmol) in toluene _{(toluene) 15ml, H 2 O} 3ml, EtOH 3ml And refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. Column chromatography gave the desired product compound 1-2.

4) Preparation of Compound 1-1

(1-2 g, 2.5 mmol), bis (pinacolato diboron, 1 g, 4 mmol), KOAc 736 mg (7.5 mmol), Pd (dppf) Cl ₂ CH ₂ Cl ₂ 183 mg 0.25 mmol) were dissolved in 21 ml of DMF and refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer is dried over MgSO ₄ and the solvent is removed by distillation under reduced pressure. The product was isolated using column chromatography to obtain the desired product compound 1-1.

5) Preparation of Compound 1

Compound 1-1 10.34g (23mmol), compound 1-3 7.5g (23mmol), Pd ( PPh 3) 4 1.3g (1.15mmol), K 2 CO 3 6.4g (46mmol) in toluene (toluene) 110ml / EtOH 20 ml / H ₂ O and refluxed for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. The desired product was obtained by column chromatography.

PREPARATION EXAMPLE 2 Preparation of Compound 2

1) Preparation of compound 2-2

9- (3-bromophenyl) -9H-carbazole, 5g, 15.5mmol), bis (pinacolato) diboron, 6.3g 4.5 g (46.5 mmol) of KOAc and 1.13 g (1.55 mmol) of Pd (dppf) Cl ₂ CH ₂ Cl ₂ were dissolved in 100 ml of DMF and refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. Column chromatography was used to separate the desired product compound 2-2.

2) Preparation of compound 2-1

Compound 2-2 14.5g (50.6mmol), 2,6- dibromo-pyridine (2,6-dibromopyridine) 24g (101mmol ), Pd (PPh 3) 4 2.9g (2.53mmol), K 2 CO 3 14g ( 101.2 mmol) was dissolved in 300 ml of toluene / 60 ml of EtOH / 60 ml of H ₂ O and refluxed for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. The desired product was obtained by column chromatography.

3) Preparation of Compound 2

0.4 g (1.5 mmol) of Compound (2-1) (0.5 g, 1.25 mmol) and (9-phenyl-9H-carbazol-3-yl) boronic acid 80 mg (0.07 mmol) of Pd (PPh ₃ ) _{4 and} 345 mg (2.5 mmol) of K ₂ CO ₃ were dissolved in toluene 7.5 ml / EtOH 1.5 ml / H ₂ O 1.5 ml and refluxed for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. The desired product compound 2 was obtained by column chromatography.

PREPARATION EXAMPLE 3 Preparation of Compound 3

0.34 g (1.5 mmol) of dibenzo [b, d] thiophen-4-ylboronic acid, Pd (PPh ₃₎ ) _{4 and} 345 mg (2.5 mmol) of K ₂ CO ₃ were dissolved in toluene 7.5 ml / EtOH 1.5 ml / H ₂ O 1.5 ml and refluxed for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. The desired product compound 3 was obtained by separation using column chromatography.

PREPARATION EXAMPLE 4 Preparation of Compound 9

1) Preparation of compound 9-2

5 g (15.5 mmol) of 9- (4-bromophenyl) -9H-carbazole and 6.3 g of bis (pinacolato diboron) 4.5 g (46.5 mmol) of KOAc and 1.13 g (1.55 mmol) of Pd (dppf) Cl ₂ CH ₂ Cl ₂ were dissolved in 100 ml of DMF and refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. Separation using column chromatography gave the desired product compound 9-2.

2) Preparation of Compound 9-1

Compound 9-2 14.5g (50.6mmol), 2,6- dibromo-pyridine (2,6-dibromopyridine) 24g (101mmol ), Pd (PPh 3) 4 2.9g (2.53mmol), K 2 CO 3 14g ( 101.2 mmol) was dissolved in 300 ml of toluene / 60 ml of EtOH / 60 ml of H ₂ O and refluxed for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. Column chromatography was used to separate the desired product compound 9-1.

3) Preparation of Compound 9

Compound 9-1 0.5g (1.25mmol), dibenzo [b, d] furan-4-Daily acid (dibenzo [b, d] furan -4-ylboronic acid) 0.3g (1.5mmol), Pd (PPh 3) ₄ 80mg (0.07mmol), was dissolved in K ₂ CO ₃ 345mg (2.5mmol) in toluene (toluene) 7.5ml / 1.5ml EtOH / H ₂ O 1.5ml was refluxed for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. The desired product was obtained by column chromatography.

PREPARATION EXAMPLE 5 Preparation of Compound 16

1) Preparation of compound 16-2

1-bromo-3-iodobenzene 1 g (3.5 mmol), (9-phenyl-9H-carbazol-1-yl) 1-yl) boronic acid, 202 mg (0.175 mmol) of Pd (PPh ₃ ) ₄ and 393 mg ( ₇ mmol) of KOH were dissolved in 15 ml of toluene, 3 ml of H ₂ O and 3 ml of EtOH, Lt; / RTI &gt; After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. Column chromatography was used to separate the desired product compound 16-2.

2) Preparation of compound 16-1

1 g (4 mmol) of bis (pinacolato diboron), 736 mg (7.5 mmol) of KOAc and 183 mg (0.25 mmol) of Pd (dppf) Cl ₂ CH ₂ Cl _2, mmol) were dissolved in 21 ml of DMF and refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. The product was isolated using column chromatography to obtain the desired product compound 16-1.

3) Preparation of Compound 16

0.5 g (1.5 mmol) of dibenzo [b, d] furan-4-ylboronic acid and 0.54 g (1.5 mmol) of Pd (PPh ₃ ) ₄ 80mg (0.07mmol), was dissolved in K ₂ CO ₃ 345mg (2.5mmol) in toluene (toluene) 7.5ml / 1.5ml EtOH / H ₂ O 1.5ml was refluxed for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. The desired product was obtained by column chromatography.

PREPARATION EXAMPLE 6 Preparation of Compound 33

(Dibenzo [b, d] thiophen-4-yl) phenyl) boronic acid (0.5 g, 1.25 mmol) (1.5 mmol) of Pd (PPh ₃ ) _{4 and} 345 mg (2.5 mmol) of K ₂ CO ₃ were dissolved in 1.5 ml of toluene / 1.5 ml of EtOH / 1.5 ml of H ₂ O And refluxed for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. The desired product compound 33 was obtained by column chromatography.

PREPARATION EXAMPLE 7 Preparation of Compound 102

1) Preparation of Compound 102-2

(3.1 mmol) of 9- (naphthalen-1-yl) -9H-carbazol-3-yl) boronic acid, , 4'-bromo-3-iodo-1,1'-biphenyl (4'-bromo-3-iodo -1,1'-biphenyl) 1g (2.8mmol), Pd (PPh 3) 4 161mg ( 772 mg (5.6 mmol) of K ₂ CO ₃ were dissolved in 15 ml of toluene, 3 ml of H ₂ O and 3 ml of EtOH, and the mixture was refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. Column chromatography was used to separate the desired product compound 102-2.

2) Preparation of Compound 102-1

1 g (4 mmol) of bis (pinacolato diboron), 736 mg (7.5 mmol) of KOAc and 183 mg (0.25 mmol) of Pd (dppf) Cl ₂ CH ₂ Cl _2, mmol) were dissolved in 21 ml of DMF and refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. Column chromatography was used to separate the desired product compound 102-1.

3) Preparation of Compound 102

349 mg (0.3 mmol) of Pd (PPh ₃ ) _{4 and} 690 mg (5 mmol) of K ₂ CO ₃ were dissolved in 15 ml of toluene, ₂ ml of H ₂ 3 ml of EtOH, and refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer is dried over MgSO ₄ and the solvent is removed by distillation under reduced pressure. Column chromatography was used to separate the desired product compound 102.

PREPARATION EXAMPLE 8 Preparation of Compound 121

1) Preparation of Compound 121-2

(3.1 mmol) of 2-bromo-6-iodonaphthalene, 4'-bromo-3-iodo-1,1'-biphenyl (4'- 161 mg (0.14 mmol) of Pd (PPh ₃ ) _{4 and} 772 mg (5.6 mmol) of K ₂ CO ₃ were dissolved in 15 ml of toluene, 3 ml of H ₂ O, EtOH And the mixture was refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. Column chromatography was used to separate the desired product compound 121-2.

2) Preparation of Compound 121-1

1 g (4 mmol) of bis (pinacolato diboron), 736 mg (7.5 mmol) of KOAc and 183 mg (2.5 mmol) of Pd (dppf) Cl ₂ CH ₂ Cl ₂ 0.25 mmol) was dissolved in 21 ml of DMF and refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. The desired product was obtained by column chromatography.

3) Preparation of Compound 121

349 mg (0.3 mmol) of Pd (PPh ₃ ) _{4 and} 690 mg (5 mmol) of K ₂ CO ₃ were dissolved in 15 ml of toluene, 5 ml of H ₂ 3 ml of EtOH, and refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. The desired product was obtained by column chromatography.

PREPARATION EXAMPLE 9 Preparation of Compound 126

1) Preparation of compound 126-5

1 g (6 mmol) of 9H-carbazole and 1 g (6 mmol) of NBS were dissolved in 100 ml of MC, followed by stirring for 6 hours. After completion of the reaction, the reaction mixture was extracted with MC / H ₂ O (Sat? NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. Separation using column chromatography gave the desired product compound 126-5.

2) Preparation of compound 126-4

Compound 126-5 1g (4mmol), phenylboronic acid (phenylboronic acid) 0.6g (4.9mmol) , Pd (PPh 3) 4 0.2g (0.2mmol) K 2 CO 3 1.1g (8mmol) in toluene (toluene) 15ml , 3 ml of H ₂ O, 3 ml of EtOH and refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. Separation using column chromatography gave the desired product compound 126-4.

3) Preparation of compound 126-3

Compound 126-4 1g (4.1mmol), 1,3- dibromo-benzene (1,3-dibromobenzene) 1.9g (8.22mmol ), Pd (PPh 3) 4 0.2g (0.2mmol) K 2 CO 3 1.1g (8 mmol) were dissolved in 15 ml of toluene, 3 ml of H ₂ O and 3 ml of EtOH, and the mixture was refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. Separation using column chromatography gave the desired product compound 126-3.

4) Preparation of compound 126-2

(5 mmol) of bis (pinacolato) diboron, 736 mg (7.5 mmol) of KOAc and 183 mg (2.5 mmol) of Pd (dppf) Cl ₂ CH ₂ Cl ₂ 0.25 mmol) was dissolved in 21 ml of DMF and refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. Separation using column chromatography gave the desired product compound 126-2.

5) Preparation of compound 126-1

Compound 126-2 1g (2.5mmol), 2,6- dibromo-pyridine (2,6-dibromopyridine) 0.7g (3mmol ), Pd (PPh 3) 4 0.2g (0.2mmol) K 2 CO 3 1.1g ( 8 mmol) were dissolved in 15 ml of toluene, 3 ml of H ₂ O and 3 ml of EtOH, and the mixture was refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. The desired product was obtained by column chromatography.

6) Preparation of compound 126

Compound 126-1 1g (2.2mmol), compound 121-1 1.3g (2.6mmol), Pd ( PPh 3) 4 0.2g (0.2mmol) K 2 CO 3 1.1g (8mmol) in toluene (toluene) 15ml, H ₂ O, 3 ml of EtOH and refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. The desired product was obtained by column chromatography.

PREPARATION EXAMPLE 10 Preparation of Compound 154

1) Preparation of compound 154-5

(9-phenyl-9H-carbazol-3-yl) boronic acid 1 g (3.5 mmol), 4-bromo-4'- 1,1'-biphenyl (4-bromo-4'-iodo -1,1'-biphenyl) 1.5g (4mmol), Pd (PPh 3) 4 0.2g (0.2mmol), K 2 CO 3 1.1g ( 8 mmol) were dissolved in 15 ml of toluene, 3 ml of H ₂ O and 3 ml of EtOH, and the mixture was refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. The desired product was obtained by column chromatography.

2) Preparation of compound 154-4

1 g (4.2 mmol) of compound 154-5, 1 g (4.2 mmol) of bis (pinacolato diboron), 0.59 mg (6 mmol) of KOAc and 146 mg of Pd (dppf) Cl ₂ CH ₂ Cl ₂ 0.2 mmol) was dissolved in 21 ml of DMF and refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. The desired product was obtained by column chromatography.

3) Preparation of compound 154-3

4-bromo-4'-iodo-1,1'-biphenyl), 1 g (6.3 mmol) of 9H-carbazole, 0.7 g (6.3 mmol) of trans-1,2-diaminocyclohexane, 2.6 g (12.6 mmol) of K ₃ PO _4, ) Was placed in 20 ml of 1,4-dioxane and refluxed for one day. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. The desired product was obtained by separation using a short filter.

4) Preparation of compound 154-2

Compound 154-3 1g (2.5mmol), bis (pinacolato) diboron (bis (pinacolato) diboron) 1.3g (5mmol), KOAc 0.7g (7.5mmol), Pd (dppf) Cl 2 CH 2 Cl 2 220mg (0.3 mmol) were dissolved in 21 ml of DMF and refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. The desired product was obtained by column chromatography.

5) Preparation of compound 154-1

Compound 154-2 1g (2.2mmol), 2,6- dibromo-pyridine (2,6-dibromopyridine) 1g (4.4mmol ), Pd (PPh 3) 4 127mg (0.11mmol), K 2 CO 3 0.6g ( 4.4 mmol) was dissolved in toluene (15 ml), H ₂ O (3 ml) and EtOH (3 ml), and the mixture was refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. The desired product was obtained by column chromatography.

6) Preparation of compound 154

Compound (154-1) A mixture of 1 g (2.1 mmol) of 9-phenyl-3- (4 &apos;-( 4,4,5,5-tetramethyl-1,3,2-dioxabororan- Biphenyl] -3-yl) -9H-carbazole (9-phenyl-3- (4 &apos;-( 4,4,5,5-tetramethyl-1,3,2-dioxaborolan- 2- yl) - [1,1'-biphenyl] -3-yl) -9H-carbazole) 1.2g (2.3mmol), Pd (PPh 3) 4 121mg (0.1mmol), K 2 CO 3 0.6g (4.2mmol) Was dissolved in 15 ml of toluene, 3 ml of H ₂ O and 3 ml of EtOH and refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. The desired product was obtained by column chromatography.

PREPARATION EXAMPLE 11 Preparation of Compound 175

1) Preparation of compound 175-5

Dibenzo [b, d] thiophen-2-ylboronic acid 1 g (4.3 mmol), 2-bromo-6 -iodonaphthalene) 1.7g (5mmol), Pd (PPh 3) 4 0.2g (0.2mmol), K 2 CO 3 1.1g ( after 8mmol) was dissolved in a toluene _{(toluene) 15ml, H 2 O} 3ml, EtOH 3ml 6 sigan Lt; / RTI &gt; After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. Column chromatography was used to separate the desired product compound 175-5.

2) Preparation of compound 175-4

1.3 g (5 mmol) of bis (pinacolato diboron), 0.7 g (7.5 mmol) of KOAc, 220 mg of Pd (dppf) Cl ₂ CH ₂ Cl _{2, 2.5} g (0.3 mmol) were dissolved in 21 ml of DMF and refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. Separation using column chromatography gave the desired product compound 175-4.

3) Preparation of compound 175-3

3.6 g (12.6 mmol) of 1,4-dibromonaphthalene, 1.2 g (6.3 mmol) of CuI, 1 g (6.3 mmol) of 9H-carbazole, 0.7 g (6.3 mmol) of trans-1,2-diaminocyclohexane and 2.6 g (12.6 mmol) of K ₃ PO ₄ were placed in 20 ml of 1,4-dioxane and refluxed for one day . After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. And then separated using a short filter to obtain the desired product compound 175-3.

4) Preparation of compound 175-2

(2.7 mmol) of compound 175-3, 1.3 g (5.4 mmol) bis (pinacolato) diboron, 0.7 g (7.5 mmol) KOAc, Pd (dppf) Cl ₂ CH ₂ Cl ₂ 220 mg (0.3 mmol) was dissolved in 21 ml of DMF and refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. The product was isolated using column chromatography to obtain the desired product compound 175-2.

5) Preparation of compound 175-1

Compound 175-2 1g (2.4mmol), 2,6- dibromo-pyridine (2,6-dibromopyridine) 1g (4.4mmol ), Pd (PPh 3) 4 127mg (0.11mmol), K 2 CO 3 0.6g ( 4.4 mmol) was dissolved in toluene (15 ml), H ₂ O (3 ml) and EtOH (3 ml), and the mixture was refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. Column chromatography was used to separate the desired product compound 175-1.

6) Preparation of compound 175

Compound 175-1 1g (2.2mmol), compound 175-4 1.1g (2.6mmol), Pd ( PPh 3) 4 121mg (0.1mmol), K 2 CO 3 0.6g (4.2mmol) in toluene (toluene) 15ml, 3 ml of H ₂ O, 3 ml of EtOH, and refluxed for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with EA / H ₂ O (Sat'd NaHCO ₃ ). The organic layer was dried over MgSO ₄ and the solvent was distilled off under reduced pressure. The desired product compound 175 was obtained by column chromatography.

The compounds were prepared in the same manner as in the above Preparation Examples, and the results of the confirmation of the synthesis were shown in Tables 1 and 2. Table 1 shows the measured values of ¹ H NMR (CDCl ₃ , 400 Mz) and Table 2 shows the measured values of FD-MS (field desorption mass spectrometry).

[Table 1]

[Table 2]

The decomposition temperatures, Tg (glass transition temperature), Tm (melting temperature) and the like of the compounds 1, 2, 3 and 33 were measured and shown in Table 3 below.

[Table 3]

4 to 23 are graphs showing PL absorption spectra measured by PL (Photoluminescence) or LTPL (Low Temperature Photoluminescence) in a specific UV wavelength region. PL was measured at room temperature using a model LS55 spectrophotometer of Perkin Elmer, and LTPL was measured at -196 ° C (77K) using liquid nitrogen at a temperature of -196 ° C (77K) using a HITACHI model F7000 instrument.

Fig. 4 shows a graph of LTPL measurement at 334 nm wavelength of Compound 1. Fig.

5 is a graph showing the UV value of Compound 1. Fig.

6 shows a PL measurement graph of Compound 1 at a wavelength of 242 nm.

7 shows a PL measurement graph of Compound 1 at a wavelength of 291 nm.

8 shows a PL measurement graph of Compound 1 at a wavelength of 334 nm.

9 is a graph showing the LTPL measurement of Compound 2 at a wavelength of 324 nm.

10 is a graph showing the UV value of Compound 2. Fig.

11 shows the PL measurement graph of Compound 2 at a wavelength of 240 nm.

Fig. 12 shows a PL measurement graph of Compound 2 at a wavelength of 293 nm.

FIG. 13 shows a PL measurement graph of Compound 2 at a wavelength of 324 nm.

14 is a graph showing the LTPL measurement of Compound 3 at a wavelength of 324 nm.

15 is a graph showing the UV value of Compound 3. Fig.

16 shows the PL measurement graph of Compound 3 at a wavelength of 240 nm.

17 shows the PL measurement graph of Compound 3 at a wavelength of 292 nm.

18 shows the PL measurement graph of Compound 3 at a wavelength of 324 nm.

19 is a graph showing the LTPL measurement at a wavelength of 292 nm of Compound 33. Fig.

20 is a graph showing UV values of Compound 33. Fig.

21 shows the PL measurement graph of Compound 33 at a wavelength of 241 nm.

22 shows the PL measurement graph of Compound 33 at a wavelength of 287 nm.

23 shows the PL measurement graph of Compound 33 at a wavelength of 292 nm.

<Experimental Example>

&Lt; Comparative Example 1 > Fabrication of organic light emitting device

An organic light emitting device was prepared in the following manner.

The glass substrate coated with ITO thin film with a thickness of 1,500 Å was washed with distilled water ultrasonic waves. After the distilled water was washed, it was ultrasonically cleaned with a solvent such as acetone, methanol, isopropyl alcohol, dried, and UV-treated for 5 minutes using UV in a UV scrubber. Subsequently, the substrate was transferred to a plasma cleaner (PT), subjected to a plasma treatment to remove ITO work function and residual film in a vacuum state, and transferred to a thermal evaporation apparatus for organic vapor deposition.

A hole injection layer 2-TNATA (4,4 ', 4 "-tris [2-naphthyl (phenyl) amino] triphenylamine) as a common layer was deposited on the ITO transparent electrode (anode) N'-Di (1-naphthyl) -N, N'-diphenyl- (1,1'-biphenyl) -4,4'-diamine).

The light emitting layer was then subjected to thermal vacuum deposition as follows. The light-emitting layer of CBP (4,4'-N, N'- dicarbazole-biphenyl), Ir as a green phosphorescent dopant _{(ppy) 3 (tris (2} -phenylpyridine) iridium) Ir (ppy) ₃ in CBP using the host 11% doped and 300Å deposited. Thereafter, BCP was deposited to a thickness of 60 Å as a hole blocking layer, and Alq ₃ was deposited to a thickness of 200 Å as an electron transport layer thereon. Finally, lithium fluoride (LiF) was deposited on the electron transport layer to a thickness of 10 Å to form an electron injection layer. An aluminum (Al) cathode was deposited on the electron injection layer to a thickness of 1,200 Å to form a cathode Thereby preparing a light emitting device.

On the other hand, all the organic compounds necessary for the organic light emitting device were vacuum sublimated and refined under the respective conditions of 10 ^-6 to 10 ^-8 torr.

Examples 1 to 10 Fabrication of an organic light emitting device

Except that each of the compounds 1, 2, 3, 9, 16, 102, 154 and 174 synthesized in this application was used instead of the host CPB used in forming the light emitting layer in Comparative Example 1, 1 to prepare an organic light emitting device.

The electroluminescence (EL) characteristics of the organic light-emitting devices fabricated in Examples 1 to 10 and Comparative Example 1 were measured by M7000 of Mitsui-Mitsubishi Electric Corporation, T90 was measured with a reference instrument (M6000) at a reference luminance of 6,000 cd / m ² . The characteristics of the organic light emitting device of the present invention are shown in Table 4 below.

[Table 4]

As can be seen from the results of Table 4, the organic light emitting device using the organic light emitting device light emitting layer material according to one embodiment of the present application had a lower driving voltage and improved light emitting efficiency as compared with Comparative Example 1, .

Claims (14)

A heterocyclic compound represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
X is NR13, S, O, SiR14R15 or CR16R17,
R13 to R17 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; -CN; A substituted or unsubstituted C ₁ to C ₆₀ straight or branched alkyl group; A substituted or unsubstituted C ₂ to C ₆₀ linear or branched alkenyl group; A substituted or unsubstituted C ₂ to C ₆₀ linear or branched alkynyl group; A substituted or unsubstituted C ₁ to C ₆₀ straight or branched chain alkoxy group; A substituted or unsubstituted C ₃ to C ₆₀ monocyclic or polycyclic cycloalkyl group; A substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heterocycloalkyl group; A substituted or unsubstituted C ₆ to C ₆₀ monocyclic or polycyclic aryl group; A substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group; -SiRR'R "; -P (= O) RR '; and C ₁ to C ₂₀ alkyl group, a substituted or unsubstituted C ₆ to C ₆₀ monocyclic or polycyclic aryl groups, or substituted or unsubstituted C ₂ And an amine group substituted or unsubstituted with a monocyclic or polycyclic heteroaryl group having a carbon number of 1 to ₆₀ ,
L1 and L2 are each independently a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylene group; A substituted or unsubstituted naphthalene group; A substituted or unsubstituted anthracene group; And a substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroarylene group, provided that when L 1 and L 2 are simultaneously a direct bond,
R1 to R12 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; -CN; A substituted or unsubstituted C ₁ to C ₆₀ straight or branched alkyl group; A substituted or unsubstituted C ₂ to C ₆₀ linear or branched alkenyl group; A substituted or unsubstituted C ₂ to C ₆₀ linear or branched alkynyl group; A substituted or unsubstituted C ₁ to C ₆₀ straight or branched chain alkoxy group; A substituted or unsubstituted C ₃ to C ₆₀ monocyclic or polycyclic cycloalkyl group; A substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heterocycloalkyl group; A substituted or unsubstituted C ₆ to C ₆₀ monocyclic or polycyclic aryl group; A substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group; -SiRR'R "; -P (= O) RR '; and C ₁ to C ₂₀ alkyl group, a substituted or unsubstituted C ₆ to C ₆₀ monocyclic or polycyclic aryl groups, or substituted or unsubstituted C ₂ Or an amine group substituted or unsubstituted with a monocyclic or polycyclic heteroaryl group having a carbon number of 1 to ₆₀ , or two or more adjacent groups of R 1 to R 12 are bonded to each other to form a substituted or unsubstituted monocyclic or polycyclic aliphatic or aromatic hydrocarbon ring Lt; / RTI &gt;
A substituted or unsubstituted C ₁ to C ₆₀ linear or branched alkyl group, a substituted or unsubstituted C ₃ to C ₆₀ linear or branched alkyl group, a substituted or unsubstituted C ₃ to C alkenyl group, for C ₆₀ monocyclic or polycyclic cycloalkyl group; or a substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group; a substituted or unsubstituted monocyclic ring of C ₆ to C ₆₀ aryl or polycyclic group. The heterocyclic compound according to claim 1, wherein the formula 1 is represented by any one of the following formulas 2 to 5:
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

In Formulas 2 to 5, X, L 1, L 2, R 3, and R 11 have the same definitions as in Formula 1. [3] The compound according to claim 1, wherein at least one of L &lt; 1 &gt; and L &
The other is a substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylene group; A substituted or unsubstituted naphthalene group; A substituted or unsubstituted anthracene group; And a substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroarylene group. [4] The compound according to claim 1, wherein L1 and L2 in Formula 1 are each independently a substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylene group; A substituted or unsubstituted naphthalene group; A substituted or unsubstituted anthracene group; And a substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroarylene group. [3] The compound according to claim 1, wherein R &lt; 2 &gt; is a substituted or unsubstituted C ₆ -C ₆₀ monocyclic or polycyclic aryl group; And a substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group. [3] The compound according to claim 1, wherein R &lt; 3 &gt; is a substituted or unsubstituted C ₆ to C ₆₀ monocyclic or polycyclic aryl group; And a substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group. [3] The compound according to claim 1, wherein R &lt; 11 &gt; is a substituted or unsubstituted C ₆ to C ₆₀ monocyclic or polycyclic aryl group; And a substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group. [4] The compound according to claim 1, wherein R13 to R17 in Formula 1 are the same or different from each other and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C ₆ to C ₆₀ monocyclic or polycyclic aryl group; And a substituted or unsubstituted C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group. [2] The compound according to claim 1, wherein the "substituted or unsubstituted" A halogen group; -CN; A C ₁ to C ₆₀ straight or branched alkyl group; A C ₂ to C ₆₀ straight or branched chain alkenyl group; A C ₂ to C ₆₀ linear or branched alkynyl group; A C ₃ to C ₆₀ monocyclic or polycyclic cycloalkyl group; A C ₂ to C ₆₀ monocyclic or polycyclic heterocycloalkyl group; A C ₆ to C ₆₀ monocyclic or polycyclic aryl group; A C ₂ to C ₆₀ monocyclic or polycyclic heteroaryl group; -SiR ' R &quot;; -P (= O) RR '; C ₁ to C ₂₀ alkylamine groups; A C ₆ to C ₆₀ monocyclic or polycyclic arylamine group; And a monocyclic or polycyclic heteroarylamine group having a carbon number of ₂ to ₆₀ , or substituted or unsubstituted with a substituent having two or more of the substituents bonded thereto, or two Wherein said substituent is substituted or unsubstituted with a substituent connected thereto. The heterocyclic compound according to claim 1, wherein the formula 1 is represented by any one of the following compounds:

An organic light emitting device comprising an anode, a cathode, and at least one organic layer provided between the anode and the cathode, wherein at least one of the organic layers includes a heterocyclic compound according to any one of claims 1 to 10. 12. The organic electroluminescent device according to claim 11, wherein the organic material layer includes at least one of a hole blocking layer, an electron injecting layer and an electron transporting layer, and at least one of the hole blocking layer, the electron injecting layer and the electron transporting layer includes the heterocyclic compound Wherein the organic light-emitting device comprises: [Claim 11] The organic light emitting device of claim 11, wherein the organic layer includes a light emitting layer, and the light emitting layer comprises the heterocyclic compound. [12] The organic EL device according to claim 11, wherein the organic material layer includes at least one of a hole injection layer, a hole transport layer, and a layer simultaneously injecting holes and transporting holes, wherein one of the layers includes the heterocyclic compound .

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