KR20180138269A - Heterocyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention relates to a heterocyclic compound represented by chemical formula 1 and an organic light emitting device comprising the same. The compound may satisfy an appropriate energy level, electrochemical stability, thermal stability, and the like, and has a chemical structure capable of performing various functions required in an organic light emitting device according to substituents.

Description

TECHNICAL FIELD [0001] The present invention relates to a heterocyclic compound and an organic light emitting device including the heterocyclic compound. [0002]

TECHNICAL FIELD The present invention relates to heterocyclic compounds and organic light emitting devices comprising 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.

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

[Chemical Formula 1]

In Formula 1,

Ar ₁ is a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Ar ₂ is a substituted or unsubstituted N-containing heterocyclic group; -SiRR'R "; or if -P (= O) RR ', and, N-containing heterocyclic group wherein Ar ₂ is a substituted or unsubstituted, and a combination of the L is a carbon-coupled by a bond between the carbon atoms,

L is a direct bond; Or a substituted or unsubstituted arylene group,

Y is NR _X , CR _Y R _Z , S or O,

R ₁ to R ₃ 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 a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group Or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted 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, An unsubstituted heteroaryl group,

R _X is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

R _Y and R _Z are the same or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group or may be bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,

a is an integer of 0 to 3,

b and d are integers of 0 to 2,

c is an integer of 0 to 4,

When a is 2 or more, two or more R < ₁ > s are the same or different from each other,

When b is 2 or more, two or more R < ₂ &_gt; s are the same or different from each other,

When c is 2 or more, two or more R ₃ are the same or different from each other.

According to an embodiment of the present application, there is provided a plasma display panel comprising: a first electrode; A second electrode facing the first electrode; And at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers comprises a heterocyclic compound represented by Formula 1, Lt; / RTI >

The compound described in this specification can be used as an organic layer material of an organic light emitting device. The compound can act as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, an electron injecting material, and the like in an organic light emitting device. In particular, the compound can be used as a light emitting layer material of an organic light emitting device.

Specifically, the compound can be used singly as a light emitting material, or as a host material or a dopant material in a light emitting layer. When the compound represented by Chemical Formula 1 is used in an organic material layer, 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 the thermal stability of the compound.

FIGS. 1 to 3 schematically show a stacked structure of organic light emitting devices according to one embodiment of the present application.

The present application will be described in detail below.

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 alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n Butyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and the like. But is not limited thereto.

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 this specification, the silyl group is a substituent including Si and a direct connection as the Si atom radical, R is represented by -SiR _{104 105} R _106, R ₁₀₄ to R ₁₀₆ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; An alkyl group; An alkenyl group; An alkoxy group; A cycloalkyl group; An aryl group; And a heterocyclic group. Specific examples of the silyl group include trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group and phenylsilyl group. But is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.

,

,

,

,

,

등이 될 수 있으나, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

,

,

,

And the like, but the present invention is not limited thereto.

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.

In the present specification, the phosphine oxide group specifically includes a diphenylphosphine oxide group, dinaphthylphosphine oxide, and the like, but is not limited thereto.

As used herein, the term " adjacent " means that the substituent is a substituent substituted on an atom directly connected to the substituted atom, a substituent stereostructically closest to the substituent, or another substituent substituted on the substituted atom . For example, two substituents substituted at the ortho position in the benzene ring and two substituents substituted at the same carbon in the aliphatic ring may be interpreted as " adjacent " groups to each other.

In one embodiment of the present application, the compound represented by Formula 1 is provided.

In one embodiment of the present application, Ar ₁ is a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

In another embodiment, Ar ₁ is a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In another embodiment, Ar ₁ is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted triphenylene group; Or a substituted or unsubstituted naphthyl group.

In another embodiment, Ar ₁ is a phenyl group substituted or unsubstituted with a cyano group or a triphenylsilyl group; Biphenyl group; Triphenylene group; Or a naphthyl group.

In another embodiment, Ar ₁ is a phenyl group substituted or unsubstituted with cyano group; A phenyl group substituted or unsubstituted with a silyl group substituted or unsubstituted with a phenyl group; Biphenyl group; Triphenylene group; Or a naphthyl group.

In one embodiment of the present application, L is a direct bond; Or a substituted or unsubstituted arylene group.

In another embodiment, L is a direct bond; Or a substituted or unsubstituted arylene group having 1 to 50 carbon atoms.

In another embodiment, L is a direct bond; Or a substituted or unsubstituted arylene group having 1 to 20 carbon atoms.

In another embodiment, L is a direct bond; Or an arylene group having 1 to 20 carbon atoms.

In another embodiment, L is a direct bond; Or a phenylene group.

In one embodiment of the present disclosure, R ₁ to R ₃ may be hydrogen.

In one embodiment of the present specification, Ar ₂ represents a substituted or unsubstituted N-containing heterocyclic group; -SiRR'R "; or -P (= O) RR ', and when Ar ₂ is a substituted or unsubstituted N-containing heterocyclic group, the bond with L may be bonded by a carbon- .

In another embodiment, Ar ₂ is a heterocyclic group containing 1 to 3 substituted or unsubstituted N; Or -P (= O) RR ', and when Ar ₂ is a heterocyclic group containing 1 to 3 substituted or unsubstituted N, the bond with L may be bonded by a carbon-carbon bond have.

In another embodiment, Ar ₂ is a monocyclic or polycyclic heterocyclic group containing 1 to 3 substituted or unsubstituted N; Or -P (= O) RR ', and when Ar ₂ is a monocyclic or polycyclic heterocyclic group containing 1 to 3 substituted or unsubstituted N, the bond with L may be a carbon-carbon bond Can be combined.

In another embodiment, Ar ₂ is a heterocyclic group containing 1 to 3 N substituted or unsubstituted with an alkyl group or a heteroaryl group; Or -P (= O) RR ', and when Ar ₂ is a heterocyclic group containing 1 to 3 N substituted or unsubstituted with an alkyl group or a heteroaryl group, the bond with L may be a carbon- . ≪ / RTI >

In another embodiment, Ar ₂ is a substituted or unsubstituted pyridine group; A substituted or unsubstituted pyrimidine group; A substituted or unsubstituted triazine group; A substituted or unsubstituted quinoline group; A substituted or unsubstituted isoquinoline group; A substituted or unsubstituted quinazoline group; A substituted or unsubstituted phenanthroline group; A substituted or unsubstituted benzimidazole group; A substituted or unsubstituted phosphine oxide group, and the bond with L may be bonded by a carbon-carbon bond.

In another embodiment, Ar ₂ is a pyridine group substituted or unsubstituted with an aryl group; A pyrimidine group substituted or unsubstituted with at least one substituent selected from an aryl group and a heteroaryl group substituted or unsubstituted with an aryl group or a cyano group; A triazine group substituted or unsubstituted with at least one substituent selected from the group consisting of an aryl group and a heteroaryl group substituted or unsubstituted with a cyano group; A quinolyl group substituted or unsubstituted with an aryl group; An isoquinoline group substituted or unsubstituted with an aryl group; A quinazoline group substituted or unsubstituted with an aryl group or a substituted or unsubstituted aryl group; A phenanthroline group substituted or unsubstituted with an aryl group; A benzimidazole group substituted or unsubstituted with an aryl group; A phosphine oxide group substituted or unsubstituted with an aryl group, and a bond with the L may be bonded by a carbon-carbon bond.

In another embodiment, Ar ₂ is a pyridine group substituted or unsubstituted with a phenyl group; A pyrimidine group substituted or unsubstituted with at least one substituent of a phenyl group or a dibenzothiophene substituted or unsubstituted with a phenyl group or a cyano group; A triazine group substituted or unsubstituted with at least one substituent of a phenyl group or a dibenzothiophene substituted or unsubstituted with a phenyl group or a cyano group; A quinolinyl group substituted or unsubstituted with a phenyl group; An isoquinoline group substituted or unsubstituted with a phenyl group; A quinazoline group substituted or unsubstituted with a phenyl group substituted or unsubstituted with a phenyl group; A phenanthroline group substituted or unsubstituted with a phenyl group; A benzimidazole group substituted or unsubstituted with a phenyl group; A phosphine oxide group substituted or unsubstituted with a phenyl group, and a bond with the L may be bonded by a carbon-carbon bond.

As with the compound of the present invention, when the heteroaryl group pulling electrons at the 4-position of fused-8-carbazole is substituted, long-life characteristics are exhibited. When the nitrogen portion of the carbazole is bonded to L or when the aryl group is substituted Since there are no substituents pulling electrons, lifetime characteristics are degraded due to imbalance between electrons and electrons.

In one embodiment of the present specification, Ar2 is a heterocyclic group containing at least one N having a substituted or unsubstituted sp2 bond; At least one of the heterocyclic groups containing at least one N having a substituted or unsubstituted sp2 bond has an adjacent C to sp2 bond, .

In another embodiment, Ar2 is a substituted or unsubstituted N-containing heterocyclic group; -SiRR'R "; or -P (= O) RR ', and when Ar2 is a substituted or unsubstituted N-containing heterocyclic group, it may contain a 6-membered ring as a ring-containing group containing N.

In another embodiment, Ar 2 is a substituted or unsubstituted monocyclic or bicyclic N-containing heterocyclic group; -SiRR'R "; or -P (= O) RR '.

In one embodiment of the present disclosure, R, R 'and R " are hydrogen; Or a substituted or unsubstituted aryl group.

In another embodiment R, R 'and R " are hydrogen; A substituted or unsubstituted aryl group having 1 to 60 carbon atoms.

In another embodiment R, R 'and R " are hydrogen; Or an aryl group having 1 to 60 carbon atoms.

In another embodiment, R, R 'and R " may be phenyl.

In one embodiment of the present application, Y can be NR _X, S, O, or CR _Y R _Z.

In one embodiment of the present application, R _X may be a substituted or unsubstituted aryl group having 1 to 60 carbon atoms.

In another embodiment, R _X may be an aryl group or an aryl group having 1 to 60 carbon atoms, which is substituted or unsubstituted with a cyano group.

In another embodiment, R _X is a phenyl group substituted or unsubstituted with cyano; Biphenyl group; Or a naphthyl group.

In one embodiment of the present application, R _Y And R _Z is a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group, or may be bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring.

In yet another embodiment, R _Y And R _Z is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or may be bonded to each other to form a substituted or unsubstituted aromatic hydrocarbon ring having 1 to 60 carbon atoms.

In yet another embodiment, R _Y And R _Z is an alkyl group having 1 to 10 carbon atoms; Or an aryl group having 6 to 30 carbon atoms, or may combine with each other to form an aromatic hydrocarbon ring having 1 to 30 carbon atoms.

In yet another embodiment, R _Y And R _Z is a methyl group; Or a phenyl group, or may be bonded to each other to form a fluorene group.

In one embodiment of the present application, d may be zero.

In one embodiment of the present application, d may be one.

In one embodiment of the present application, 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 6

The definitions of Ar ₁ , Ar ₂ , L, R ₁ , R ₂ , R ₃ , Y, a, b, c and d are the same as those of formula (1).

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

In addition, compounds having intrinsic properties of the substituent introduced by introducing various substituents into the structures of the above formulas (1) to (7) can be synthesized. For example, by introducing a substituent mainly used for a hole injecting layer material, a hole transporting material, a light emitting layer material, an electron transporting layer material, and a charge generating layer material used in manufacturing an organic light emitting device into the core structure, Can be synthesized.

In addition, by introducing various substituents into the structures of the formulas (1) to (7), it is possible to finely control the energy band gap and improve the properties at the interface between the organic materials, .

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

In addition, in one embodiment of the present application, the first electrode; A second electrode facing the first electrode; And at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers comprises a heterocyclic compound according to Formula 1, to provide.

The details of the heterocyclic compound represented by the formula (1) are the same as described above.

The organic light emitting device of the present invention can be manufactured by a conventional method and materials for manufacturing an organic light emitting device, except that the above-described heterocyclic compound is used to form one or more organic compound layers.

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.

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer as an organic material layer. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number of organic layers.

In the organic light emitting device of the present invention, the organic layer may include a light emitting layer, and the light emitting layer may include the heterocyclic compound.

In another organic light emitting device, the organic layer includes a light emitting layer, the light emitting layer includes a host material, and the host material may include the heterocyclic compound.

As another example, the organic material layer containing the heterocyclic compound may include a heterocyclic compound represented by Formula 1 as a host, and may be used together with an iridium dopant.

In the organic light emitting device of the present invention, the organic material layer may include an electron injection layer or an electron transport layer, and the electron transport layer or the electron injection layer may include the heterocyclic compound.

In another organic light emitting device, the organic layer may include an electron blocking layer or a hole blocking layer, and the electron blocking layer or the hole blocking layer may include the heterocyclic compound.

The organic light emitting device of the present invention includes a light emitting layer, a hole injecting layer, and a hole transporting layer. An electron injection layer, an electron transport layer, an electron blocking layer, and a hole blocking layer.

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

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

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

The organic material layer containing the above-described Chemical Formulas 1 to 7 may further include other materials as needed.

In the organic light emitting device according to one embodiment of the present application, materials other than the compounds represented by Chemical Formulas 1 to 7 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-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (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. At this time, two or more luminescent materials may be used as a separate source of vapor deposition, or may be premixed and deposited as a single source. 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.

When a host of a light emitting material is mixed and used, a host of the same series may be used in combination, or a host of another series may be mixed and used. For example, two or more kinds of materials of an n-type host material or a P-type host material may be selected and used as a host material of a light-emitting layer.

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.

< Manufacturing example >

< Manufacturing example  1> Preparation of Compound B1

1) Preparation of compound A1-1

2-iodo-9-phenyl-9H-carbazole (30.0 g, 81.25 mmol), 2-bromo-3-chloroaniline (16.7 g, 81.25 mmol), Tris (dibenzylideneacetone) dipalladium (11 g, 121.88 mmol) and 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl (5.1 g, 8.25 mmol) in toluene 450 mL), and the mixture was stirred at 120 ^° C for 19 hours. The reaction temperature was lowered to room temperature, washed with water and then extracted with Mc. 9-phenyl-9H-carbazol-4-amine (A1-1) was purified by silica-gel column chromatography using Mc / Hx = 1/10 eluting solvent to obtain N- (2-bromo-3-chlorophenyl ) &Lt; / RTI &gt; (25.1 g, 69%).

2) Preparation of Compound B1

(25.1 g, 56.1 mmol), Palladium (II) acetate (0.6 g, 2.80 mmol) and Tri-tert-butylphosphine (2.7 mL, 6.72 mmol) were added to a single round bottom flask A mixture of 1,8-diazabicyclo (5.4.0) undec-7-ene (8.4 mL, 56.1 mmol) was added to a solution of Xylene (250 mL) and stirred at 160 ^° C for 18 h. The solvent was removed from the reaction mixture and purified by silica-gel column using HX: EA = 10: 1 developing solvent to obtain 8-chloro-5-phenyl-5,12-dihydroindolo [3,2-a] carbazole (B1) g, 50%).

The intermediate compounds B2 to B14 were synthesized in the same manner as in the production example 1 except that A2 to A14 in the following Table a1 were used instead of A1 in the above-mentioned Production Example 1.

In the following Table a1, the definition of the compound indicates the number of the final embodiment of the present invention and the kind of the intermediate compound, which means that the compounds B2 to B14 were synthesized by the same method as the preparation of Preparation Example 1. For example, compounds 138 and 139-B1 in Table a1 below are representative of the synthesis up to intermediate compound B1 using compounds A1 and A1-1 to synthesize final embodiments 138 and 139 herein.

< Manufacturing example  2> Preparation of Compound D1

B1 (10 g, 27.3 mmol) , C1 (8.3 g, 40.9 mmol), Tris (dibenzylideneacetone) dipalladium (0) (1.3 g, 1.36 mmol) in one round bottom flask (One neck RBF), Sodium tert -butoxide ( 0.0 g, 0 mmol) and tri-tert-butylphosphine (1.6 mL, 3.3 mmol) in toluene (100 mL) and the mixture was stirred at 120 ^° C for 15 hours. After the reaction temperature was lowered to room temperature, the reaction mixture was rinsed with water and extracted with Mc. After removal of the extracted organic solvent, D1 (11.36 g, 94%) was obtained by silica-gel column purification (using Mc / Hx = 1/4).

The intermediate compounds D2 to D54 were synthesized in the same manner as in the preparation example 2 except that B2 to B14 in the following Table b1 were used instead of the above B1 in Production Example 2 and C2 to C6 in the following Table b1 were used in place of the C1, Respectively.

In the following Table b1, the definition of the compound indicates the number of the final embodiment of the present invention and the kind of the intermediate compound, which means that the intermediate compounds D2 to D54 were synthesized by the same method as the preparation of Preparation Example 2. For example, in Scheme b1 below, compounds 138-139-D1 illustrate the synthesis of intermediate compounds D1 using compounds B1 and C1 to synthesize final embodiments 138 and 139 herein.

< Manufacturing example  3> Preparation of compound G1

1) Preparation of compound E1

D1 (10g, 22.6 mmol), Bis (pinacolato) diboron (6.9 g, 27.1mmol), Pd (dba) 2 (1.3g, 2.3 mmol) in one of a round bottom flask (One neck RBF), 2- Dicyclohexylphosphino-2 , 4 '', 6'-triisopropylbiphenyl (2.2 g, 4.5 mmol) and potassium acetate (4.4 g, 45.2 mmol) were placed in 100 mL of 1,4-dioxane and stirred at 110 ^° C for 17 hours. The reaction temperature was lowered to room temperature, the inorganic material was washed with water, and the organic layer was extracted with Mc solvent. The organic solvent of the extracted organic layer was removed under reduced pressure and purified by silica-gel column to obtain E1 (9.1 g, 75%).

2) Preparation of compound G1

In one round bottom flask (One neck RBF) E1 (5.0 g, 9.4 mmol), F1 (3 g, 11.2mmol), Pd (PPh 3) 4 (0.5g, 0.5 mmol), Potassium carbonate (3.9 mL, 28.2 mmol) was dissolved in 50 mL / 10 mL of 1,4-dioxane / H ₂ O, and the mixture was stirred at 110 ^° C. for 17 hours. The reaction temperature was lowered to room temperature, the inorganic material was washed with water, and the organic layer was extracted with Mc solvent. The organic solvent of the extracted organic layer was removed under reduced pressure, and silica-gel column was purified to obtain G1 (4.3 g, 71%).

Except that D1 to D4, D6, D25 and D50 to D54 of the following Table c1 were used in place of D1 in Production Example 3 and F1 to F7 of the following Table c1 were used instead of F1: To thereby synthesize the target compounds G1 to G25.

In the following Table c1, the definition of the compound indicates the number of the final embodiment of the present invention and the kind of the target compound, which means that the target compounds G2 to G25 were synthesized by the same method as the preparation of Production Example 3. For example, in the following Table c1, compound 138-G1 represents the synthesis up to the target compound G1 using compounds D1, E1 and F1 to synthesize the final embodiment 138 herein.

<Examples>

1) Fabrication of organic light emitting device

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

On the ITO transparent electrode (anode), a hole injection layer 2-TNATA (4,4 ', 4 "-tris [2-naphthyl (phenyl) amino] triphenylamine) and a hole transport layer NPB (N, N'-Di (1-naphthyl) -N, N'-diphenyl- (1,1'-biphenyl) -4,4'-diamine.

The light emitting layer was then subjected to thermal vacuum deposition as follows. The light emitting layer is a compound represented by the following Table [A] as a host, Ir (ppy) ₃ Ir (ppy) ₃ was doped into the host by tris (2-phenylpyridine) iridium to a thickness of 400Å by doping 7% of the thickness of the light emitting layer. Then, BCP was deposited to a thickness of 60Å as a hole blocking layer, and Alq ₃ . Finally, lithium fluoride (LiF) was deposited to a thickness of 10 Å on the electron transport layer to form an electron injection layer. An aluminum (Al) cathode was deposited on the electron injection layer to a thickness of 1200 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 electroluminescent device

Electroluminescence (EL) characteristics of the organic electroluminescent device fabricated as described above were measured with a M7000 of Mitsubishi Electric Corporation, and the reference luminance was 6,000 through a life span measuring instrument (M6000) manufactured by Mac Science Co., When cd / m ² , T ₉₀ was measured. The characteristics of the organic electroluminescent device of the present invention are shown in Table 1 below.

compound Driving voltage
(V) efficiency
(cd / A) Color coordinates
(x, y) life span
(T ₉₀ ) Example 1 2 4.62 63.3 (0.297, 0.673) 124 Example 2 7 3.97 62.6 (0.287, 0.684) 179 Example 3 14 3,83 62.9 (0.288, 0.653) 188 Example 4 22 4.38 67.4 (0.278, 0.654) 147 Example 5 25 3.99 63.9 (0.293, 0.655) 176 Example 6 29 3.81 66.8 (0.284, 0.654) 164 Example 7 32 4.45 57.8 (0.284, 0.672) 144 Example 8 76 4.06 66.9 (0.297, 0.655) 177 Example 9 80 3.99 62.3 (0.310, 0.673) 182 Example 10 138 3.96 67.6 (0.286, 0.664) 178 Example 11 139 3.99 73.2 (0.289, 0.652) 169 Example 12 152 4.21 63.7 (0.262, 0.655) 153 Example 13 154 4.42 66.7 (0.266, 0.651) 152 Example 14 163 4.10 73.5 (0.275, 0.655) 165 Example 15 164 3.76 65.2 (0.281, 0.654) 156 Example 16 173 3.79 59.5 (0.289, 0.656) 181 Example 17 175 4.23 63.1 (0.286, 0.657) 172 Example 18 248 4.16 65.5 (0.277, 0.655) 164 Example 19 249 3.99 66.6 (0.292, 0.654) 161 Example 20 267 3.98 63.6 (0.290, 0.673) 179 Example 21 268 4.21 67.7 (0.280, 0.684) 172 Example 22 269 3.86 66.9 (0.280, 0.655) 167 Example 23 271 3.97 63.8 (0.284, 0.680) 172 Example 24 273 4.11 62.3 (0.286, 0.692) 168 Example 25 274 4.21 73.3 (0.293, 0.655) 172 Example 26 317 3.99 61.4 (0.286, 0.684) 161 Example 27 321 3.89 60.4 (0.281, 0.672) 178 Example 28 323 4.21 59.4 (0.285, 0.653) 162 Example 29 327 4.32 64.8 (0.292, 0.675) 169 Example 30 331 4.12 64.7 (0.289, 0.683) 172 Example 31 340 3.97 67.2 (0.277, 0.675) 168 Example 32 342 4.11 57.3 (0.279, 0.682) 165 Example 33 344 4.24 58.4 (0.302, 0.689) 168 Comparative Example 1 A 5.62 58.7 (0.298, 0.670) 47 Comparative Example 2 B 4.33 52.3 (0.297, 0.654) 84 Comparative Example 3 C 4.23 54.9 (0.287, 0.659) 38 Comparative Example 4 D 4.12 59,2 (0.274, 0.659) 40 Comparative Example 5 E 4.18 58.5 (0.286, 0.648) 43 Comparative Example 6 F 5.24 59.4 (0.295, 0.661) 38 Comparative Example 7 G 5.42 51.2 (0.298, 0.659) 32

[Compound A]

[Compound B]

[Compound C]

[Compound D]

[Compound E]

[Compound F]

[Compound G]

As a result of the evaluation of the device, it was confirmed that the efficiency of the heterocyclic compound of the present invention, in particular, the lifetime characteristics was excellent. Long-life characteristics are the most important factors for commercialization of materials.

Compared with the above-mentioned compounds B, C, D and E, the heterocyclic compound of the present invention is a bipolar compound, and the structure in which the heteroaryl group substituted for the electron withdrawing group is substituted for the fused-carbazole is the same. However, Is different. As long as the compound of the present invention is replaced with a heteroaryl group which attracts electrons to the 4-position of fused-8-carbazole, it is confirmed that the long-life characteristic is exhibited.

A heteroaryl group serving to stabilize electrons injected into the light emitting layer when the device is driven is substituted at positions 1 and 3 of fused-carbazole in the case of the comparative compounds B, C, D, and E. The position of 1,3 of fused-carbazole is similar to the ortho, para-oriented position of N which gives electrons and is directly affected by nitrogen atoms. The electrons injected with the heteroaryl group can not be stabilized due to the electron-donating nature of nitrogen, thereby deteriorating the lifetime characteristics.

In the case of the comparative compounds F and G, when carbazole and an aryl group are substituted at the 4-position of fused-carbazole, lifetime characteristics are degraded due to unbalance between electrons and electrons because there is no substituent to pull electrons.

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 (11)

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

In Formula 1,
Ar ₁ is a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
Ar ₂ is a substituted or unsubstituted N-containing heterocyclic group; -SiRR'R "; or if -P (= O) RR ', and, N-containing heterocyclic group wherein Ar ₂ is a substituted or unsubstituted, and a combination of the L is a carbon-coupled by a bond between the carbon atoms,
L is a direct bond; Or a substituted or unsubstituted arylene group,
Y is NR _X , CR _Y R _Z , S or O,
R ₁ to R ₃ 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 &quot;; -P (= O) RR ', and an amine group substituted or unsubstituted with a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group Or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted 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, An unsubstituted heteroaryl group,
R _X is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
R _Y and R _Z are the same or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group or may be bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,
a is an integer of 0 to 3,
b and d are integers of 0 to 2,
c is an integer of 0 to 4,
When a is 2 or more, two or more R &lt; ₁ &gt; s are the same or different from each other,
When b is 2 or more, two or more R &lt; ₂ &_gt; s are the same or different from each other,
When c is 2 or more, two or more R ₃ are the same or different from each other. _{2. The} compound according to claim 1, wherein Ar &lt; 2 &gt; is a substituted or unsubstituted pyridine group; A substituted or unsubstituted pyrimidine group; A substituted or unsubstituted triazine group; A substituted or unsubstituted quinoline group; A substituted or unsubstituted isoquinoline group; A substituted or unsubstituted quinazoline group; A substituted or unsubstituted phenanthroline group; A substituted or unsubstituted benzoimidazole group; And a substituted or unsubstituted arylphosphine oxide group. 2. The heterocyclic compound according to claim 1, wherein R ₁ to R ₃ are hydrogen. 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 6,
The definitions of Ar ₁ , Ar ₂ , L, R ₁ , R ₂ , R ₃ , Y, a, b, c and d are the same as those of formula (1). The heterocyclic compound according to claim 1, wherein the formula 1 is represented by any one of the following compounds:

A first electrode; A second electrode facing the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the heterocyclic compound according to any one of claims 1 to 5 Lt; / RTI &gt; 7. The organic light emitting device according to claim 6, wherein the organic layer includes a light emitting layer, and the light emitting layer comprises the heterocyclic compound. 7. The organic light emitting device according to claim 6, wherein the organic layer includes a light emitting layer, the light emitting layer includes a host material, and the host material includes the heterocyclic compound. 7. The organic light emitting device according to claim 6, wherein the organic material layer includes an electron injection layer or an electron transport layer, and the electron transport layer or the electron injection layer includes the heterocyclic compound. 7. The organic light emitting device according to claim 6, wherein the organic material layer includes an electron blocking layer or a hole blocking layer, and the electron blocking layer or the hole blocking layer includes the heterocyclic compound. 7. The organic electroluminescent device of claim 6, wherein the organic light emitting device comprises a light emitting layer, a hole injecting layer, and a hole transporting layer. An electron injection layer, an electron transport layer, an electron blocking layer, and a hole blocking layer.

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