KR101773936B1 - New organic electroluminescent compounds and organic electroluminescent device comprising the same - Google Patents

Abstract

More particularly, the present invention relates to an organic light emitting device capable of realizing excellent light emitting efficiency, light emission luminance, color purity, (ETM), a light emitting layer (EML), a hole transporting layer (HTM), and the like. The first electrode and the second electrode, such as an electron transport layer It is possible to develop a material which can be used in various ways such as various organic films between electrodes, to improve the performance such as the efficiency increase and the reduction of the driving voltage, and to maximize the capability as the OLED material.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device including the same.

The present invention relates to an organic compound and an organic electroluminescent device using the same. More particularly, the present invention relates to an organic electroluminescent device capable of realizing excellent luminescence efficiency, luminescence brightness, color purity and lifetime, Organic optical devices and optical compounds used therein.

An electroluminescence device (EL device) is a self-emissive type display device having a high response speed and a wide viewing angle. In 1987, Eastman Kodak Company first developed an organic EL device using a low molecular aromatic diamine and an aluminum complex as a light emitting layer material [Appl. Phys. Lett. 51, 913, 1987].

The most important factor for determining the luminous efficiency in an OLED is a luminescent material, and a phosphorescent material in a luminescent material can improve luminous efficiency up to 4 times the theoretical value of a fluorescent material. Until now, iridium (III) complexes and carbazole-based materials have been widely known as phosphorescent materials, and new phosphorescent materials are being studied in recent years.

The principle of organic electroluminescence is that when a voltage is applied between two electrodes when there is an organic layer between the cathode and the anode, electrons and holes are injected into the organic layer from the cathode and the anode, respectively. Electrons and holes injected into the organic layer are recombined to form an exciton, and the exciton falls back to the ground state to emit light. An organic light emitting device using this principle may be generally composed of an organic material layer including a cathode, an anode, and an organic thin film layer disposed therebetween, for example, a hole injecting layer, a hole transporting layer, a light emitting layer, and an electron transporting layer.

Most of materials used in organic electroluminescent devices are pure organic materials or complexes in which an organic material and a metal form a complex with each other. Depending on the application, a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, Can be distinguished. As the hole injecting material and the hole transporting material, an organic material having a p-type property, that is, an organic material which is easily oxidized and electrochemically stable at the time of oxidation, is mainly used. On the other hand, as an electron injecting material and an electron transporting material, an organic material having an n-type property, that is, an organic material which is easily reduced and electrochemically stable at the time of reduction is mainly used. As the light emitting layer material, a material having both a p-type property and an n-type property, that is, a material having both a stable state in oxidation and in a reduced state is preferable, and a material having a high luminous efficiency for converting an exciton into light desirable.

Accordingly, there is a need in the art to develop new organic materials having the above-described requirements.

Korean Patent Laid-Open No. 10-2009-0068193 discloses a carbazole-based organic compound capable of generating fluorescence and phosphorescence from red to blue wavelengths and being applicable as a host material of an organic light emitting layer of an organic electroluminescence device, It has:

Korean Patent Laid-Open No. 10-2013-0062583 discloses a carbazole-based organic compound which can be applied as a phosphorescent host material in an organic light emitting layer of an organic electroluminescent device:

However, the materials developed in this field including the above-mentioned materials have not provided satisfactory results in terms of driving voltage, luminous efficiency, luminance, thermal stability, color purity, and device lifetime of the organic electroluminescent device .

Korea Patent Publication No. 10-2009-0068193 Korean Patent Publication No. 10-2013-0062583

The present invention can be applied to an organic electroluminescent device as a light emitting layer material, a hole injecting layer material, a hole transporting layer material, an electron injecting layer material, an electron transporting layer material, an electron blocking layer material and a hole blocking layer material, It is an object of the present invention to provide a novel organic compound capable of lowering the driving voltage of a device and improving luminous efficiency, luminance, thermal stability, color purity, and device life.

It is another object of the present invention to provide an organic electroluminescent device using the organic compound.

In one embodiment of the present invention, there is provided an organic compound represented by the following general formula (1).

[Chemical Formula 1]

A1, A2, R1 and R2 are, each independently,

Hydrogen; heavy hydrogen; halogen; A nitro group; Acyl; A carboxyl group; A hydroxyl group; Or an amide group; A substituted or unsubstituted C1 to C50 alkyl group; A substituted or unsubstituted C1-C20 alkoxy group; An amino group; A substituted or unsubstituted C6-C60 aryl group; And a substituted or unsubstituted C3 to C60 heteroaryl group; and the substituted A1, A2, R1, and R2 are each a substituted or unsubstituted C1-C60 alkyl group wherein at least one of the unsubstituted A1, A2, R1, and R2 is substituted with a first additional substituent and, the first additional substituents include deuterium, _{halo, CN, Si (CH 3)} 2, CF 3, substituted or unsubstituted alkyl group unsubstituted C1 ~ C50, a substituted or unsubstituted C2 ~ C50 alkenyl group, a substituted or unsubstituted A substituted or unsubstituted C3 to C50 cycloalkyl group and a substituted or unsubstituted C1 to C20 alkoxy group;

L is a single bond; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroarylene group having 3 to 60 carbon atoms, said substituted L is at least one hydrogen of said unsubstituted L is substituted with a second additional substituent and the second additional substituents include deuterium, halo, CN, Si (CH _{3) 2,} CF _3, substituted or unsubstituted alkenyl group, a substituted or unsubstituted in the alkyl group of C1 ~ C50, a substituted or unsubstituted C2 ~ C50 A substituted or unsubstituted C 3 to C 50 cycloalkyl group and a substituted or unsubstituted C 1 to C 20 alkoxy group;

The heteroatoms included in the substituents listed above are at least one selected from B, N, O, S, P (= O), Si and P,

Wherein the substituted first additional substituent and the substituted second additional substituent are each such that at least one of the unsubstituted first additional substituent and the unsubstituted second additional substituent is substituted with a tertiary additional substituent, car more substituents deuterium, _{halogen, CN, Si (CH 3)} 2, CF 3, substituted or unsubstituted C1 ~ C50 alkenyl group, a substituted or unsubstituted in the alkyl group, a substituted or unsubstituted C2 of ~ C50 unsubstituted C3 ~ C50 cycloalkyl group and substituted or unsubstituted C1-C20 alkoxy group.

In another embodiment of the present invention,

An organic electroluminescent device having an organic thin film layer sandwiched between a cathode and an anode and comprising one or more layers including at least a light emitting layer,

Wherein at least one of the organic thin film layers contains the organic compound singly or in combination of two or more kinds.

When the organic compound according to the present invention is applied to an organic light emitting device as a light emitting layer material, a hole injecting layer material, a hole transporting layer material, an electron injecting layer material, an electron transporting layer material, an electron blocking layer material, and a hole blocking layer material, And improves the luminous efficiency, brightness, thermal stability, color purity, and device lifetime.

In addition, the organic electroluminescent device manufactured using the organic compound of the present invention has high efficiency and long life characteristics.

1 is a ¹ H-NMR graph of the compound [31] synthesized in Example 1.
2 is a thermogravimetric analysis (TGA) graph for the compound [31] synthesized in Example 1. FIG.
FIG. 3 is a graph of differential scanning calorimetry (DSC) measurement for the compound [31] synthesized in Example 1. FIG.
4 is a ¹ H-NMR spectrum of the compound [2000] synthesized in Comparative Example 1. Fig.
FIG. 5 is a thermogravimetric analysis (TGA) graph of the compound [2000] synthesized in Comparative Example 1. FIG.
FIG. 6 is a graph of differential scanning calorimetry (DSC) measurement for the compound [2000] synthesized in Comparative Example 1. FIG.
FIG. 7 is a ¹ H-NMR spectrum of the compound [3000] synthesized in Comparative Example 2. FIG.
FIG. 8 is a graph showing lifetime characteristics of the compounds [31] and [2000] synthesized in Example 1 and Comparative Example 1. FIG.
FIG. 9 is a graph showing lifetime characteristics of the compounds [42] and [3000] synthesized in Example 2 and Comparative Example 2. FIG.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the term " comprising " or " consisting of ", or the like, refers to the presence of a feature, a number, a step, an operation, an element, a component, But do not preclude the presence or addition of one or more other features, integers, steps, operations, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

In the present specification, "substituted" unless otherwise defined includes, but is not limited to, deuterium, a halogen atom, a C1 to C30 alkyl group, a C3 to C50 cycloalkyl group, a C2 to C30 alkenyl group, a C3 to C50 cycloalkenyl group, A silyl group, a C 1 to C 20 alkoxy group, a C 6 to C 60 aryl group, a C 3 to C 60 heteroaryl group, a C 7 to C 60 arylalkyl group, and a C 6 to C 60 arylalkyl group, And a substituent selected from the group consisting of < RTI ID = 0.0 >

In the present specification, "a combination thereof" means that two or more substituents are connected or condensed to each other, unless otherwise defined.

In the structural formulas of the present specification, "*" means the same or different atom or moiety connected to the formula.

"Hetero" as used herein, unless otherwise defined, means containing a heteroatom in one compound or substituent, wherein the heteroatom is selected from the group consisting of N, O, S, P, Lt; / RTI > For example, it may mean one to three heteroatoms in the one compound or substituent, and the remainder is carbon.

In one embodiment of the present invention, there is provided a novel organic compound represented by the following general formula (1).

[Chemical Formula 1]

A1, A2, R1 and R2 are, each independently,

Hydrogen; heavy hydrogen; halogen; A nitro group; Acyl; A carboxyl group; A hydroxyl group; Or an amide group; A substituted or unsubstituted C1 to C50 alkyl group; A substituted or unsubstituted C1-C20 alkoxy group; An amino group; A substituted or unsubstituted C6-C60 aryl group; And a substituted or unsubstituted C3 to C60 heteroaryl group; and the substituted A1, A2, R1, and R2 are each a substituted or unsubstituted C1-C60 alkyl group wherein at least one of the unsubstituted A1, A2, R1, and R2 is substituted with a first additional substituent and, the first additional substituents include deuterium, _{halo, CN, Si (CH 3)} 2, CF 3, substituted or unsubstituted alkyl group unsubstituted C1 ~ C50, a substituted or unsubstituted C2 ~ C50 alkenyl group, a substituted or unsubstituted A substituted or unsubstituted C3 to C50 cycloalkyl group and a substituted or unsubstituted C1 to C20 alkoxy group;

L is a single bond; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroarylene group having 3 to 60 carbon atoms, said substituted L is at least one hydrogen of said unsubstituted L is substituted with a second additional substituent and the second additional substituents include deuterium, halo, CN, Si (CH _{3) 2,} CF _3, substituted or unsubstituted alkenyl group, a substituted or unsubstituted in the alkyl group of C1 ~ C50, a substituted or unsubstituted C2 ~ C50 A substituted or unsubstituted C 3 to C 50 cycloalkyl group and a substituted or unsubstituted C 1 to C 20 alkoxy group;

The heteroatoms included in the substituents listed above are at least one selected from B, N, O, S, P (= O), Si and P,

Wherein the substituted first additional substituent and the substituted second additional substituent are each such that at least one of the unsubstituted first additional substituent and the unsubstituted second additional substituent is substituted with a tertiary additional substituent, car more substituents deuterium, _{halogen, CN, Si (CH 3)} 2, CF 3, substituted or unsubstituted C1 ~ C50 alkenyl group, a substituted or unsubstituted in the alkyl group, a substituted or unsubstituted C2 of ~ C50 unsubstituted C3 ~ C50 cycloalkyl group and substituted or unsubstituted C1-C20 alkoxy group.

The formula (1) may be any one of the following formulas (2-1) to (2-4).

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Chemical Formula 2-4]

In the above Chemical Formulas 2-1 to 2-4,

A2, R1, R2 and L are as defined in claim 1,

E, are each independently, carbon, oxygen, sulfur, C = O, C- (CH 3) 2, C- (CF 3) 2, or N-Ph,

X is each independently nitrogen or C-A2, the ring formed by X comprises an aromatic ring, the aromatic ring formed by X contains 0-2 X, and when X is nitrogen, adjacent X Is not nitrogen,

m, n, o, and p are each independently 0 or 1.

In one embodiment, in Formula 1 or 2-1 to 2-4, A1, R1 and R2 may each independently be selected from substituents represented by the following structures.

In one embodiment, in Formula 1 or 2-1 to 2-4, A2 may be selected from a substituent represented by the following structure.

In one embodiment, in Formula 1 or 2-1 to 2-4, L may be selected from substituents represented by the following structures.

In the above structure,

E, are each independently, carbon, oxygen, sulfur, C = O, C- (CH 3) 2, C- (CF 3) 2, or N-Ph,

X is each independently nitrogen or C-A2, the ring formed by X comprises an aromatic ring, the aromatic ring formed by X contains 0-2 X, and when X is nitrogen, adjacent X Is not nitrogen,

m, n, o and p are each independently 0 or 1,

In the above substituents, the linkage of the carbazole ring carbon or the carbazole nitrogen is carried out through *.

Specifically, the organic compound represented by the formula (1) may be represented by any one of the following formulas (3-1) to (3-21).

In the above Chemical Formulas 3-1 to 3-21,

A1, A2, R1, R2 and L are the same as defined in the above formula (1).

More specifically, the organic compound represented by the formula (1) may be represented by any one of the following formulas (4-1) to (4-108).

In Formulas 4-1 to 4-108,

A2, R1, R2 and L are as defined in claim 1,

E, are each independently, carbon, oxygen, sulfur, C = O, C- (CH 3) 2, C- (CF 3) 2, or N-Ph,

X is each independently nitrogen or C-A2, the ring formed by X comprises an aromatic ring, the aromatic ring formed by X contains 0-2 X, and when X is nitrogen, adjacent X Is not nitrogen,

m, n, o, and p are each independently 0 or 1.

In another embodiment, in the organic compound represented by Formula 1,

Wherein A1 is a halogen, CN, Si (CH) _3, CF _3, substituted or non-substituted substituted or unsubstituted of C1 ~ C10 unsubstituted alkyl group, a substituted or non-substituted of C3 ~ C10 unsubstituted cycloalkyl group, C1 ~ C10 unsubstituted alkoxy group Substituted or unsubstituted with at least one substituent selected from the group consisting of a phenyl group, a naphthyl group, and a biphenyl group;

,

, 또는

이거나; A phenyl group, a pyridyl group, a pyrimidyl group, a pyrazinyl group, a naphthalenyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazole group, a fluorenyl group, a triphenylenyl group,

,

, or

;

A halogen atom, a C 1 -C 10 alkoxy group, a phenyl group, a naphthyl group, a biphenyl group, a dibenzofuranyl group, and a dibenzo furanyl group such as a halogen, CN, Si (CH ₃ ) ₂ , CF ₃ , a C 1 to C 10 alkyl group, a C 3 to C 10 cycloalkyl group, Substituted or unsubstituted with at least one substituent selected from the group consisting of < RTI ID = 0.0 >

,

, 및

로 이루어진 군으로부터 선택된 적어도 하나로 치환 또는 비치환된:A phenyl group, a biphenyl group, a pyridyl group, a pyrimidyl group, a carbazole group, a fluorenyl group, a triphenylrenyl group, a dibenzofuranyl group,

,

, And

≪ / RTI > unsubstituted or substituted with at least one group selected from the group consisting of:

,

, 또는

이며;A phenyl group, a biphenyl group, a pyridyl group, a pyrimidyl group, a naphthalene group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazole group, a fluorenyl group,

,

, or

;

Wherein X is a nitrogen atom or a carbon atom, at least one X of the above structures is a nitrogen atom, and the nitrogen atoms are not adjacent to each other;

R1 and R2 are each, independently,

Hydrogen; heavy hydrogen; halogen; A nitro group; Acyl; A carboxyl group; A hydroxyl group; Amide group; Si (CH) ₃ ; methyl; Isopropyl; Butyl butyl; A C1 to C10 substituted or unsubstituted alkyl group; Phenyl; A pyridyl group; 9,9-dimethylfluorene; Biphenyl; Or a methyl group, an isopropyl group, a tert-butyl group, or a phenyl group having a C1-C10 substituted or unsubstituted alkyl group;

A2 is hydrogen; heavy hydrogen; halogen; A nitro group; Acyl; A carboxyl group; A hydroxyl group; Amide group; methyl; Isopropyl; Butyl butyl; A C1 to C10 substituted or unsubstituted alkyl group; Phenyl; A pyridyl group; 9,9-dimethylfluorene; Biphenyl; Or a methyl group, an isopropyl group, a tert-butyl group, or a phenyl group having a C1-C10 substituted or unsubstituted alkyl group;

L is a phenylene group substituted or unsubstituted with at least one member selected from the group consisting of a pyridyl group, a pyrimidyl group, a triazinyl group and a phenyl group; Divalent of 9,9-dimethylfluorene; Biphenylene group; The divalent of pyridine; Divalent of pyrimidine substituted or unsubstituted with phenyl group; Divalent triazines substituted or unsubstituted with phenyl groups; Or naphthalene.

For example, the organic compound may be any one of compounds 1 to 1159 (hereinafter, referred to as compounds 1 to 1159) described in Table 1 below.

The organic compound may be at least one selected from the group consisting of a light emitting layer material, a hole injecting layer material, a hole transporting layer material, an electron injecting layer material, an electron transporting layer material, an electron blocking layer material and a hole blocking layer material in the organic film material for an organic electroluminescence device Can be used.

The light emitting layer material may be a phosphorescent or fluorescent host, and a phosphorescent or fluorescent dopant material.

In another embodiment of the present invention, there is provided an ink composition comprising at least one of the organic luminescent compounds.

The ink composition may be a solution or suspension comprising a solvent and the solvent is selected from the group consisting of anisole, dimethyl anisole, xylene, o-xylene, m-xylene, p-xylene, toluene, But are not limited to, tetrahydrofuran, tetrahydrofuran, methylene benzoate, dioxane, terahydrofuran, methyltetrahydrofuran, tetrahydropyrane, tetralin, veratrol, chlorobenzene, N-methylpyrrolidone, And a combination thereof.

After the ink composition is applied, the organic thin film layer can be formed by removing the solvent to form a film.

The ink composition may further comprise a pigment or a dye.

The ink composition may further comprise a phosphorescent dopant or a fluorescent dopant.

In another embodiment of the present invention, in the organic electroluminescent device in which one or more organic thin film layers including at least a light emitting layer are sandwiched between an anode and a cathode, at least one of the organic thin film layers is formed of the organic compound Are contained singly or in combination of two or more kinds.

The organic electroluminescent compound contained in the organic thin film layer of the organic electroluminescent device is the compound represented by the general formula (1), and a detailed description thereof is as described above.

The organic thin film layer may be prepared according to a known manufacturing method of forming or laminating an organic thin film layer, or the organic thin film layer may be formed by a solution process using an ink composition containing at least one organic compound as described above Or the like.

The organic thin film layer may include a layer formed by including at least one selected from the group consisting of a light emitting layer material, a hole injection layer material, a hole transport layer material, an electron injection layer material, an electron transport layer material, . ≪ / RTI >

The light emitting layer material may be a phosphorescent or fluorescent host and a phosphorescent or fluorescent dopant material.

The organic electroluminescent device may have a structure in which an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, and a cathode are stacked in this order.

The light emitting layer may include a phosphorescent or fluorescent dopant including red, green, blue or white together with at least one or more organic light emitting compounds. For example, the phosphorescent dopant may be an organometallic compound including at least one element selected from the group consisting of Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb and Tm.

The hole transport layer, the hole injection layer, the hole blocking layer, the electron injection transport layer, the electron transport layer, the electron injection layer, and the electron blocking layer may be formed using known materials, One or more of them may be included.

Hereinafter, the organic electroluminescent device of the present invention will be described by way of example. However, the following examples do not limit the organic electroluminescent device of the present invention.

The organic electroluminescent device of the present invention may have a structure in which a cathode (a hole injection electrode), a hole injection layer (HIL) and / or a hole transport layer (HTL), a light emitting layer (EML) Preferably, an electron blocking layer (EBL) may be additionally provided between the anode and the light emitting layer, and an electron transport layer (ETL), an electron injection layer (EIL) or a hole blocking layer (HBL) have.

In the method of manufacturing an organic electroluminescent device according to the present invention, a cathode material is coated on the surface of a substrate by a conventional method to form a cathode. At this time, the substrate to be used is preferably a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness. As the material for the positive electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity may be used.

Next, a hole injection layer (HIL) material is formed on the surface of the anode by vacuum thermal deposition or spin coating using a conventional method. As the hole injection layer material, the organic compound of the present invention can be used. In addition, copper phthalocyanine (CuPc), 4,4 ', 4 "-tris (3-methylphenylamino) triphenylamine (m-MTDATA) , 4 ', 4 "-tris (3-methylphenylamino) phenoxybenzene (m-MTDAPB), and starburst type amines 4,4' TCTA), 4,4 ', 4 "-tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine (2-TNATA) or IDE406 available from Idemitsu have.

A hole transport layer (HTL) material is vacuum-deposited or spin coated on the surface of the hole injection layer by a conventional method to form a hole transport layer. In this case, the organic compound of the present invention can be used as the hole transport layer material, and besides, bis (N- (1-naphthyl-n-phenyl)) benzidine (? -NPD), N, (NPB) or N, N'-biphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl- - diamine (TPD).

A light emitting layer (EML) material is formed on the surface of the hole transport layer by vacuum thermal deposition or spin coating using a conventional method. In this case, the organic compound of the present invention can be used as a light emitting host material among the light emitting layer materials used. In addition, tris (8-hydroxyquinolinolato) aluminum (Alq3), Balq (8-hydroxyquinoline beryllium salt) , DPVBi (4,4'-bis (2,2-biphenylethenyl) -1,1'-biphenyl) series, Spiro material, Spiro- DPVBi (spiro- (Biphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazolyl) -phenol lithium salt), bis (biphenylvinyl) benzene, aluminum-quinoline metal Metal complexes of imidazole, thiazole and oxazole, and the like can be used.

The compound of the present invention can be used as a dopant which can be used together with a light emitting host among the light emitting layer materials, IDE102 and IDE105 available as a fluorescent dopant from Idemitsu and phosphorescent dopants such as tris (2- Iridium (III) (Ir (ppy) 3), iridium (III) bis [(4,6-difluorophenyl) pyridinate-N, C-2 '] picolinate (II) octaethylporphyrin (PtOEP), TBE002 (Cobion), and the like can be used.

An electron transport layer (ETL) material is formed on the surface of the light emitting layer by vacuum thermal deposition or spin coating using a conventional method. At this time, the electron transport layer material used may be an organic compound of the present invention, and tris (8-hydroxyquinolinolato) aluminum (Alq3) or the like may be used.

Alternatively, by further forming a hole blocking layer (HBL) between the light emitting layer and the electron transporting layer and using a phosphorescent dopant together with the light emitting layer, it is possible to prevent the phenomenon that the triplet excitons or holes are diffused into the electron transporting layer.

The hole blocking layer can be formed by vacuum thermal evaporation and spin coating using a hole blocking layer material by a conventional method, and the organic compound of the present invention can be used for the hole blocking layer material. In addition, (8-hydroxy Quinolinolato) lithium (Liq), bis (8-hydroxy-2-methylquinolinonato) -aluminum biphenoxide (BAlq), bathocuproine (BCP) and LiF .

An electron injection layer (EIL) material is formed on the surface of the electron transport layer by vacuum thermal deposition or spin coating using a conventional method. As the electron injection layer material used herein, the organic compound of the present invention may be used. In addition, materials such as LiF, Liq, Li2O, BaO, NaCl, and CsF may be used.

Finally, a negative electrode is formed on the surface of the electron injecting layer by vacuum thermal deposition using a conventional method.

At this time, as the negative electrode material to be used, lithium, aluminum, aluminum-lithium, calcium, magnesium, (Mg-Ag) or the like may be used. In the case of a top emission organic electroluminescent device, indium tin oxide (ITO) or indium zinc oxide (IZO) may be used to form a transparent cathode which can transmit light.

The organic electroluminescent device according to the present invention may be manufactured in the order as described above, that is, in the order of anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode, Electron injection layer / electron transporting layer / hole blocking layer / light emitting layer / hole transporting layer / hole injecting layer / anode.

In another embodiment of the present invention, there is provided an electronic device including the organic electroluminescent device.

The organic electroluminescent device can be applied to various applications. For example, the electronic device to which the organic electroluminescent device is applied may include an organic integrated circuit (O-IC), an organic field effect transistor (O-FET), an organic thin film transistor (O- LET), an organic solar cell (O-SC), an organic optical detector, an organic photoreceptor, an organic field-quench device (O-FQD), a luminescent electrochemical cell (LEC), an organic laser diode Device (OLED).

Hereinafter, a method of synthesizing the compounds of the present invention will be described with reference to representative examples. However, the method of synthesizing the compounds of the present invention is not limited to the following exemplified methods, and the compounds of the present invention can be produced by the methods exemplified below and by methods known in the art.

( Example )

Hereinafter, the reaction examples and the comparative examples are specifically exemplified, but the present invention is not limited to the following synthesis examples and examples. In the following reaction examples, the intermediate compounds are indicated by adding the serial number to the final product number. For example, Compound 1 is represented by the compound [1], and the intermediate compound of the above compound is represented by [1-1] or the like. In the present specification, the numbers of the compounds are represented by the numbers of the formulas shown in Table 1 above. For example, compounds designated 1 in Table 1 are designated Compound 1.

Example  1: Preparation of compound [31]

Compound [31] was synthesized according to Reaction Scheme 1 below.

[Reaction Scheme 1]

Preparation of compound [31]

To the reaction flask was added 6.24 g (18.78 mmol) of 3-bromo-9-phenyl-9H-carbazole, 5 g (15.65 mmol) of 3,6-diphenyl-9H- carbazole and 2.25 g (23.48 mmol) , And 150 ml of toluene, and the mixture is stirred at room temperature. 0.43 g (0.47 mmol) of tris (dibenzylideneacetone) dipalladium (0) and 0.16 mL (0.47 mmol) of triethylphosphine (50 wt%) were charged and refluxed under nitrogen stream for 12 hours. After completion of the reaction, the reaction mixture was slowly cooled to room temperature, and then the reaction solution was poured into a saturated aqueous solution of ammonium chloride and extracted with ethyl acetate. The organic layer was separated, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and purified by column chromatography to obtain 4.5 g (51% by weight) of the target compound [31] as a white solid.

^{1 H NMR (400 MHz, THF} ): δ8.61 (d, 2H), 8.48 (d, 1H), 8.26 (d, 1H), 7.82 ~ 7.80 (m, 4H), 7.73 ~ 7.45 (m, 17H) , 7.34-7.30 (m, 3H)

MS / FAB: 560 (M ^< ^{+ &} gt ^; ).

1 is a ¹ H-NMR spectrum of the obtained compound [31].

2 is a thermogravimetric analysis (TGA) graph of the obtained compound [31].

3 is a graph of differential scanning calorimetry (DSC) measurement for the compound [31] obtained above.

Example  2: Preparation of compound [42]

Compound [42] was synthesized according to Reaction Scheme 2 below.

[Reaction Scheme 2]

The reaction flask was charged with 7.48 g (18.78 mmol) of 9 - ([1,1'-biphenyl] -3-yl) -3-bromo-9H- carbazole, 5 g of 3,6-diphenyl-9H- 2.25 g (23.48 mmol) of sodium butoxide and 150 ml of toluene are placed in a 250 ml three-neck flask, and the mixture is stirred at room temperature. 0.43 g (0.47 mmol) of tris (dibenzylideneacetone) dipalladium (0) and 0.16 mL (0.47 mmol) of triethylphosphine (50 wt%) were charged and refluxed under nitrogen stream for 12 hours. After completion of the reaction, the reaction mixture was slowly cooled to room temperature, and then the reaction solution was poured into a saturated aqueous solution of ammonium chloride and extracted with ethyl acetate. The organic layer was separated, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and purified by column chromatography to obtain 4.8 g (48 wt%) of the target compound [42] as a white solid.

^{1 H NMR (400 MHz, THF} ): δ 8.62 (d, 2H), 8.50 (d, 1H), 8.27 (d, 1H), 8.10 (s, 1H), 7.83 ~ 7.80 (m, 4H), 7.75 ~ 7.42 (m, 20H), 7.34-7.28 (m, 3H)

MS / FAB: 636 (M ^< ^{+ &} gt ^; ).

Comparative Example  1: Synthesis of Comparative Compound [2000]

A compound [2000] represented by the following formula (2000) was synthesized according to the following Reaction Scheme 3.

(2000)

[Reaction Scheme 3]

To the reaction flask, 7.2 g (21.53 mmol) of 3-bromo-9-phenyl-9H-carbazole, 3 g (17.94 mmol) of 9H-carbazole, 2.59 g (26.91 mmol) of sodium butoxide and 50 ml of xylene, Lt; / RTI > 0.5 g (0.54 mmol) of tris (dibenzylideneacetone) dipalladium (0) and 0.26 mL (0.54 mmol) of triethylphosphine (50 wt%) were charged and refluxed under stirring in a nitrogen stream for 12 hours. After completion of the reaction, the reaction mixture was slowly cooled to room temperature, and then the reaction solution was poured into a saturated aqueous solution of ammonium chloride and extracted with ethyl acetate. The organic layer was separated, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and purified by column chromatography to obtain 5.8 g (80% by weight) of the target compound [2000] as a white solid.

^{1 H NMR (200 MHz, THF} ): δ 8.38 (d, 1H), 8.19 ~ 8.15 (m, 3H), 7.70 ~ 7.69 (m, 4H), 7.63 (d, 1H), 7.57 ~ 7.51 (m, 2H 2H), 7.35 (d, 4H), 7.29-7.25 (m, 1H), 7.24-7.20 (m, 2H)

MS / FAB: 408 (M ^< ^{+ &} gt ^; ).

4 is a ¹ H-NMR spectrum of the obtained compound [2000].

5 is a thermogravimetric analysis (TGA) graph for the obtained compound [2000].

FIG. 6 is a graph of differential scanning calorimetry (DSC) measurement for the obtained compound [2000].

Comparative Example  2: Synthesis of Comparative Compound [3000]

A compound [3000] represented by the following formula (3000) was synthesized according to the following Reaction Scheme 4.

≪ EMI ID =

[Reaction Scheme 4]

(25.1 mmol) of 9H-carbazole, 10 g (25.1 mmol) of 3- (4-bromophenyl) -9-phenyl-9H- carbazole, 3.6 g (37.65 mmol) of tetrabutoxysodium, And the mixture is stirred at room temperature. 0.34 g (0.38 mmol) of tris (dibenzylideneacetone) dipalladium (0) and 0.36 ml (0.75 mmol) of triethylphosphine (50 wt%) were charged and refluxed under stirring in a nitrogen stream for 12 hours. After completion of the reaction, the reaction mixture was slowly cooled to room temperature, and the resulting solid was filtered under reduced pressure. The resulting solid was refluxed in acetone and filtered under reduced pressure to obtain 5.7 g (47 wt%) of the target compound [3000].

^{1 H NMR (400 MHz, THF} ): δ 8.62 (s, 1H), 8.31 (d, 1H), 8.20 (d, 2H), 8.09 (d, 2H), 7.87 ~ 7.84 (m, 1H), 7.74 ~ (M, 4H), 7.47-7.40 (m, 4H), 7.34-7.32 (m, 3H)

MS / FAB: 484 (M ^< ^{+ &} gt ^; ).

7 is a ¹ H-NMR spectrum of the obtained compound [3000].

Comparative Example  3

A compound represented by the following formula (a) is used as a phosphorescent green host, and a compound c represented by the following formula (c) is used as a phosphorescent green dopant, and 2-TNATA (4,4 ' 2-yl) -N-phenylamino) -triphenylamine was used as a hole injection layer material and α-NPD (N, N'-di (naphthalene- (30 nm) / a-NPD (30 nm) / compound a + compound c (30 nm) / Alq ₃ (30 nm) was used as an organic electroluminescent device having the following structure: ITO / 2-TNATA ) / Liq (1 nm) / Al (100 nm).

The anode was prepared by cutting Corning's 15 Ω / cm ² (1000 Å) ITO glass substrate to a size of 25 mm × 25 mm × 0.7 mm, ultrasonically cleaning it in acetone isopropyl alcohol and pure water for 15 minutes each, UV ozone cleaning was used. 2-TNATA was vacuum deposited on the substrate to form a hole injection layer having a thickness of 80 nm. On top of the hole injection layer, α-NPD was vacuum deposited to form a hole transport layer having a thickness of 30 nm. A compound (a) represented by Formula (a) and a compound (c) represented by Formula (c) (10 wt%) were vacuum-deposited on the hole transport layer to form a 30 nm thick light emitting layer. Then, an Alq ₃ compound was vacuum deposited on the light emitting layer to a thickness of 30 nm to form an electron transporting layer. Liq 1 nm (electron injection layer) and Al 100 nm (cathode) were sequentially vacuum-deposited on the electron transport layer to prepare an organic light emitting device. This is referred to as Comparative Sample 1.

Comparative Example  4

(4,4 ', 4 "-tris (N-naphthalen-2-yl) phthalocyanine), using compound b shown below as a phosphorescent green host and compound c shown below as a phosphorescent green dopant. 2-yl) -N-phenylamino) -triphenylamine was used as a hole injection layer material and α-NPD (N, N'-di (naphthalene- (30 nm) /? -NPD (30 nm) / compound b + compound c (30 nm) / Alq ₃ (30 nm) was used as the organic light emitting device having the following structure: ITO / 2-TNATA ) / Liq (1 nm) / Al (100 nm).

The anode was prepared by cutting Corning's 15 Ω / cm ² (1000 Å) ITO glass substrate to a size of 25 mm × 25 mm × 0.7 mm, ultrasonically cleaning it in acetone isopropyl alcohol and pure water for 15 minutes each, UV ozone cleaning was used. 2-TNATA was vacuum deposited on the substrate to form a hole injection layer having a thickness of 80 nm. On top of the hole injection layer,? -NPD was vacuum deposited to form a hole transport layer having a thickness of 30 nm. A compound represented by the formula (b) and a compound represented by the formula (c) (doping ratio: 10 wt%) were vacuum-deposited on the hole transport layer to form a 30 nm thick light emitting layer. Then, an Alq ₃ compound was vacuum deposited on the light emitting layer to a thickness of 30 nm to form an electron transporting layer. Liq 1 nm (electron injection layer) and Al 100 nm (cathode) were sequentially vacuum-deposited on the electron transport layer to prepare an organic light emitting device. This is referred to as Comparative Sample 2.

(Formula a) < Formula b >

 <Formula c>

Example  3-4

In the same manner as in Comparative Example 3 except that phosphorescent green host chemistry a was used instead of phosphorescent green host a in Examples 3 and 4, and ITO / 2 (30 nm) / Alq ₃ (30 nm) / Liq (1 nm) / Al (100 nm) / TNTA (80 nm) / alpha -NPD (30 nm) / [Compound 31 or Compound 42 + Compound c ) Was fabricated. These are referred to as Sample 1 and Sample 2, respectively.

Comparative Example  5-6

In the same manner as in Comparative Example 3, except that phosphorescent green host chemistry a was used instead of phosphorescent green host compound a in Comparative Example 3, and compounds 2000 and 3000 synthesized in Comparative Example 1 and Comparative Example 2 were used as phosphorescent green hosts, ITO / 2 (30 nm) / Alq ₃ (30 nm) / Liq (1 nm) / Al (100 nm) / TNTA (80 nm) /? -NPD (30 nm) / [Compound 2000 or Compound 3000 + Compound c ) Was fabricated. These are referred to as Comparative Sample 3 and Comparative Sample 4, respectively.

Evaluation example  1: Evaluation of luminescence characteristics of Comparative Samples 1-4 and 1-2

The luminescence brightness, the luminescence efficiency and the luminescent peak were evaluated using Keithley source meter "2400" and KONIKA MINOLTA "CS-2000" for Comparative Samples 1-4 and 1-2, respectively, . The samples showed green emission peak values in the range of 513-515 nm.

Sample No. Phosphorescent green host
No. Phosphorescent green dopant
No. Voltage
OP. V Luminance
[cd / m ² ] efficiency
[cd / A] Emission peak
[nm] Comparative Sample 1 a c 5.12 4759 47.59 514 Comparative Sample 2 b c 4.89 4652 46.52 513 Comparative Sample 3 2000 c 4.3 4836 48.36 514 Comparative Sample 4 3000 c 4.2 4925 49.25 514 One 31 c 4.6 5257 52.57 513 2 42 c 4.5 5434 54.34 515

As shown in Table 1, Sample 1-2 exhibited improved luminescence characteristics compared to Comparative Sample 1-2.

In addition, Sample 1-2 exhibited improved luminescent properties compared to Sample 3-4 without phenyl in the carbazole ring.

Evaluation example  2: Evaluation of life characteristics of Comparative Samples 1-4 and 1-2

For Comparative Samples 1-4 and 1-2, the time at which the life span reached 97% on the basis of 3000 nits was measured using an LTS-1004AC life measuring device manufactured by ENC technology, and the results are shown in Table 3 Respectively.

Sample No. Phosphorescent green host
No. Phosphorescent green dopant
No. Life Time [Hours] Comparative Sample 1 a c 25 Comparative Sample 2 b c 29 Comparative Sample 3 2000 c 33 Comparative Sample 4 3000 c 36 One 31 c 68 2 42 c 52

As shown in Table 2, Sample 1-2 exhibited improved life characteristics compared to Comparative Sample 1-2.

In addition, Sample 1-2 exhibited improved lifetime characteristics, respectively, compared to Sample 3-4 in which no phenyl was present in the carbazole ring.

8 is a graph showing lifetime characteristics of the compounds [31] and [2000] synthesized in Example 1 and Comparative Example 1 according to the obtained results.

9 is a graph showing lifetime characteristics of the compounds [42] and [3000] synthesized in Example 2 and Comparative Example 2 according to the obtained results.

As shown in FIG. 8 and FIG. 9, the compound 2000 showed better lifetime characteristics than the compound 31, and the compound 3000 showed a better life characteristic than the compound 42.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.

Claims (20)

An organic compound represented by the following formula (1):
[Chemical Formula 1]

A1 is a substituted or unsubstituted C6-C60 aryl group,
A2 is hydrogen; heavy hydrogen; halogen; A nitro group; Acyl; A carboxyl group; A hydroxyl group; Or an amide group; A substituted or unsubstituted C1 to C50 alkyl group; A substituted or unsubstituted C1-C20 alkoxy group; Or a substituted or unsubstituted C6-C60 aryl group,
R1 and R2 are the same as each other and are hydrogen; heavy hydrogen; halogen; A nitro group; Acyl; A carboxyl group; A hydroxyl group; Or an amide group; A substituted or unsubstituted C1 to C50 alkyl group; A substituted or unsubstituted C1-C20 alkoxy group; Or a substituted or unsubstituted C6-C60 aryl group,
The substituted A1, A2, R1 and R2 are the first additional substituent is deuterium, halogen, CN, at least one hydrogen of the unsubstituted A1, A2, R1 and R2 being substituted at a first more substituents, CF ₃ , A substituted or unsubstituted C1 to C50 alkyl group, a substituted or unsubstituted C2 to C50 alkenyl group, a substituted or unsubstituted C3 to C50 cycloalkyl group, and a substituted or unsubstituted C1 to C20 alkoxy group At least one selected;
L is a single bond,
Wherein the substituted first additional substituent and the substituted second additional substituent are each such that at least one of the unsubstituted first additional substituent and the unsubstituted second additional substituent is substituted with a tertiary additional substituent, The carboxy addition substituent is selected from the group consisting of deuterium, halogen, CN, CF ₃ , a substituted or unsubstituted C1 to C50 alkyl group, a substituted or unsubstituted C2 to C50 alkenyl group, a substituted or unsubstituted C3 to C50 cycloalkyl group, And an unsubstituted C1-C20 alkoxy group. The method according to claim 1,
The organic compound represented by Formula 1 is any one of the following Formulas 2-1 to 2-4:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Chemical Formula 2-4]

In the above Chemical Formulas 2-1 to 2-4,
A2, R1, R2 and L are as defined in claim 1,
E and X are carbon,
m, n, o, and p are each independently 0 or 1. The method according to claim 1,
A1 is selected from a substituent represented by the following structure,

In the above formula
E and X are carbon,
m, n, o and p are each independently 0 or 1,
R1 and R2 are the same and are selected from substituents represented by the following structures,

In the above formula
E and X are carbon,
m, n, o and p are each independently 0 or 1,
A2 is selected from a substituent represented by the following structure,

And L is a single bond. delete delete The method according to claim 1,
A1 is halogen, CN, CF _3, substituted or unsubstituted of C1 ~ C10 unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group of C3 ~ C10, a substituted or unsubstituted of C1 ~ C10 unsubstituted alkoxy group, a phenyl group, a naphthyl group, and Substituted or unsubstituted with at least one substituent selected from the group consisting of &lt; RTI ID = 0.0 &gt;
A phenyl group;
Halogen, CN, CF _3, an alkyl group of C1 ~ C10, a substituted or unsubstituted with at least one substituent selected from cycloalkyl, alkoxy, phenyl, the group consisting of a naphthyl group and a biphenyl group of C1 ~ C10 of C3 ~ C10:
Phenyl group, biphenyl group,

And

&Lt; / RTI &gt; unsubstituted or substituted with at least one group selected from the group consisting of:
A phenyl group, a biphenyl group, a naphthalene group, a fluorenyl group, a triphenylrenyl group,

or

;
Wherein X is a carbon atom,
R1 and R2 are the same as each other,
Hydrogen; heavy hydrogen; halogen; A nitro group; Acyl; A carboxyl group; A hydroxyl group; Amide group; methyl; Isopropyl; Butyl butyl; Phenyl; 9,9-dimethylfluorene; Biphenyl; Or a methyl group, an isopropyl group, a tert-butyl group, or a phenyl group having a C1-C10 substituted or unsubstituted alkyl group;
A2 is hydrogen; heavy hydrogen; halogen; A nitro group; Acyl; A carboxyl group; A hydroxyl group; Amide group; methyl; Isopropyl; Butyl butyl; Phenyl; 9,9-dimethylfluorene; Biphenyl; Or a methyl group, an isopropyl group, a tert-butyl group, or a phenyl group having a C1-C10 substituted or unsubstituted alkyl group;
And L is a single bond. The method according to claim 1,
The organic compound is at least one of the following compounds 1-2, 4-18, 20-21, 25-26, 30-32, 34-48, 50-51, 55-56, 60-62, 64-78, 80-81, 85-86, 90-92, 94-108, 110-111, 115-116, 120-121, 123, 125, 127, 129, 131, 133, 136, 138, 140-142, 144, 152, 154-156, 160-167, 169-171, 175-180, 183, 185-186, 193, 195-196, 201, 208, 210-211, 214, 216-217, 219-221, 223- 225, 228-233, 235-236, 240, 976-977, 979-986, 990-992, 994-1001, 1005-1007, 1009-1016, 1020 and 1156-1159. compound.

The method according to any one of claims 1 to 3, 6, and 7,
Wherein the organic compound is at least one selected from the group consisting of a light emitting layer material, a hole injecting layer material, a hole transporting layer material, an electron injecting layer material, an electron transporting layer material, an electron blocking layer material and a hole blocking layer material in the organic film material for an organic electroluminescence device Characterized in that it is used for the purpose of
Organic compounds. 9. The method of claim 8,
Wherein the light emitting layer material is a phosphorescent or fluorescent host, and a phosphorescent or fluorescent dopant material. An ink composition comprising at least one organic compound according to any one of claims 1 to 3, 6 and 7. 11. The method of claim 10,
Wherein the ink composition is a solution or suspension further comprising a solvent
Ink composition. 11. The method of claim 10,
Characterized in that the ink composition further comprises a pigment or a dye
Ink composition. 11. The method of claim 10,
Characterized in that the ink composition further comprises a phosphorescent dopant or a fluorescent dopant
Ink composition. An organic electroluminescent device having an organic thin film layer sandwiched between a cathode and an anode and comprising one or more layers including at least a light emitting layer,
Wherein at least one of the organic thin film layers contains the organic compound according to claim 1 singly or in combination of two or more kinds. 15. The method of claim 14,
The organic thin film layer may include a layer formed by including at least one selected from the group consisting of a light emitting layer material, a hole injection layer material, a hole transport layer material, an electron injection layer material, an electron transport layer material, &Lt; RTI ID = 0.0 &gt;
Organic electroluminescent device. The method of claim 15, wherein
Wherein the light emitting layer material is a phosphorescent or fluorescent host and a phosphorescent or fluorescent dopant material
Organic electroluminescent device. The method of claim 14, wherein
An anode, a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, and a cathode stacked in this order
Organic electroluminescent device. 15. The method of claim 14,
Wherein the organic thin film layer is formed by coating an ink composition containing at least one organic compound by a solution process,
Organic electroluminescent device. An electronic device comprising the organic electroluminescent device according to claim 14. The method of claim 19, wherein
The electronic device includes: an organic integrated circuit (O-IC), an organic field effect transistor (O-FET), an organic thin film transistor (O- ), An organic optical detector, an organic photoreceptor, an organic field-quench device (O-FQD), a luminescent electrochemical cell (LEC), an organic laser diode (O-
Electronics.

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