KR101882221B1 - 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 the lifetime, efficiency, electrochemical stability, and thermal stability of an organic light emitting device, and an organic light emitting device in which the heterocyclic compound is contained in an organic compound layer.

Description

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

This application claims the benefit of Korean Patent Application Nos. 10-2015-0060829 and 10-2015-0060836 filed on April 29, 2015, the entire contents of which are incorporated herein by reference.

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,

R1 is hydrogen or deuterium, or is represented by - (L1) p- (Y1) q,

R2 is hydrogen, deuterium or naphthyl, or - (L2) r- (Y2) s,

L1 and L2 each independently represent a substituted or unsubstituted arylene group; And a substituted or unsubstituted ring or polycyclic heteroarylene group,

Y1 and Y2 are hydrogen; heavy hydrogen; A halogen group; -CN; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted heterocycloalkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; -SiRR'R "; -P (= O) RR 'and an amine group substituted or unsubstituted with an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

p is from 0 to 10, q is from 1 to 10,

r is from 0 to 10, s is from 1 to 10,

R3 to R10 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; -CN; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted heterocycloalkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; -SiRR'R "; -P (= O) RR 'and an amine group substituted or unsubstituted with an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, Are bonded to each other to form a substituted or unsubstituted monocyclic or polycyclic aliphatic or aromatic hydrocarbon ring,

R, R 'and R "are the same or different from each other and each independently represents hydrogen, deuterium, -CN, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, Gt; is an unsubstituted heteroaryl 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 includes an organic light emitting Device.

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 4 schematically show a laminated structure of an organic light emitting diode according to one embodiment of the present application.
5 shows the PL measurement graph of Compound 16 at 286 nm wavelength.
6 shows a PL measurement graph of Compound 16 at a wavelength of 328 nm.
FIG. 7 shows a PL measurement graph of the compound 16 at a wavelength of 404 nm.
Fig. 8 shows a PL measurement graph of Compound 209 at a wavelength of 239 nm.
FIG. 9 shows a graph of PL measurement at a wavelength of 292 nm of Compound 209.
FIG. 10 shows a graph of PL measurement at a wavelength of 338 nm of Compound 209.
Fig. 11 shows a PL measurement graph of Compound 209 at a wavelength of 408 nm.
12 shows a PL measurement graph of Compound 44 at a wavelength of 280 nm.
13 shows the PL measurement graph of Compound 44 at 414 nm wavelength.

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 (7).

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the above formulas 2 to 7,

The definitions of R1 to R10 are the same as those in the above formula (1)

R11 are each independently selected from the group consisting of hydrogen; heavy hydrogen; A halogen group; -CN; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted heterocycloalkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; -SiRR'R "; -P (= O) RR 'and an amine group substituted or unsubstituted with an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

R, R 'and R "are the same or different from each other and each independently represents hydrogen, deuterium, -CN, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, An unsubstituted heteroaryl group,

m is independently an integer of 0 to 7, and when m is 2 or more, two or more R < 11 > s are the same or different from each other,

n is independently an integer of 0 to 5, and when n is 2 or more, two or more R11 are the same or different from each other.

In one embodiment of the present application, when R2 in Formula 1 is hydrogen or deuterium, R1 may be represented by - (L1) p- (Y1) q.

In one embodiment of the present application, L1 in Formula 1 is a substituted or unsubstituted arylene group, Y is hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; And -P (= O) RR '.

In one embodiment of the present application, R11 in the above formulas (2) to (4) are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; And -P (= O) RR '.

In one embodiment of the present application, when R1 in the formula (1) is hydrogen or deuterium, R2 may be represented by a naphthyl group or - (L2) r- (Y2) s. The R2 may be an unsubstituted naphthyl group.

In one embodiment of the present application, L2 in Formula 1 is a substituted or unsubstituted arylene group, Y2 is a substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; And -P (= O) RR '.

In one embodiment of the present application, R11 in the formulas (5) to (7) each independently represents a substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; And -P (= O) RR '.

In one embodiment of the present application, p and r in Formula 1 may each independently be 0 to 10, and may be 1 to 10.

In one embodiment of the present application, R 3 to R 10 in Formula 1 may each independently be hydrogen or deuterium.

In the present application, the substituents of the formulas (1) to (7) 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,

A halogen atom, -CN, a C ₁ to C ₂₀ alkyl group, a C ₆ to C ₆₀ aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, and C ₂ to C ₆₀ substituted heteroaryl or unsubstituted alkyl group of C ₁ to C _60; an aryl group of deuterium, halogen, -CN, C ₁ to C ₂₀ alkyl group, C ₆ to C ₆₀ a, and C ₂ to a substituted or unsubstituted group of the C ₆₀ heteroaryl C ₃ to C ₆₀ cycloalkyl group; a deuterium, a halogen, -CN, an alkyl group of C ₁ to C _20, C ₆ to C ₆₀ aryl, and C ₂ to C ₆₀ substituted or unsubstituted group heteroaryl C ₆ to C ₆₀ aryl group; or an alkyl group of deuterium, halogen, -CN, C ₁ to C _20, C ₆ to C ₆₀ aryl, and C ₂ to C ₆₀ the heteroaryl group is a heteroaryl group, a substituted or unsubstituted C ₂ to C _60.

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.

이고, 상기 X3 및 X4는 치환 또는 비치환된 방향족 탄화수소 고리; 또는 치환 또는 비치환된 방향족 헤테로 고리일 수 있다.According to one embodiment of the present application, Y1 or Y2 in the formula (1)

X3 and X4 represent a substituted or unsubstituted aromatic hydrocarbon ring; Or a substituted or unsubstituted aromatic heterocycle.

는 하기 구조식들 중 어느 하나로 표시될 수 있으나, 이에만 한정되는 것은 아니다.remind

May be represented by any one of the following structural formulas, but it is not limited thereto.

In the above structural formulas, Z ₁ to Z ₃ are the same or different from each other and are each independently S or O,

Z < ₄ > to Z < ₉ > are the same or different from each other and each independently CR &

R 'and R "are the same or different from each other, and each independently hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

According to one embodiment of the present application, the above-mentioned formula (1) may be represented by any one of the following [Group 1] compounds, but the present invention is not limited thereto.

[Group 1]

According to one embodiment of the present application, the above-mentioned Formula 1 may be represented by any one of the following Group 2 compounds, but the present invention is not limited thereto.

[Group 2]

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, wherein 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.

Further, the organic light emitting element according to one embodiment of the present application includes two or more stacks each provided between an anode, a cathode, and an anode and a cathode, each of the two or more stacks includes a light emitting layer, And the charge generation layer comprises a heterocyclic compound represented by the above formula (1).

The organic light emitting device according to one embodiment of the present application includes a positive electrode, a first stack provided on the positive electrode and including a first light emitting layer, a charge generation layer provided on the first stack, A second stack including a second light emitting layer, and a cathode provided on the second stack. At this time, the charge generation layer may include a heterocyclic compound represented by the general formula (1). The first and second stacks may further include at least one of the hole injection layer, the hole transport layer, the hole blocking layer, the electron transport layer, and the electron injection layer described above independently.

The charge generation layer may be an N-type charge generation layer, and the charge generation layer may further include a dopant known in the art in addition to the heterocyclic compound represented by Formula (1).

An organic light emitting device having a two-stack tandem structure as an organic light emitting device according to one embodiment of the present application is schematically shown in Fig.

At this time, the first electron blocking layer, the first hole blocking layer, the second hole blocking layer, and the like described in FIG. 4 may be omitted in some cases.

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 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 device according to one embodiment of the present application may be a top 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.

< Example >

1. Preparation of compounds of group 1

< Manufacturing example  1> Preparation of compound 1

1) Preparation of Compound 1-1

After dissolving 2-fluoronitrobenzene (1 eq.) In 600 mL of DMF, indole (1 eq.) Was added, cesium carbonate (2.3 eq.) Was added thereto, and the mixture was stirred at room temperature for 18 hours . At the end of the reaction, cesium carbonate was filtered through a filter paper, and the filtrate was extracted with ethyl acetate and H ₂ O. After filtration, The extract was separated and purified by column chromatography to obtain Compound 1-1.

2) Preparation of Compound 1-2

Compound 1-1 (1 eq.) Was dissolved in ethanol: H ₂ O = 10: 7, then ammonium chloride (4 eq.) And iron (5 eq.) Were added in this order and heated for 3 hours . After the reaction was completed the solvent was concentrated and extracted with ethyl acetate (ethyl acetate) and H ₂ O. The extract was separated and purified by column chromatography to obtain a compound 1-2.

3) Preparation of compound 1

Compound 1-2 (1 eq.) Was dissolved in 500 mL of toluene. 1-naphthaldehyde (1.1 eq.) And p-toluene sulfonic acid (0.1 eq.) Were placed in a flask and heated for 24 hours. After the reaction was completed, dichloromethane and H ₂ O were extracted. The extract was separated and purified by column chromatography to obtain Compound 1.

< Manufacturing example  2> Preparation of compound 2

1) Preparation of Compound 1-1

Was prepared in the same manner as in the preparation of 1-1 in Production Example 1.

2) Preparation of Compound 1-2

Was prepared in the same manner as in the preparation of 1-2 in Production Example 1.

3) Preparation of Compound 2

Compound 1-2 (1 eq.) Was dissolved in 500 mL of toluene. 2-naphthaldehyde (1.1 eq.) And p-toluene sulfonic acid (0.1 eq.) Were placed in a flask and heated for 24 hours. After the reaction was completed, dichloromethane and H ₂ O were extracted. The extract was separated and purified by column chromatography to obtain Compound 2.

< Manufacturing example  3> Preparation of compounds having a substituent shown in the following Table 1

1) Preparation of Compound 1-1

Was prepared in the same manner as in the preparation of 1-1 in Production Example 1.

2) Preparation of Compound 1-2

Was prepared in the same manner as in the preparation of 1-2 in Production Example 1.

3) Preparation of compound 1-3

Compound 1-2 (1 eq.) Was dissolved in 500 mL of toluene. 4-bromobenzaldehyde (1.1 eq.) And p-toluene sulfonic acid (0.1 eq.) Were added thereto, followed by heating for 24 hours. After the reaction was completed, dichloromethane and H ₂ O were extracted. The extract was separated and purified by column chromatography to obtain Compound 1-3.

4) Preparation of compounds 1-4

Compound 1-3 (1 eq.) Was dissolved in 500 mL of 1.4-dioxane. 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2' -bis (1,3,2-dioxaborolane) (4,4,4' 4, 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane), 2 eq.), Potassium acetate (3 eq.), PdCl ₂ dppf) (0.05 eq.) were added and heated for 4 hours.

After the reaction was completed, dichloromethane and H ₂ O were extracted. The extract was separated and purified by column chromatography to obtain the compound 1-4.

5) Preparation of compound P3

The compound 1-4 (2.2 eq.) Was dissolved in a ratio of 1.4-dioxane: H ₂ O = 4: 1 and then Pd (PPh ₃ ) ₄ (0.05 eq.) And K ₂ CO ₃ 3eq.) And the compound S-1 (1 eq.) Were placed and heated for 4 hours. After the reaction was completed, dichloromethane and H ₂ O were extracted. The extract was separated and purified by column chromatography to obtain the desired compound P3 (yield: 42 to 75%).

[Table 1]

< Manufacturing example  4> Preparation of a compound having a substituent shown in the following Table 2

1) Preparation of Compound 1-1

Was prepared in the same manner as in the preparation of 1-1 in Production Example 1.

2) Preparation of Compound 1-2

Was prepared in the same manner as in the preparation of 1-2 in Production Example 1.

3) Preparation of compound 1-3

Compound 1-2 (1 eq.) Was dissolved in 500 mL of toluene. 3-bromobenzaldehyde (1.1 eq.) And p-toluene sulfonic acid (0.1 eq.) Were added thereto, followed by heating for 24 hours. After the reaction was completed, dichloromethane and H ₂ O were extracted. The extract was separated and purified by column chromatography to obtain Compound 1-3.

4) Preparation of compounds 1-4

Compound 1-3 (1 eq.) Was dissolved in 500 mL of 1.4-dioxane. 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2' -bis (1,3,2-dioxaborolane) (4,4,4' 4, 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane), 2 eq.), Potassium acetate (3 eq.), PdCl ₂ dppf) (0.05 eq.) were added and heated for 4 hours.

After the reaction was completed, dichloromethane and H ₂ O were extracted. The extract was separated and purified by column chromatography to obtain the compound 1-4.

5) Preparation of compound P4

The compound 1-4 (2.2 eq.) Was dissolved in a ratio of 1.4-dioxane: H ₂ O = 4: 1 and then Pd (PPh ₃ ) ₄ (0.05 eq.) And K ₂ CO ₃ 3eq.) And the compound S-1 (1 eq.) Were placed and heated for 4 hours. After the reaction was completed, dichloromethane and H ₂ O were extracted. The extract was separated and purified by column chromatography to obtain the desired compound P4 (yield: 43-78%).

[Table 2]

< Manufacturing example  5> Preparation of Compound 18

1) Preparation of Compound 1-1

Was prepared in the same manner as in the preparation of 1-1 in Production Example 1.

2) Preparation of Compound 1-2

Was prepared in the same manner as in the preparation of 1-2 in Production Example 1.

3) Preparation of compound 1-3

Was prepared in the same manner as in the preparation of 1-3 in Production Example 3.

4) Preparation of Compound 18

Compound 1-3 (1 eq.) Was dissolved in 50 mL of anhydrous THF and cooled to -78 ° C. n-butyllithium (2.5 in hexane, 1 eq.) was slowly added dropwise thereto, followed by stirring for 1 hour. To this solution was added dropwise chlorodiphenylphosphine (1 eq.) To the solution and stirred at room temperature for 12 hours. The reaction mixture was extracted with MC / H ₂ O and then distilled under reduced pressure. The reaction mixture was dissolved in MC (250 ml) and stirred with 20 ml of 30% aqueous H ₂ O ₂ solution at room temperature for 1 hour. After the reaction mixture was extracted with MC / H ₂ O, the concentrated mixture was separated by column chromatography (SiO ₂ , MC: Methanol = 25: 1) to obtain the target compound 18 in a yield of 22%.

< Manufacturing example  6> Preparation of Compound 98

1) Preparation of Compound 1-1

Was prepared in the same manner as in the preparation of 1-1 in Production Example 1.

2) Preparation of Compound 1-2

Was prepared in the same manner as in the preparation of 1-2 in Production Example 1.

3) Preparation of compound 1-3

Was prepared in the same manner as in the preparation of 1-3 in Production Example 4.

4) Preparation of compound 98

Compound 1-3 (1 eq.) Was dissolved in 50 mL of anhydrous THF and cooled to -78 ° C. n-butyllithium (2.5 in hexane, 1 eq.) was slowly added dropwise thereto, followed by stirring for 1 hour. To this solution was added dropwise chlorodiphenylphosphine (1 eq.) To the solution and stirred at room temperature for 12 hours. The reaction mixture was extracted with MC / H ₂ O and then distilled under reduced pressure. The reaction mixture was dissolved in MC (250 ml) and stirred with 20 ml of 30% aqueous H ₂ O ₂ solution at room temperature for 1 hour. After the reaction mixture was extracted with MC / H ₂ O, the concentrated mixture was separated by column chromatography (SiO ₂ , MC: Methanol = 25: 1) to obtain the target compound 98 in a yield of 22%.

< Manufacturing example  7> Preparation of Compound 146

1) Preparation of Compound A-1

(9,9-dimethyl-9H-fluoren-2-yl) boronic acid, 2 eq.) In a one neck round bottom flask (One neck rbf) ), 1-bromo-2-nitrobenzene (1 eq.), Pd (PPh ₃ ) ₄ (0.05 eq.) And K ₂ CO ₃ (2 eq.) In THF ) / H ₂ O (50 ml) was refluxed and stirred for 24 hours. After the water layer was removed, the organic layer was dried with MgSO ₄ . After concentration was purified by column chromatography _{(column chromatography, SiO 2, Hexane} : MC = 2: 1) to give a yellow solid separated as a compound A-1.

2) Preparation of Compound A-2

A mixture of o-DCB (300 ml) of A-1 (1 eq.) And PPh ₃ (3 eq.) In a one neck round bottom flask under nitrogen was refluxed for 18 hours. The o-DCB was distilled off under reduced pressure vacuum (vacuum distillation) after removal of the column chromatography _{(column chromatography, SiO 2, Hexane} : MC = 3: 1) to give a white solid to separate compound A-2.

3) Preparation of Compound 1-1

Was prepared in the same manner as in the preparation of 1-1 in Production Example 1.

4) Preparation of Compound 1-2

Was prepared in the same manner as in the preparation of 1-2 in Production Example 1.

5) Preparation of compound 1-3

Was prepared in the same manner as in the preparation of 1-3 in Production Example 3.

6) Preparation of compound P7

(1 eq.), A-2 (2 eq.), Cu (0.05 eq.) 18-crown-6-ether (18 crown-6-ether) were added to a one neck round bottom flask under nitrogen. 0.05 eq.) And o-DCB (80 ml) of K ₂ CO ₃ (2 eq.) Was refluxed for 12 hours. o-DCB was removed by vacuum distillation and then separated by column chromatography (SiO ₂ , Hexane: MC = 4: 1) to obtain the target compound P7 in a yield of 54%.

< Manufacturing example  8> Preparation of Compound 165

1) Preparation of compound B-1

Under a nitrogen atmosphere, 1,2-dichlorohexanone (1 eq.) And phenylhydrazine hydrochloride (2 eq.) In ethanol (ethanol, 1,000 ml) were added to a one neck round bottom flask ) Sulfuric acid (1 eq.) Was slowly added dropwise to the mixture, followed by stirring at 60 ° C for 4 hours. The solution cooled to room temperature was filtered to obtain a tan solid.

Trifluoroacetic acid (2 eq.) Was added to a mixture of the above solid (68.9 g, 0.25 mol) and acetic acid (700 ml) in a round neck flask (One neck rbf) and stirred at 100 ° C for 15 hours Respectively. The solution cooled to room temperature was washed with acetic acid and hexane and filtered to obtain an ivory solid B-1.

2) Preparation of compound B-2

(1 eq.), Iodobenzene (1.5 eq.), Cu (0.05 eq.), 18-crown-6-ether (18-crown-6-ether) were added to a two neck round bottom flask under nitrogen. -6-ether, 0.05 eq.) And K ₂ CO ₃ (2 eq.) In o-DCB (20 ml) was refluxed for 16 hours. The solution cooled to room temperature was extracted with MC / H ₂ O, concentrated, and separated by column chromatography (SiO ₂ , Hexane: Ethyl acetate = 10: 1) to obtain a white solid compound B-2.

3) Preparation of Compound 1-1

Was prepared in the same manner as in the preparation of 1-1 in Production Example 1.

4) Preparation of Compound 1-2

Was prepared in the same manner as in the preparation of 1-2 in Production Example 1.

5) Preparation of compound 1-3

Was prepared in the same manner as in the preparation of 1-3 in Production Example 3.

6) Preparation of compound 165

(1 eq.), A-2 (2 eq.), Cu (0.05 eq.) 18-crown-6-ether (18 crown-6-ether) were added to a one neck round bottom flask under nitrogen. 0.05 eq.) And o-DCB (80 ml) of K ₂ CO ₃ (2 eq.) Was refluxed for 12 hours. The o-DCB was distilled off under reduced pressure vacuum (vacuum distillation) to remove after column chromatography _{(column chromatography, SiO 2, Hexane} : MC = 4: 1) to separate, to thereby prepare a target compound 165 in 51% yield.

The compounds were prepared in the same manner as in the above Preparation Examples, and the results of confirmation of the synthesis were shown in the table. Table 3 shows measured values of FD-MS (field desorption mass spectrometry), and Table 4 shows NMR values.

[Table 3]

[Table 4]

5 shows the PL measurement graph of Compound 16 at 286 nm wavelength.

6 shows the PL measurement graph of Compound 16 at a wavelength of 328 nm.

FIG. 7 shows a PL measurement graph of the compound 16 at a wavelength of 404 nm.

Fig. 8 shows a PL measurement graph of Compound 209 at a wavelength of 239 nm.

FIG. 9 shows a graph of PL measurement at a wavelength of 292 nm of Compound 209.

FIG. 10 shows a graph of PL measurement at a wavelength of 338 nm of Compound 209.

Fig. 11 shows a PL measurement graph of Compound 209 at a wavelength of 408 nm.

12 shows a PL measurement graph of Compound 44 at a wavelength of 280 nm.

13 shows the PL measurement graph of Compound 44 at 414 nm wavelength.

2. Preparation of the compounds of group 2

< Manufacturing example  Preparation of Compounds Having Substituents in Table 5

1) Preparation of Compound 1-1

Pd (OAc) ₂ (0.01 eq.) And F ₃ CCO (0.1 eq.) Were added to 500 mL of PhCl after adding 4-bromophenyl hydrazine (1.2 eq. ₂ H (1 eq.), 10-phenanthroline (0.5 eq.) Were added and the mixture was heated for 5 hours. After the reaction was completed, the reaction mixture was extracted with ethyl acetate and H ₂ O. [ The extract was separated and purified by column chromatography to obtain Compound 1-1.

2) Preparation of Compound 1-2

2-Fluoronitrobenzene (1 eq.) Was dissolved in DMF (600 mL), and then 1-1 (1 eq.) Was added. Then, caesium carbonate (2.3 eq.) Was added thereto and stirred at room temperature for 18 hours . When the reaction was completed, caesium carbonate was filtered through a filter paper, and the filtrate was extracted with ethyl acetate and H ₂ O. After filtration, The extract was separated and purified by column chromatography to obtain a compound 1-2.

3) Preparation of compound 1-3

Compound 1-2 (1 eq.) Was dissolved in ethanol: H ₂ O = 10: 7, and then ammonium chloride (4 eq.) And iron (5 eq.) Were added in this order and heated for 3 hours . After the reaction was completed the solvent was concentrated and extracted with ethyl acetate (ethyl acetate) and H ₂ O. The extract was separated and purified by column chromatography to obtain a compound 1-3.

4) Preparation of compounds 1-4

Compound 1-3 (1 eq.) Was dissolved in 500 mL of toluene. Formaldehyde (1.1 eq.) And p-toluene sulfonic acid (0.1 eq.) Were added and heated for 24 hours. After the reaction was completed, dichloromethane and H ₂ O were extracted. After extraction, it was separated and purified by column chromatography to obtain Compound 1-4.

5) Preparation of compound 1-5

Compound 1-4 (1 eq.) Was dissolved in 500 mL of 1.4-dioxane. 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2' -bis (1,3,2-dioxaborolane) (4,4,4' 4, 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane), 2 eq.), Potassium acetate (3 eq.), PdCl ₂ dppf) (0.05 eq.) were added and heated for 4 hours.

After the reaction was completed, dichloromethane and H ₂ O were extracted. The extract was separated and purified by column chromatography to obtain a compound 1-5.

6) Preparation of compound P8

Compound 1-5 (2.2 eq.) Was dissolved in a ratio of 1.4-dioxane: H ₂ O = 4: 1 and then Pd (PPh ₃ ) ₄ (0.05 eq.) And K ₂ CO ₃ 3eq.) And the compound S-1 (1 eq.) Were placed and heated for 4 hours. After the reaction was completed, dichloromethane and H ₂ O were extracted. The extract was separated and purified by column chromatography to obtain the desired compound P8 (yield: 43-82%).

[Table 5]

< Manufacturing example  Preparation of Compounds Having Substituents in Table 6

1) Preparation of Compound 1-1

Pd (OAc) ₂ (0.01 eq.), F ₃ CCO (2-bromophenyl) hydrazine (1.2 eq.) Was dissolved in 500 mL of PhCl, ₂ H (1 eq.), 10-phenanthroline (0.5 eq.) Were added and the mixture was heated for 5 hours. After the reaction was completed, the reaction mixture was extracted with ethyl acetate and H ₂ O. [ The extract was separated and purified by column chromatography to obtain Compound 1-1.

2) Preparation of Compound 1-2

Was prepared in the same manner as in the preparation of 1-2 in Production Example 1.

3) Preparation of compound 1-3

Was prepared in the same manner as in the preparation of 1-3 in Preparation Example 1.

4) Preparation of compounds 1-4

Was prepared in the same manner as in the preparation of 1-4 in Production Example 1.

5) Preparation of compound 1-5

Was prepared in the same manner as in the preparation of 1-5 in Preparation Example 1.

6) Preparation of compound P9

Compound 1-5 (2.2 eq.) Was dissolved in a ratio of 1.4-dioxane: H ₂ O = 4: 1 and then Pd (PPh ₃ ) ₄ (0.05 eq.) And K ₂ CO ₃ 3eq.) And the compound S-1 (1 eq.) Were placed and heated for 4 hours. After the reaction was completed, dichloromethane and H ₂ O were extracted. The extract was separated and purified by column chromatography to obtain the target compound P9 (yield: 43-78%).

[Table 6]

< Manufacturing example  11> Preparation of Compound 237

1) Preparation of Compound 1-1

Was prepared in the same manner as in the preparation of 1-1 in Production Example 9.

2) Preparation of Compound 1-2

Was prepared in the same manner as in the preparation of 1-2 in Production Example 9.

3) Preparation of compound 1-3

Was prepared in the same manner as in the preparation of 1-3 in Production Example 9.

4) Preparation of compounds 1-4

Was prepared in the same manner as in the preparation of 1-4 in Production Example 9.

5) Preparation of compound 237

Compound 1-4 (1 eq.) Was dissolved in 50 mL of anhydrous THF and cooled to -78 ° C. n-butyllithium (2.5 in hexane, 1 eq.) was slowly added dropwise thereto, followed by stirring for 1 hour. To this solution was added dropwise chlorodiphenylphosphine (1 eq.) To the solution and stirred at room temperature for 12 hours. The reaction mixture was extracted with MC / H ₂ O and then distilled under reduced pressure. The reaction mixture was dissolved in MC (250 ml) and stirred with 20 ml of 30% aqueous H ₂ O ₂ solution at room temperature for 1 hour. After the reaction mixture was extracted with MC / H ₂ O, the concentrated mixture was separated by column chromatography (SiO ₂ , MC: Methanol = 25: 1) to obtain the target compound 237 (yield: 58%).

< Manufacturing example  12> Preparation of Compound 317

1) Preparation of Compound 1-1

Was prepared in the same manner as in the preparation of 1-1 in Production Example 10.

2) Preparation of Compound 1-2

Was prepared in the same manner as in the preparation of 1-2 in Production Example 10.

3) Preparation of compound 1-3

Was prepared in the same manner as in the preparation of 1-3 in Production Example 10.

4) Preparation of compounds 1-4

Was prepared in the same manner as in the preparation of 1-4 in Production Example 10.

5) Preparation of compound 317

Compound 1-4 (1 eq.) Was dissolved in 50 mL of anhydrous THF and cooled to -78 ° C. n-butyllithium (2.5 in hexane, 1 eq.) was slowly added dropwise thereto, followed by stirring for 1 hour. To this solution was added dropwise chlorodiphenylphosphine (1 eq.) To the solution and stirred at room temperature for 12 hours. The reaction mixture was extracted with MC / H ₂ O and then distilled under reduced pressure. The reaction mixture was dissolved in MC (250 ml) and stirred with 20 ml of 30% aqueous H ₂ O ₂ solution at room temperature for 1 hour. After the reaction mixture was extracted with MC / H ₂ O, the concentrated mixture was separated by column chromatography (SiO ₂ , MC: Methanol = 25: 1) to obtain the target compound 317 (yield: 62%).

The compounds were prepared in the same manner as in the above Preparation Examples, and the results of confirmation of the synthesis are shown in the following table. Table 7 shows measured values of FD-MS (field desorption mass spectrometry), and Table 8 shows NMR values.

[Table 7]

[Table 8]

< Experimental Example  1> Organic light emitting device using Group 1 compound

1) Fabrication of organic light emitting device

The glass substrate coated with ITO thin film with a thickness of 1500Å 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 for removing ITO work function and residual film in a vacuum state, and transferred to a thermal evaporation apparatus for organic vapor deposition.

An organic material was formed on the ITO transparent electrode (anode) in a two-stack WOLED (White Organic Light Device) structure. In the first stack, a hole transport layer was formed by thermally vacuum depositing TAPC to a thickness of 300 ANGSTROM. After forming a hole transporting layer, a light emitting layer was formed thereon by thermal vacuum deposition as follows. The light emitting layer was doped with TCp1 as a host with blue phosphorescent dopant FIrpic in an amount of 8% to deposit 300Å. The electron transporting layer was formed with a thickness of 400 angstroms by using TmPyPB, and then doped with Cs ₂ CO ₃ in a concentration of 20% to form a charge generation layer in the compound described in Table 7 to form 100 Å.

In the second stack, first, MoO ₃ was thermally vacuum-deposited to a thickness of 50 Å to form a hole injection layer. A hole transport layer as a common layer was formed by doping TAPC with 20% MoO ₃ to form 100 Å, followed by deposition of TAPC to 300 Å. On the phosphorescent layer, dopant Ir (ppy) _3, which is a green phosphorescent dopant, And then 600 Å was formed using TmPyPB as an electron transport layer. 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 required for OLED device fabrication were vacuum sublimated and refined under 10 ^-6 ~ 10 ^-8 torr for each material, and used for OLED fabrication.

2) Driving voltage and luminous efficiency of organic light emitting device

Electroluminescence (EL) characteristics of the organic light emitting diode fabricated as described above were measured with M7000 of Mitsubishi Electric Corporation, and the reference luminance was 3,500 cd / m &lt; 2 &gt; through a life measuring device (M6000) m &lt; ^{2 &} gt ;, T ₉₅ was measured. Table 9 shows the results of measuring the driving voltage, the luminous efficiency, the external quantum efficiency, and the color coordinates (CIE) of the white organic light emitting device manufactured according to the present invention.

[Table 9]

As can be seen from the results of Table 9, the organic light emitting device using the charge generating layer material of the two-stack white organic light emitting device of the present invention had a lower driving voltage and improved light emitting efficiency as compared with Comparative Example 1. [

The reason for this result is that the compound of the present invention used as an N type charge generation layer composed of an inventive skeleton having suitable length, strength and flat characteristics and a suitable hetero compound capable of binding with metal is an alkali metal or an alkaline earth metal It is presumed that a gap state is formed in the N-type charge generation layer and electrons generated from the P-type charge generation layer are easily injected into the electron transport layer through the gap state fished in the N-type charge generation layer . Therefore, the P-type charge generation layer can be electron-injected and electron-transferred to the N-type charge generation layer well, so that the driving voltage of the organic light emitting device is lowered and the efficiency and lifetime are improved.

< Experimental Example  2> Organic light emitting device using Group 1 compound

1) Fabrication of organic light emitting device

The transparent electrode ITO thin film obtained from the glass for OLED (manufactured by Samsung Corning) was ultrasonically cleaned for 5 minutes each using trichlorethylene, acetone, ethanol and distilled water sequentially, and stored in isopropanol before use.

Next, an ITO substrate was placed on a substrate folder of a vacuum deposition apparatus, and 4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenylamine 4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenyl amine: 2-TNATA).

Subsequently, the chamber was evacuated until the degree of vacuum reached 10 ^-6 torr. Then, a current was applied to the cell to evaporate 2-TNATA, thereby depositing a 600 Å thick hole injection layer on the ITO substrate.

N'-bis (? - naphthyl) -N, N'-diphenyl-4,4'-diamine (N, N'-diphenyl-4,4'-diamine: NPB) was added, and a current was applied to the cell to evaporate the hole transport layer to deposit a 300 Å thick hole transport layer.

After the hole injecting layer and the hole transporting layer were formed as described above, a blue light emitting material having the following structure was vapor-deposited as a light emitting layer thereon. Specifically, H1, a blue light emitting host material, was vacuum deposited on one cell in a vacuum deposition apparatus to a thickness of 200 Å, and D1, a blue light emitting dopant material, was vacuum deposited by 5% on the host material.

Next, a compound of the following structural formula E1 was deposited as an electron transporting layer to a thickness of 300 Å.

Lithium fluoride (LiF) was deposited as an electron injection layer to a thickness of 10 Å, and an Al cathode was formed to a thickness of 1000 Å to fabricate an OLED device.

On the other hand, all organic compounds required for OLED device fabrication were vacuum sublimated and refined at 10 ^-6 to 10 ^-8 torr for each material,

2) Driving voltage and luminous efficiency of organic light emitting device

Electroluminescence (EL) characteristics of the thus fabricated organic electroluminescent device were measured with a M7000 of Mitsubishi Electric Corporation, and the reference luminance was 700 cd / m &lt; 2 &gt; through a life measuring device (M6000) / m ² , T ₉₅ was measured. Table 10 shows the results of measuring the driving voltage, the luminous efficiency, the external quantum efficiency, and the color coordinates (CIE) of the organic electroluminescent device manufactured according to the present invention.

[Table 10]

As can be seen from the results of Table 10, the organic light emitting device using the electron transport layer material of the blue organic light emitting device of the present invention had a lower driving voltage, significantly improved luminous efficiency and lifetime,

The reason for this result is that, when the inventive compound having appropriate length, strength, and flat characteristics is used as an electron transport layer, it is possible to produce an excited state compound under the specific conditions of an electron and, in particular, It is considered that the excited heteroatomic skeleton site is moved to a stable state before the other excitation and the relatively stable compound can efficiently transfer the electrons without decomposition or destruction of the compound. For reference, we consider that those that are stable when excited are aryl or ashene compounds or polyhedral heterocycles. Therefore, it is considered that the compound of the present invention improves the improved electron-transporting property or the improved stability, which leads to excellent driving, efficiency and lifetime in all respects.

< Experimental Example  3> Organic light emitting device using Group 2 compound

1) Fabrication of organic light emitting device

The glass substrate coated with ITO thin film with a thickness of 1500Å 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 for removing ITO work function and residual film in a vacuum state, and transferred to a thermal evaporation apparatus for organic vapor deposition.

An organic material was formed on the ITO transparent electrode (anode) in a two-stack WOLED (White Organic Light Device) structure. In the first stack, a hole transport layer was formed by thermally vacuum depositing TAPC to a thickness of 300 ANGSTROM. After forming a hole transporting layer, a light emitting layer was formed thereon by thermal vacuum deposition as follows. The light emitting layer was doped with TCp1 as a host with blue phosphorescent dopant FIrpic in an amount of 8% to deposit 300Å. The electron transport layer was formed to a thickness of 400 ANGSTROM by using TmPyPB, and then doped with Cs ₂ CO ₃ by 20% in the compound shown in Table 5 below as a charge generation layer to form 100 Å.

In the second stack, first, MoO ₃ was thermally vacuum-deposited to a thickness of 50 Å to form a hole injection layer. A hole transport layer as a common layer was formed by doping TAPC with 20% MoO ₃ to form 100 Å, followed by deposition of TAPC to 300 Å. On the phosphorescent layer, dopant Ir (ppy) _3, which is a green phosphorescent dopant, And then 600 Å was formed using TmPyPB as an electron transport layer. 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 required for OLED device fabrication were vacuum sublimated and refined under 10 ^-6 ~ 10 ^-8 torr for each material, and used for OLED fabrication.

2) Driving voltage and luminous efficiency of organic light emitting device

Electroluminescence (EL) characteristics of the organic light emitting diode fabricated as described above were measured with M7000 of Mitsubishi Electric Corporation, and the reference luminance was 3,500 cd / m &lt; 2 &gt; through a life measuring device (M6000) m &lt; ^{2 &} gt ;, T ₉₅ was measured. Table 11 shows the results of measuring the driving voltage, the luminous efficiency, the external quantum efficiency, and the color coordinates (CIE) of the white organic light emitting device manufactured according to the present invention.

[Table 11]

As can be seen from the results of Table 11, the organic light emitting device using the charge generating layer material of the 2-stack white organic light emitting device of the present invention had a lower driving voltage and improved light emitting efficiency as compared with Comparative Example 3. The reason for this result is that the compound of the present invention used as an N type charge generation layer composed of an inventive skeleton having suitable length, strength and flat characteristics and a suitable hetero compound capable of binding with metal is an alkali metal or an alkaline earth metal It is presumed that a gap state is formed in the N type charge generation layer and electrons generated from the P type charge generation layer are easily injected into the electron transport layer through the gap state fished in the N type charge generation layer . Therefore, the P-type charge generation layer can be electron-injected and electron-transferred to the N-type charge generation layer well, so that the driving voltage of the organic light emitting device is lowered and the efficiency and lifetime are improved.

< Experimental Example  4> Organic light emitting device using group 2 compound

1) Fabrication of organic light emitting device

The transparent electrode ITO thin film obtained from the glass for OLED (manufactured by Samsung Corning) was ultrasonically cleaned for 5 minutes each using trichlorethylene, acetone, ethanol and distilled water sequentially, and stored in isopropanol before use.

Next, an ITO substrate was placed on a substrate folder of a vacuum deposition apparatus, and 4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenylamine 4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenyl amine: 2-TNATA).

Subsequently, the chamber was evacuated until the degree of vacuum reached 10 ^-6 torr. Then, a current was applied to the cell to evaporate 2-TNATA, thereby depositing a 600 Å thick hole injection layer on the ITO substrate.

N'-bis (? - naphthyl) -N, N'-diphenyl-4,4'-diamine (N, N'-diphenyl-4,4'-diamine: NPB) was added, and a current was applied to the cell to evaporate the hole transport layer to deposit a 300 Å thick hole transport layer.

After the hole injecting layer and the hole transporting layer were formed as described above, a blue light emitting material having the following structure was vapor-deposited as a light emitting layer thereon. Specifically, H1, a blue light emitting host material, was vacuum deposited on one cell in a vacuum deposition apparatus to a thickness of 200 Å, and D1, a blue light emitting dopant material, was vacuum deposited by 5% on the host material.

Next, a compound of the following structural formula E1 was deposited as an electron transporting layer to a thickness of 300 Å.

Lithium fluoride (LiF) was deposited as an electron injection layer to a thickness of 10 Å, and an Al cathode was formed to a thickness of 1000 Å to fabricate an OLED device.

On the other hand, all organic compounds required for OLED device fabrication were vacuum sublimated and refined at 10 ^-6 to 10 ^-8 torr for each material,

2) Driving voltage and luminous efficiency of organic light emitting device

Electroluminescence (EL) characteristics of the thus fabricated organic electroluminescent device were measured with a M7000 of Mitsubishi Electric Corporation, and the reference luminance was 700 cd / m &lt; 2 &gt; through a life measuring device (M6000) / m ² , T ₉₅ was measured. Table 12 shows the results of measuring driving voltage, luminous efficiency, external quantum efficiency, and color coordinates (CIE) of the organic light emitting device manufactured according to the present invention.

[Table 12]

As can be seen from the results of Table 12, the organic electroluminescent device using the electron transport layer material of the blue organic light emitting device of the present invention had a lower driving voltage, significantly improved luminous efficiency and lifetime,

The reason for this result is that, when the inventive compound having appropriate length, strength, and flat characteristics is used as an electron transport layer, it is possible to produce an excited state compound under the specific conditions of an electron and, in particular, It is considered that the excited heteroatomic skeleton site is moved to a stable state before the other excitation and the relatively stable compound can efficiently transfer the electrons without decomposition or destruction of the compound. For reference, we consider that those that are stable when excited are aryl or ashene compounds or polyhedral heterocycles. Therefore, it is considered that the compound of the present invention improves the improved electron-transporting property or the improved stability, which leads to excellent driving, efficiency and lifetime in all respects.

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

Claims (17)

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

In Formula 1,
R1 is hydrogen or is represented by - (L1) p- (Y1) q,
R2 is hydrogen or represented by - (L2) r- (Y2) s,
R2 is - (L2) r- (Y2) s when R1 is hydrogen, R2 is hydrogen when R1 is - (L1) p- (Y1) q,
L1 and L2 each independently represent a substituted or unsubstituted arylene group; And a substituted or unsubstituted ring or polycyclic heteroarylene group,
Y1 and Y2 represent a halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; And -P (= O) RR '
p is 1 to 10, q is 1 to 10,
r is 1 to 10, s is 1 to 10,
R3 to R10 are hydrogen,
R, R 'and R "are the same or different and are each independently a substituted or unsubstituted aryl group. delete delete The heterocyclic compound according to claim 1, wherein the formula 1 is represented by any one of the following formulas 2 to 7:
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the above formulas 2 to 7,
The definition of R3 to R10 is the same as defined in the above formula (1)
R1 and R2 are hydrogen,
R11 each independently represents a halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; And -P (= O) RR '
R, R 'and R "are the same or different and are each independently a substituted or unsubstituted aryl group,
m is independently an integer of 1 to 7, and when m is 2 or more, two or more R &lt; 11 &gt; s are the same as or different from each other,
n is independently an integer of 1 to 5, and when n is 2 or more, two or more R11 are the same or different from each other. [3] The compound according to claim 1, wherein L1 and L2 in Formula 1 are each independently a substituted or unsubstituted arylene group,
Y1 and Y2 each independently represent a substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; And -P (= O) RR &apos;.&lt; / RTI &gt; delete [Claim 4] The compound according to claim 4, wherein R11 in the formulas (2) to (7) each independently represents a substituted or unsubstituted aryl group; A substituted or unsubstituted heteroaryl group; And -P (= O) RR '. &lt; / RTI &gt; The compound according to claim 1, wherein Y1 or Y2 is

X3 and X4 represent a substituted or unsubstituted aromatic hydrocarbon ring; Or a substituted or unsubstituted aromatic heterocyclic ring. The method of claim 8,

Is a heterocyclic compound represented by any one of the following structural formulas:

In the above structural formulas, Z ₁ to Z ₃ are the same or different from each other and are each independently S or O,
Z &lt; ₄ &gt; to Z &lt; ₉ &gt; are the same or different from each other and each independently CR &
R 'and R "are the same or different from each other, and each independently hydrogen, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. 2. The heterocyclic compound according to claim 1, wherein the formula 1 is represented by any one of the following Group 1 compounds:
[Group 1]

The heterocyclic compound according to claim 1, wherein the compound represented by Formula 1 is represented by any one of the following Group 2 compounds:
[Group 2]

A cathode, and at least one organic layer provided between the anode and the cathode, wherein at least one of the organic layers comprises a heterocyclic compound according to any one of claims 1, 4, 5 and 7 to 11 Organic light emitting device. [12] The organic EL device according to claim 12, wherein the organic material layer comprises at least one of a hole blocking layer, an electron injection layer and an electron transporting layer, and at least one layer of the hole blocking layer, electron injection layer and electron transporting layer includes the heterocyclic compound Wherein the organic light-emitting device comprises: [Claim 13] The organic light emitting device of claim 12, wherein the organic layer includes a light emitting layer, and the light emitting layer comprises the heterocyclic compound. [12] The organic electroluminescent device according to claim 12, wherein the organic layer includes at least one of a hole injecting layer, a hole transporting layer, and a layer simultaneously injecting holes and transporting holes, wherein one of the layers includes the heterocyclic compound . 13. The organic light emitting device according to claim 12, wherein the organic layer includes a charge generation layer, and the charge generation layer includes the heterocyclic compound. 17. The organic electroluminescent device according to claim 16, wherein the organic light emitting device comprises: an anode; a first stack provided on the anode and including a first light emitting layer; a charge generating layer provided on the first stack; A second stack including a second light emitting layer, and a cathode provided on the second stack.

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