KR101774643B1 - Heterocyclic compound including nitrogen and organic light emitting device using the same - Google Patents

Abstract

The present invention provides a nitrogen-containing heterocyclic compound and an organic light-emitting device comprising the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a nitrogen-containing heterocyclic compound and an organic light-emitting device using the same. BACKGROUND ART < RTI ID = 0.0 >

This application claims the benefit of the filing date of Korean Patent Application No. 10- 2014-0119113 filed with the Korean Intellectual Property Office on Sep. 5, 2014, the entire contents of which are incorporated herein by reference.

The present specification relates to nitrogen-containing heterocyclic compounds and organic electronic devices using the same.

The organic light emission phenomenon is one example in which current is converted into visible light by an internal process of a specific organic molecule. The principle of organic luminescence phenomenon is as follows.

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

As a material used in an organic light emitting device, a pure organic material or a complex in which an organic material and a metal form a complex is mostly used. Depending on the application, a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, . As the hole injecting material and the hole transporting material, an organic material having a p-type property, that is, an organic material that is easily oxidized and electrochemically stable at the time of oxidation is mainly used. On the other hand, as an electron injecting material or an electron transporting material, an organic material having an n-type property, that is, an organic material that is easily reduced and electrochemically stable when being reduced is mainly used. As the light emitting layer material, a material having both a p-type property and an n-type property, that is, a material having both a stable form in oxidation and in a reduced state is preferable, and a material having a high luminous efficiency for converting an exciton into light desirable.

Therefore, there is a need in the art to develop new organic materials.

Korean Patent Publication No. 2000-0051826

The present invention provides a nitrogen-containing heterocyclic compound and an organic light emitting device using the same.

In one embodiment of the present disclosure, there is provided a heterocyclic compound represented by the following Formula 1:

[Chemical Formula 1]

In formula (1)

X is O, S or NR,

R1 and R2 are each hydrogen or combine to form a ring,

R1 'and R2' are each hydrogen or combine to form a ring,

R3 and R4 are bonded to each other to form a ring, or R5 and R6 are bonded to each other to form a ring, the formed ring includes a substituent (R10) d,

a is an integer of 1 to 3,

b is an integer of 1 to 6,

c is an integer of 1 to 6,

d is an integer of 1 to 4,

when a is 2 or more, plural R < 7 > are the same as or different from each other,

When b is 2 or more, a plurality of R < 8 > s are the same as or different from each other,

When c is 2 or more, plural R < 9 > are the same or different from each other,

When d is 2 or more, a plurality of R < 10 > are the same as or different from each other,

R is hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

A group not forming a ring in R 3 to R 6 and R 7 to R 10 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted arylphosphine group; Or a substituted or unsubstituted heterocyclic group or may combine with adjacent groups to form a ring.

In one embodiment of the present disclosure, the first electrode; A second electrode facing the first electrode; And at least one organic compound layer including a light emitting layer provided between the first electrode and the second electrode, wherein at least one of the organic compound layers comprises the heterocyclic compound do.

Heterocyclic compounds according to embodiments of the present disclosure have suitable energy levels and are excellent in electrochemical stability and thermal stability. Thus, the organic light emitting device comprising the compound provides high efficiency and / or high driving stability.

1 to 5 are cross-sectional views illustrating the structure of an organic light emitting device according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail.

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

Examples of such substituents are described below, but are not limited thereto.

또는

는 다른 치환기에 연결되는 부위를 의미한다. In this specification

or

Quot; refers to a moiety that is connected to another substituent.

As used herein, the term " substituted or unsubstituted " A halogen group; A nitrile group; A nitro group; An amino group; Phosphine oxide groups; An alkoxy group; An aryloxy group; An alkyloxy group; Arylthioxy group; An alkylsulfoxy group; Arylsulfoxy group; Silyl group; Boron group; An alkyl group; A cycloalkyl group; An alkenyl group; An aryl group; Aralkyl groups; An aralkenyl group; An alkylaryl group; An alkylamine group; A heteroarylamine group; An arylamine group; Or a heterocyclic group, or that at least two of the substituents exemplified above are substituted or unsubstituted with a substituent to which they are linked. 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.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, But are not limited thereto.

In the present specification, the boron group specifically includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, and a phenylboron group.

In the present specification, the carbon number of the carbonyl group is not particularly limited, but is preferably 1 to 50 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the ester group may be substituted with a straight-chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms in the ester group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the amide group may be mono- or di-substituted by nitrogen of the amide group with hydrogen, a straight-chain, branched-chain or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec- N-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-hexyl, Cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl and the like.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and specifically includes cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, But are not limited to, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert- butylcyclohexyl, cycloheptyl, Do not.

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, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, N-hexyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, But is not limited thereto.

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.

In the present specification, the aryl group may be a monocyclic aryl group or a polycyclic aryl group, and includes a case where an alkyl group having 1 to 25 carbon atoms or an alkoxy group having 1 to 25 carbon atoms is substituted. In addition, an aryl group in the present specification may mean an aromatic ring.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 25 carbon atoms. Specific examples of the monocyclic aryl group include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, and a stilbenyl group.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. And preferably has 10 to 24 carbon atoms. Specific examples of the polycyclic aryl group include naphthyl, anthracenyl, phenanthryl, pyrenyl, perylenyl, klychenyl, fluorenyl, and the like.

In the present specification, a fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.

,

,

, 및

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

,

,

, And

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

In the present specification, the number of carbon atoms of the amine group 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, an anthracenylamine group, a 9- , A diphenylamine group, a phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine group, a triphenylamine group, and the like, but are not limited thereto.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group having at least two aryl groups may contain a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time.

Specific examples of the arylamine group include phenylamine, naphthylamine, biphenylamine, anthracenylamine, 3-methylphenylamine, 4-methyl-naphthylamine, 2-methyl- But are not limited to, cenylamine, diphenylamine, phenylnaphthylamine, ditolylamine, phenyltolylamine, carbazole and triphenylamine groups.

In the present specification, the heterocyclic group is a heterocyclic group containing at least one of O, N and S as a heteroatom. The number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furane group, a furyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, A pyridazinyl group, a pyrazinopyrazinyl group, an isoquinoline group, a pyrazinyl group, a pyrazinyl group, a pyrazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, , An indole group, a carbazole group, a benzoxazole group, a benzoimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline, An isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.

In the present specification, the aryl group in the aryloxy group, arylthioxy group, arylsulfoxy group and aralkylamine group is the same as the aforementioned aryl group. Specific examples of the aryloxy group include phenoxy, p-tolyloxy, m-tolyloxy, 3,5-dimethyl-phenoxy, 2,4,6-trimethylphenoxy, Naphthyloxy, 4-methyl-1-naphthyloxy, 5-methyl-2-naphthyloxy, 1-anthryloxy, 2-anthryl Phenanthryloxy, 9-phenanthryloxy and the like. Examples of the arylthioxy group include phenylthio group, 2-methylphenylthio group, 4-tert-butylphenyl And the like. Examples of the aryl sulfoxy group include a benzene sulfoxy group and a p-toluenesulfoxy group, but the present invention is not limited thereto.

In the present specification, the heteroaryl group in the heteroarylamine group can be selected from the examples of the above-mentioned heterocyclic group.

In the present specification, the alkyl group in the alkylthio group and the alkylsulfoxy group is the same as the alkyl group described above. Specific examples of the alkyloxy group include a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group and an octylthio group. Examples of the alkylsulfoxy group include a mesyl group, an ethylsulfoxy group, a propylsulfoxy group, But are not limited thereto.

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.

In the present specification, the term " forming a ring by bonding to adjacent groups " means forming a ring by bonding to adjacent groups to form a substituted or unsubstituted aliphatic hydrocarbon ring; A substituted or unsubstituted aromatic hydrocarbon ring; A substituted or unsubstituted aliphatic heterocycle; Or a substituted or unsubstituted aromatic heterocycle.

As used herein, the term "adjacent group" means a group in which the substituent is substituted with an atom directly bonded to the atom to which the substituted atom is substituted, a substituent having the closest stereostructure to the substituent, It can mean. 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 ".

In the present specification, an aliphatic hydrocarbon ring means a ring which is a non-aromatic ring and consists only of carbon and hydrogen atoms.

In the present specification, examples of the aromatic hydrocarbon ring include a phenyl group, a naphthyl group, and an anthracenyl group, but are not limited thereto.

As used herein, an aliphatic heterocycle refers to an aliphatic ring containing one or more of the N, O, or S atoms as heteroatoms.

As used herein, an aromatic heterocycle refers to an aromatic ring containing one or more of N, O, or S atoms as heteroatoms.

In the present specification, the aliphatic ring, aromatic ring, aliphatic heterocyclic ring and aromatic heterocyclic ring may be monocyclic or polycyclic.

In one embodiment of the present invention, the heterocyclic compound represented by Formula 1 is represented by Formula 2 or Formula 3 below.

(2)

(3)

In the general formulas (2) and (3)

X, a to d, R, R1 ', R2' and R1 to R10 are the same as defined in the above formula (1).

In one embodiment of the present disclosure, c is one.

In one embodiment of the present invention, the heterocyclic compound represented by Formula 1 is represented by Formula 4 or 5 below.

[Chemical Formula 4]

[Chemical Formula 5]

In the general formulas (4) and (5)

X, a, b, d, R, R1 ', R2' and R1 to R10 are the same as defined in the above formula (1).

In one embodiment of the present invention, the heterocyclic compound represented by the formula (1) is represented by the following formula (6) or (7).

[Chemical Formula 6]

(7)

In the above formulas (6) and (7)

X, a, b, d, R, R1 ', R2' and R1 to R10 are the same as defined in the above formula (1).

In one embodiment of the present invention, the heterocyclic compound represented by the formula (1) is represented by any one of the following formulas (8) to (11).

[Chemical Formula 8]

 [Chemical Formula 9]

[Chemical formula 10]

(11)

In the above Chemical Formulas 8 to 11,

a to d, X, R 1 ', R 2' and R 1 to R 10 are as defined in the above formula (1).

In one embodiment of the present disclosure, X is S or O.

In one embodiment of the present disclosure, X is S.

In one embodiment of the present disclosure, X is O.

In another embodiment, X is NR.

In one embodiment of the present invention, the heterocyclic compound represented by Formula 1 is represented by any one of the following Formulas 1-a-1 to 1-a-24.

In the above structural formulas, R is the same as defined in formula (1).

In one embodiment of the present invention, the heterocyclic compound represented by Formula 1 is represented by any one of the following Formulas 1-b-1 to 1-b-48.

In the above structural formulas, R and R9 are the same as defined in formula (1).

In one embodiment of the present disclosure, R1 and R2 are each hydrogen.

In one embodiment of the present specification, R 1 and R 2 combine with each other to form a 5-membered condensed ring.

In one embodiment of the present disclosure, R 1 and R 2 combine with each other to form a 5-membered fused ring, and R 1 ', R 2', and R 7 to R 10 are both hydrogen.

In one embodiment of the present disclosure, R1 'and R2' are each hydrogen.

In one embodiment of the present specification, R1 'and R2' are bonded to each other to form a 5-membered condensed ring.

In another embodiment, R1 'and R2 are bonded to each other to form a 5-membered fused ring, and R1, R2, and R7 to R10 are both hydrogen.

In one embodiment of the present disclosure, R 3 is hydrogen.

In one embodiment of the present disclosure, R4 is hydrogen.

In one embodiment of the present disclosure, R5 is hydrogen.

In one embodiment of the present disclosure, R6 is hydrogen.

In one embodiment of the present disclosure, R7 is hydrogen.

In one embodiment of the present disclosure, R8 is hydrogen.

In one embodiment of the present disclosure, R9 is hydrogen.

In one embodiment of the present disclosure, R10 is hydrogen.

In one embodiment of the present disclosure, R9 is selected from the group consisting of hydrogen; A nitrile group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heterocyclic group; A substituted or unsubstituted arylamine group; Or a substituted or unsubstituted arylphosphine group.

In one embodiment of the present disclosure, R9 is selected from the group consisting of hydrogen; A nitrile group; A substituted or unsubstituted C6 to C30 aryl; A substituted or unsubstituted heterocyclic group containing at least one N atom; A substituted or unsubstituted arylamine group; Or a substituted or unsubstituted arylphosphine group.

In another embodiment, R9 is selected from the group consisting of hydrogen; A nitrile group; A substituted or unsubstituted phenyl group; A substituted or unsubstituted naphthalene group; A substituted or unsubstituted phenanthrene group; A substituted or unsubstituted triphenylene group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; A substituted or unsubstituted pyridine group; A substituted or unsubstituted pyrimidine group; A substituted or unsubstituted triazine group; A substituted or unsubstituted benzimidazole group; A substituted or unsubstituted 1,10-phenanthroline group; A substituted or unsubstituted arylphosphine group; Or a substituted or unsubstituted arylamine group.

In one embodiment of the present disclosure, R9 is selected from the group consisting of hydrogen; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted arylphosphine group; And any one of the following substituents.

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

In the substituent,

e is an integer of 1 to 4,

f, g, i and 1 are each an integer of 1 to 7,

h is an integer of 1 to 4,

j and k are each an integer of 1 to 9,

L1 is a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,

R11 to R27 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted imine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heterocyclic group, or two or more adjacent groups may be bonded to each other to form a ring.

In one embodiment of the present disclosure, L1 is a direct bond; A substituted or unsubstituted phenylene group; Or a substituted or unsubstituted divalent carbazole group.

In one embodiment of the present specification, L < 1 > is a direct bond or a substituted or unsubstituted phenylene group.

In one embodiment of the present disclosure, L1 is a direct bond.

In one embodiment of the present specification, L 1 is a substituted or unsubstituted arylene group.

In one embodiment of the present specification, L 1 is a substituted or unsubstituted phenylene group.

이다. In one embodiment of the present disclosure, L1 is a phenylene group, and specifically

to be.

이다. In one embodiment of the present disclosure, L1 is a phenylene group, and specifically

to be.

In one embodiment of the present specification, L 1 is a substituted or unsubstituted divalent aromatic heterocyclic group containing at least one of N, O and S atoms.

In one embodiment of the present specification, L < 1 > is a substituted or unsubstituted divalent carbazole group.

이다. In one embodiment of the present specification, L1 is a divalent carbazole group, and specifically

to be.

이다. In one embodiment of the present specification, L1 is a divalent carbazole group, and specifically

to be.

In one embodiment of the present specification, R9 is a substituted or unsubstituted arylamine group.

In one embodiment of the present specification, R9 is an arylamine group substituted or unsubstituted with a substituted or unsubstituted C6-C30 aryl group.

In one embodiment of the present disclosure, R9 is an arylamine group substituted with a phenyl group, a biphenyl group, or a terphenyl group.

In one embodiment of the present specification, R9 is a substituted or unsubstituted arylphosphine group.

In one embodiment of the present specification, R9 is an arylphosphine group substituted or unsubstituted with a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In one embodiment of the present specification, R9 is an arylphosphine group substituted or unsubstituted with a phenyl group or a naphthalene group.

In one embodiment of the present specification, R9 is a substituted or unsubstituted fluorenyl group.

In one embodiment of the present specification, R9 is a fluorenyl group substituted or unsubstituted with a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

In another embodiment, R9 is a fluorenyl group substituted or unsubstituted with a methyl group.

이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

to be.

이고, R11 및 R12은 서로 동일하거나 상이하고, 각각 독립적으로 치환 또는 비치환된 아릴기이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

, R11 and R12 are the same or different and are each independently a substituted or unsubstituted aryl group.

이고, R11 및 R12은 페닐기이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

And R11 and R12 are phenyl groups.

이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

to be.

이고, R11 및 R12은 서로 동일하거나 상이하고, 각각 독립적으로 치환 또는 비치환된 아릴기이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

, R11 and R12 are the same or different and are each independently a substituted or unsubstituted aryl group.

이고, R11및 R12은 서로 동일하거나 상이하고, 각각 독립적으로 치환 또는 비치환된 아릴기이며, R13은 수소이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

, R11 and R12 are the same or different and are each independently a substituted or unsubstituted aryl group, and R13 is hydrogen.

이고, R11 및 R12은 페닐기이며, R13은 수소이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

, R11 and R12 are phenyl groups, and R13 is hydrogen.

이다.In another embodiment, R9 is < RTI ID = 0.0 >

to be.

이며, R11 및 R13은 서로 동일하거나 상이하고, 각각 독립적으로 치환 또는 비치환된 아릴기이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

, R11 and R13 are the same or different and are each independently a substituted or unsubstituted aryl group.

이며, R11 및 R13은 서로 동일하거나 상이하고, 각각 독립적으로 치환 또는 비치환된 아릴기이며, R12는 수소이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

, R11 and R13 are the same or different and are each independently a substituted or unsubstituted aryl group, and R12 is hydrogen.

이며, R11 및 R13은 페닐기이며, R12는 수소이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

, R11 and R13 are phenyl groups, and R12 is hydrogen.

이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

to be.

이고, R11 및 R13은 서로 동일하거나 상이하고, 각각 독립적으로 치환 또는 비치환된 아릴기이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

, R11 and R13 are the same or different and are each independently a substituted or unsubstituted aryl group.

이고, R11 및 R13는 서로 동일하거나 상이하고, 각각 독립적으로 치환 또는 비치환된 아릴기이고, R12 및 R14는 수소이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

, R11 and R13 are the same or different and are each independently a substituted or unsubstituted aryl group, and R12 and R14 are hydrogen.

이다.In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

to be.

이고, R17는 치환 또는 비치환된 알킬기이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

And R17 is a substituted or unsubstituted alkyl group.

이고, R17는 치환 또는 비치환된 알킬기이고, R18은 수소이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

, R17 is a substituted or unsubstituted alkyl group, and R18 is hydrogen.

이고, R17는 메틸기이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

And R17 is a methyl group.

이고, R17는 치환 또는 비치환된 아릴기이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

And R < 17 > is a substituted or unsubstituted aryl group.

이고, R17는 치환 또는 비치환된 아릴기이고, R18는 수소이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

, R17 is a substituted or unsubstituted aryl group, and R18 is hydrogen.

이고, R17는 페닐기이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

And R17 is a phenyl group.

이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

to be.

이고, L1은 치환 또는 비치환된 아릴렌기이다.In another embodiment, R9 is < RTI ID = 0.0 >

And L < 1 > is a substituted or unsubstituted arylene group.

이고, L1은 치환 또는 비치환된 페닐렌기이다.In another embodiment, R9 is < RTI ID = 0.0 >

And L < 1 > is a substituted or unsubstituted phenylene group.

이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

to be.

이고, R19는 수소이다.In another embodiment, R9 is < RTI ID = 0.0 >

And R19 is hydrogen.

이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

to be.

이고, R25는 수소이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

And R25 is hydrogen.

이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

to be.

In another embodiment, R < 233 > is a substituted or unsubstituted aryl group.

In one embodiment of the present specification, R 23 is a substituted or unsubstituted phenyl group.

In one embodiment of the present specification, R23 is a phenyl group, and R22 is hydrogen.

이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

to be.

In one embodiment of the present disclosure, j is 2.

In one embodiment of the present specification, R24 is a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R24 is a methyl group.

이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

to be.

이고, R20 및 R21은 수소이다. In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

And R20 and R21 are hydrogen.

이다, In one embodiment of the present disclosure, R9 is < RTI ID = 0.0 >

to be,

In one embodiment of the present specification, R15 and R16 are the same or different and each independently a substituted or unsubstituted aryl group.

In one embodiment of the present specification, R15 and R16 are the same or different and each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, Lt; / RTI >

In one embodiment of the present specification, R15 and R16 are biphenyl groups.

In one embodiment of the present specification, R15 and R16 are the same or different from each other and are each independently a phenyl group or a biphenyl group.

In one embodiment of the present specification, R15 and R16 are the same as or different from each other and are each independently a phenyl group or a terphenyl group.

In one embodiment of the present invention, R15 and R16 are the same or different from each other and each independently a fluorenyl group substituted with a biphenyl group or an alkyl group.

이다. In one embodiment of the present specification, the biphenyl group is

to be.

이다. In one embodiment of the present specification, the biphenyl group is

to be.

이다. In one embodiment of the present specification, the biphenyl group is

to be.

In another embodiment, at least one of R and R3 through R10 is hydrogen; A substituted or unsubstituted arylamine group; A substituted or unsubstituted aryl group; Substituted or unsubstituted arylphosphine group substituted or unsubstituted silyl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present disclosure, at least one of R and R3 through R10 is hydrogen; An arylamine group substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms; A substituted or unsubstituted C6 to C30 aryl; An arylphosphine group substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms; A silyl group substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.

In another embodiment, R is selected from the group consisting of hydrogen; A substituted or unsubstituted arylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted silyl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present disclosure, R is hydrogen; An arylamine group substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms; A substituted or unsubstituted C6 to C30 aryl; An arylphosphine group substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms; A silyl group substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.

In one embodiment of the present disclosure, at least one of R and R3 through R10 is hydrogen; And substituents of the following [A-1].

[A-1]

In one embodiment of the present disclosure, at least one of R and R3 through R10 is hydrogen; And the substituents in the following [A-2].

[A-2]

In one embodiment of the present disclosure, at least one of R and R3 through R10 is hydrogen; And the substituents in the following [A-3].

[A-3]

In one embodiment of the present disclosure, at least one of R and R3 through R10 is hydrogen; And the substituents in the following [A-4].

[A-4]

In one embodiment of the present disclosure, at least one of R and R3 through R10 is hydrogen; And the substituents in the following [A-5].

[A-5]

In one embodiment of the present invention, the heterocyclic compound represented by Formula 1 may be selected from the following structural formulas.

In one embodiment of the present invention, the heterocyclic compound represented by Formula 1 may be selected from the following structural formulas.

In one embodiment of the present invention, the heterocyclic compound represented by Formula 1 may be selected from the following structural formulas.

When X in the heterocyclic compound represented by the formula (1) is O or S, it can be prepared based on the following production example. According to one embodiment, it can be prepared in the same manner as in the following Reaction Schemes 1 to 4, Reaction I and Reaction Scheme II.

[Reaction Scheme I]

R7 to R10, R15, R16 and d are as defined above, X is S or O, and A 'is any one selected from A-1 to A-4.

After preparing at least one of A-1 to A-4, the heterocyclic compound represented by the general formula (1) can be prepared by condensing a brominated carbazole group or a brominated triphenylamine group, as in the above-mentioned production method.

The compounds corresponding to the above A-1 to A-4 can be synthesized to have various substituents by introducing a substituent to the reaction material. The method of introducing a substituent may be any condition as long as it is a reaction condition known in the art.

In this case, various heterocyclic compounds represented by the formula (1) can be prepared by changing R7 to R10, R15 and R16.

According to one embodiment, when X is NR among the heterocyclic compounds represented by the above formula (1), it may be prepared based on the following production example. According to one embodiment, it can be prepared in the same manner as in the following Reaction Schemes 5 to 8.

Bromo-10-phenyl-10H-spiro [acridine-9,9'-fluorene] was used instead of the compound a-1 in the above Reaction Scheme 5, Can be manufactured.

Except that 2'-bromo-10-phenyl-10H-spiro [acridine-9,9'-fluorene] was used instead of the compound a-1 in the above Reaction Scheme 6, Can be manufactured.

Except that 4'-bromo-10-phenyl-10H-spiro [acridine-9,9'-fluorene] was used instead of the compound b-1 in the above Reaction Scheme 7, Can be manufactured.

Except that 4'-bromo-10-phenyl-10H-spiro [acridine-9,9'-fluorene] was used instead of the compound b-1 in the above Reaction Scheme 8, Can be manufactured.

The synthetic procedure may be carried out by methods known in the art, for example, Stephen L. Buchwald, J. Am. Chem. Soc. 1998, 120, 6621-6622.

In this case, it is possible to introduce a substituent by changing the reaction conditions, reactants and the like using a method known in the art, and using this, various heterocyclic compounds represented by the formula (1) can be prepared.

The present invention also provides an organic light emitting device comprising the heterocyclic compound represented by Formula 1.

In one embodiment of the present disclosure, 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 includes the heterocyclic compound.

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, an electron injecting layer, and an electron blocking 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 another embodiment, the organic material layer includes an electron transporting layer, an electron injecting layer, a layer which simultaneously transports electrons and electrons, a light emitting layer, a hole transporting layer, a hole injecting layer, or a layer simultaneously transporting holes and injecting holes, The electron transporting layer, the electron injecting layer, the layer that simultaneously transports electrons and injects electrons, the light emitting layer, the hole transporting layer, the hole injecting layer, or the layer that simultaneously transports holes and injects holes includes the above heterocyclic compound.

In one embodiment of the present invention, the organic layer includes a hole transporting layer, and the hole transporting layer includes the heterocyclic compound.

In one embodiment of the present invention, the organic layer includes an electron blocking layer, and the electron blocking layer includes the heterocyclic compound.

In one embodiment of the present invention, the organic material layer includes an electron transporting layer, an electron injection layer, or a layer that simultaneously performs electron transport and electron injection, and the electron transport layer, the electron injection layer, And the above heterocyclic compound.

In one embodiment of the present invention, the light emitting layer includes the heterocyclic compound.

In one embodiment of the present invention, the light emitting layer includes the heterocyclic compound as a host.

In one embodiment of the present invention, the organic material layer includes a hole injecting layer, a hole transporting layer, or a layer simultaneously transporting holes and injecting holes, wherein the hole injecting layer, the hole transporting layer, And the above heterocyclic compound.

In one embodiment of the present invention, the hole transferring material, the host material in the light emitting layer, or the electron transferring material may be used depending on the nature of the substituent represented by formula (1).

In one embodiment of the present invention, the organic material layer may further include a hole injection layer or a hole transport layer containing a compound containing an arylamino group, a carbazole group or a benzocarbazole group in addition to the organic compound layer containing the heterocyclic compound.

In one embodiment of the present invention, the organic compound layer containing the heterocyclic compound includes the heterocyclic compound as a host, and may include another organic compound, metal or metal compound as a dopant.

In another embodiment, the organic light emitting device may be a normal type organic light emitting device in which an anode, at least one organic layer, and a cathode are sequentially stacked on a substrate.

 In another embodiment, the organic light emitting device may be an inverted type organic light emitting device in which a cathode, at least one organic material layer, and an anode are sequentially stacked on a substrate.

For example, the structure of the organic light emitting device according to the present invention is illustrated in FIGS.

1 shows an organic light emitting device in which an anode 2, a hole injecting layer 3, a hole transporting layer 4, a light emitting layer 5, an electron transporting layer 6 and a cathode 7 are sequentially stacked on a substrate 1 Structure is illustrated. In such a structure, the compound represented by Formula 1 may be included in the hole injecting layer 3, the hole transporting layer 4, the light emitting layer 5, or the electron transporting layer 6.

2 illustrates a structure of an organic light emitting device in which an anode 2, a hole injecting layer 3, a hole transporting layer 4, a light emitting layer 5, and a cathode 7 are sequentially laminated on a substrate 1. In such a structure, the compound represented by Formula 1 may be included in the hole injecting layer 3, the hole transporting layer 4, or the electron transporting layer 6.

3 illustrates a structure of an organic light emitting device in which an anode 2, a hole transporting layer 4, a light emitting layer 5, an electron transporting layer 6, and a cathode 7 are sequentially laminated on a substrate 1. In such a structure, the compound represented by Formula 1 may be included in the hole transport layer 4, the light emitting layer 5, or the electron transport layer 6.

4 shows a structure of an organic light emitting device in which an anode 2, a light emitting layer 5, an electron transport layer 6 and a cathode 7 are sequentially laminated on a substrate 1. [ In such a structure, the compound represented by Formula 1 may be included in the light-emitting layer 5 or the electron-transporting layer 6.

5 illustrates a structure of an organic light emitting device in which an anode 2, a light emitting layer 5, and a cathode 7 are sequentially laminated on a substrate 1. [ In such a structure, the compound represented by Formula 1 may be included in the light emitting layer 5.

When the organic light emitting diode includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

The organic light-emitting device of the present invention can be manufactured by materials and methods known in the art, except that one or more of the organic layers include the compound of the present invention, i.e., the heterocyclic compound.

For example, the organic light emitting device of the present invention can be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, a PVD (Physical Vapor Deposition) method such as sputtering or e-beam evaporation is used to deposit a metal or a metal oxide having conductivity or an alloy thereof on a substrate to form a positive electrode Forming an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer and an electron transporting layer thereon, and depositing a material usable as a cathode thereon. In addition to such a method, an organic light emitting device can be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

In addition, the compound of Formula 1 may be formed into an organic material layer by a solution coating method as well as a vacuum evaporation method in the production of an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating and the like, but is not limited thereto.

In addition to such a method, an organic light emitting device may be fabricated by sequentially depositing an organic material layer and a cathode material on a substrate from a cathode material (International Patent Application Publication No. 2003/012890). However, the manufacturing method is not limited thereto.

In one embodiment of the present invention, the first electrode is an anode and the second electrode is a cathode.

In another embodiment, the first electrode is a cathode and the second electrode is a cathode.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode material that can be used in the present invention 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] (PEDOT), polypyrrole and polyaniline.

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

The hole injecting material is a layer for injecting holes from the electrode. The hole injecting material has a hole injecting effect, a hole injecting effect in the anode, and an excellent hole injecting effect in the light emitting layer or the light emitting material. A compound which prevents the exciton from migrating to the electron injection layer or the electron injection material and is also excellent in the thin film forming ability is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene- , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

The hole transport layer is a layer that transports holes from the hole injection layer to the light emitting layer. The hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer. The material is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a heterocyclic compound. Specific examples of the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds. Examples of the heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specific examples of the aromatic amine derivatives include condensed aromatic ring derivatives having substituted or unsubstituted arylamino groups, and examples thereof include pyrene, anthracene, chrysene, and peripherrhene having an arylamino group. Examples of the styrylamine compound include substituted or unsubstituted Wherein at least one aryl vinyl group is substituted with at least one aryl vinyl group, and at least one substituent selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group is substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like. Examples of the metal complex include iridium complex, platinum complex, and the like, but are not limited thereto.

The electron transporting material is a layer that receives electrons from the electron injecting layer and transports electrons to the light emitting layer. The electron transporting material is a material capable of transferring electrons from the cathode well to the light emitting layer. Is suitable. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transporting layer can be used with any desired cathode material as used according to the prior art. In particular, an example of a suitable cathode material is a conventional material having a low work function followed by an aluminum layer or a silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer for injecting electrons from the electrode. The electron injection layer has the ability to transport electrons, has an electron injection effect from the cathode, and has an excellent electron injection effect with respect to the light emitting layer or the light emitting material. A compound which prevents migration to a layer and is excellent in a thin film forming ability is preferable. Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, A complex compound and a nitrogen-containing five-membered ring derivative, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8- Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8- hydroxyquinolinato) gallium, bis (10- Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8- quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, and the like, But is not limited thereto.

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

In one embodiment of the present invention, the heterocyclic compound may be included in an organic solar cell or an organic transistor in addition to an organic light emitting device.

Hereinafter, the present invention will be described in detail by way of examples with reference to the drawings. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the embodiments described below. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art.

< Manufacturing example  1>

After adding sodium tert-butoxide (2.76 g, 28.68 mmol) to a 500 ml round-bottomed flask in a nitrogen atmosphere, the compound A (12.0 g, 22.06 mmol) and Iodobenzene (4.95 g, 24.26 mmol) tert- butylphosphine) palladium (0) (0.11 g, 0.22 mmol) were added thereto, followed by heating and stirring for 2 hours. After the temperature was lowered to room temperature, and the base was removed by filtration, the xylene was concentrated under reduced pressure, and the obtained compound 1 (9.56 g, yield: 70%) was obtained by column chromatography with tetrahydrofuran: hexane = 1:16.

MS [M + H] &lt; ⁺ &gt; = 621

< Manufacturing example  2>

Compound A (12.0 g, 22.06 mmol) and 4-iodo-1,1'-biphenyl (6.79 g, 24.26 mmol) were completely dissolved in 220 ml of xylene in a 500 ml round-bottomed flask under nitrogen atmosphere and sodium tert- was added 28.68mmol), and after inserting the Bis (tri- tert -butylphosphine) palladium ( 0) (0.11g, 0.22mmol) was added and the mixture was heated and stirred for 3 hours. The temperature was lowered to room temperature, and the base was removed by filtration. The xylene was concentrated under reduced pressure, and the residue was subjected to column chromatography with tetrahydrofuran: hexane = 1: 10 to prepare Compound 2 (12.11 g, yield: 79%).

MS [M + H] &lt; ⁺ &gt; = 697

< Manufacturing example  3>

Compound A (12.0 g, 22.06 mmol) and 4-iodo-1,1'-biphenyl (6.60 g, 24.26 mmol) were dissolved in 240 ml of xylene in a 500 ml round-bottomed flask under nitrogen atmosphere and sodium tert- (0.11 g, 0.22 mmol) of bis (tri- tert- butylphosphine) palladium (0) was added thereto, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, and the base was removed by filtration. The Xylene was concentrated under reduced pressure, and the residue was subjected to column chromatography using tetrahydrofuran: hexane = 1: 12 to prepare Compound 3 (13.92 g, yield: 86%).

MS [M + H] &lt; ⁺ &gt; = 737

< Manufacturing example  4>

Compound A (12.0 g, 22.06 mmol), 4-bromo-N and N-diphenylaniline (6.54 g, 24.26 mmol) were dissolved in 280 ml of xylene in a 500 ml round bottom flask under nitrogen atmosphere and sodium tert- mmol) and Bis (tri- tert- butylphosphine) palladium (0) (0.11 g, 0.22 mmol) were added and the mixture was heated with stirring for 5 hours. The temperature was lowered to room temperature, and the base was removed by filtration. The xylene was concentrated under reduced pressure, and the residue was subjected to column chromatography with tetrahydrofuran: hexane = 1: 18 to prepare Compound 4 (12.65 g, yield: 73%).

MS [M + H] &lt; ⁺ &gt; = 788

< Manufacturing example  5>

Compound A (12.0 g, 22.06 mmol) and 3-bromo-9-phenyl-9H-carbazole (6.54 g, 24.26 mmol) were dissolved in 320 ml of xylene in a 500 ml round bottom flask under a nitrogen atmosphere and sodium tert-butoxide , 28.68 mmol) was added, and Bis (tri- tert- butylphosphine) palladium (0) (0.11 g, 0.22 mmol) was added and the mixture was heated with stirring for 8 hours. The temperature was lowered to room temperature, and the base was removed by filtration. The xylene was concentrated under reduced pressure, and the residue was subjected to column chromatography with tetrahydrofuran: hexane = 1: 14 to prepare Compound 5 (11.39 g, yield 66%).

MS [M + H] &lt; ⁺ &gt; = 786

< Manufacturing example  6>

Compound A (12.0 g, 22.06 mmol) and 9- (4-bromophenyl) -9H-carbazole (6.54 g, 24.26 mmol) were dissolved in 320 ml of xylene in a 500 ml round bottom flask under a nitrogen atmosphere and sodium tert-butoxide , 28.68 mmol) was added, and Bis (tri- tert- butylphosphine) palladium (0) (0.11 g, 0.22 mmol) was added and the mixture was heated with stirring for 7 hours. The temperature was lowered to room temperature, the base was removed by filtration, the xylene was concentrated under reduced pressure, and the residue was subjected to column chromatography with tetrahydrofuran: hexane = 1: 13 to prepare Compound 6 (10.26 g, yield: 60%).

MS [M + H] &lt; ⁺ &gt; = 786

< Manufacturing example  7>

Compound A (12.0 g, 22.06 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (6.69 g, 24.26 mmol) were dissolved in 240 ml of xylene in a 500 ml round- tert-butoxide (2.76 g, 28.68 mmol) was added, and bis (tri- tert- butylphosphine) palladium (0) (0.11 g, 0.22 mmol) was added and the mixture was heated with stirring for 7 hours. The temperature was lowered to room temperature, and the base was removed by filtration. The Xylene was concentrated under reduced pressure, and the residue was subjected to column chromatography with tetrahydrofuran: hexane = 1: 13 to prepare Compound 7 (15.20 g, yield: 89%).

MS [M + H] &lt; ⁺ &gt; = 776

< Manufacturing example  8>

Compound A (12.0 g, 22.06 mmol) and 2-chloro-4-phenylquinazoline (6.69 g, 24.26 mmol) were dissolved in 240 ml of xylene in a 500 ml round-bottom flask under nitrogen atmosphere and sodium tert-butoxide (2.76 g, 28.68 mmol) Butyl (tri- tert- butylphosphine) palladium (0) (0.11 g, 0.22 mmol) was added thereto, followed by heating and stirring for 7 hours. The temperature was lowered to room temperature, and the base was removed by filtration. The Xylene was concentrated under reduced pressure, and the residue was subjected to column chromatography with tetrahydrofuran: hexane = 1: 13 to prepare Compound 8 (13.26 g, yield: 80%).

MS [M + H] &lt; ⁺ &gt; = 749

 < Manufacturing example  9 to 16>

The compounds 9 to 16 were prepared in the same manner as in Preparation Examples 1 to 8 except that Compound B was used instead of Compound A in Preparation Examples 1 to 8 above.

< Manufacturing example  17 to 24>

The compounds 17 to 24 were prepared in the same manner as in Preparation Examples 1 to 8 except that Compound C was used instead of Compound A in Production Examples 1 to 8 above.

< Manufacturing example  25 to 32>

The compounds 25 to 32 were prepared in the same manner as in Preparation Examples 1 to 8 except that Compound D was used instead of Compound A in Preparation Examples 1 to 8.

< Manufacturing example  33 to 40>

The compounds 33 to 40 were prepared in the same manner as in Preparation Examples 1 to 8 except that Compound E was used instead of Compound A in Preparation Examples 1 to 8.

< Manufacturing example  41 to 48>

The compounds 41 to 48 were prepared in the same manner as in Preparation Examples 1 to 8 except that Compound F was used instead of Compound A in Preparation Examples 1 to 8.

< Manufacturing example  49 to 56>

The compounds 49 to 56 were prepared in the same manner as in Preparation Examples 1 to 8 except that Compound G was used instead of Compound A in Production Examples 1 to 8 above.

< Manufacturing example  57 to 64>

Preparation Examples 1 to 8 were prepared in the same manner as in Preparation Examples 1 to 8 except that Compound H was used instead of Compound A in Preparation Examples 1 to 8, to thereby prepare the above Compounds 57 to 64.

< Experimental Example  1-1>

The glass substrate coated with ITO (indium tin oxide) thin film with a thickness of 1,000 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. In this case, Fischer Co. was used as a detergent, and distilled water filtered by a filter of Millipore Co. was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

On this ITO transparent electrode, hexanitrile hexaazatriphenylene (HAT) of the following chemical formula was thermally vacuum deposited to a thickness of 500 Å to form a hole injection layer.

N-phenylamino] biphenyl (NPB) (300 Å) was vacuum-deposited on the hole injection layer to form a hole transport layer, which is a material for transporting holes, and the following compound 4-4'-bis [N- (1-naphthyl) Respectively.

Subsequently, the following compound 1 was vacuum deposited on the hole transport layer to a thickness of 100 ANGSTROM to form an electron blocking layer.

Subsequently, BH and BD were vacuum deposited on the electron blocking layer to a thickness of 300 ANGSTROM at a weight ratio of 25: 1 to form a light emitting layer.

The compound ET1 and the compound LiQ (Lithium Quinolate) were vacuum deposited on the light emitting layer at a weight ratio of 1: 1 to form an electron injection and transport layer having a thickness of 300 Å. Lithium fluoride (LiF) and aluminum were deposited to a thickness of 2000 Å on the electron injecting and transporting layer sequentially to form a cathode.

Was maintained at the deposition rate was 0.4 ~ 0.7Å / sec for organic material in the above process, the lithium fluoride of the cathode was 0.3Å / sec, aluminum is deposited at a rate of 2Å / sec, the degree of vacuum upon deposition ⅹ10 2 ^-7 To 5 x 10 &lt; ^-6 &gt; torr, thereby fabricating an organic light emitting device.

<Experimental Example 1-2>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 2 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-3>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 3 was used instead of Compound 1 in Experimental Example 1-1.

 <Experimental Example 1-4>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 4 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-5>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 5 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-6>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 6 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-7>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 9 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-8>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 10 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-9>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 11 was used instead of Compound 1 in Experimental Example 1-1.

 <Experimental Example 1-10>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 12 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-11>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 13 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-12>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 14 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-13>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 20 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-14>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 21 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-15>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 28 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-16>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 29 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-17>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 36 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-18>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 37 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-19>

An organic light emitting device was prepared in the same manner as in Experimental Example 1-1, except that Compound 44 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-20>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 45 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-21>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 52 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-22>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 53 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-23>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 60 was used instead of Compound 1 in Experimental Example 1-1.

<Experimental Example 1-24>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 61 was used instead of Compound 1 in Experimental Example 1-1.

&Lt; Comparative Example 1-1 >

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound EB1 was used instead of Compound 1 in Experimental Example 1-1.

&Lt; Comparative Example 1-2 >

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that the following compound EB2 was used in place of Compound 1 in Experimental Example 1-1.

The results shown in Table 1 were obtained when current was applied to the organic light-emitting devices fabricated in Examples 1-1 to 1-24 and Comparative Examples 1-1 and 1-2.

compound
(Electron blocking layer) Voltage
(V @ 10 mA / cm ² ) efficiency
(cd / A @ 10mA / cm 2) Color coordinates
(x, y) Experimental Example 1-1 Compound 1 3.89 6.45 (0.138, 0.127) Experimental Example 1-2 Compound 2 3.74 6.55 (0.139, 0.122) Experimental Example 1-3 Compound 3 3.65 6.56 (0.138, 0.126) Experimental Examples 1-4 Compound 4 3.61 6.75 (0.138, 0.127) Experimental Examples 1-5 Compound 5 3.54 6.85 (0.137, 0.125) Experimental Example 1-6 Compound 6 3.72 6.47 (0.136, 0.125) Experimental Example 1-7 Compound 9 3.70 6.51 (0.136, 0.127) Experimental Examples 1-8 Compound 10 3.77 6.35 (0.136, 0.125) Experimental Examples 1-9 Compound 11 3.76 6.34 (0.137, 0.125) Experimental Example 1-10 Compound 12 3.75 6.31 (0.138, 0.125) Experimental Example 1-11 Compound 13 3.85 6.33 (0.136, 0.125) Experimental Example 1-12 Compound 14 3.81 6.32 (0.137, 0.125) Experimental Example 1-13 Compound 20 3.65 6.74 (0.138, 0.127) Experimental Example 1-14 Compound 21 3.54 6.85 (0.137, 0.125) Experimental Example 1-15 Compound 28 3.66 6.70 (0.138, 0.127) Experimental Example 1-16 Compound 29 3.58 6.88 (0.137, 0.125) Experimental Example 1-17 Compound 36 3.67 6.77 (0.138, 0.127) Experimental Example 1-18 Compound 37 3.59 6.81 (0.137, 0.125) Experimental Example 1-19 Compound 44 3.62 6.72 (0.138, 0.127) Experimental Example 1-20 Compound 45 3.51 6.89 (0.137, 0.125) Experimental Example 1-21 Compound 52 3.63 6.78 (0.138, 0.127) Experimental Example 1-22 Compound 53 3.55 6.82 (0.137, 0.125) Experimental Example 1-23 Compound 60 3.64 6.74 (0.138, 0.127) Experimental Example 1-24 Compound 61 3.56 6.84 (0.137, 0.125) Comparative Example 1-1 EB1 (TCTA) 4.53 5.41 (0.137, 0.126) Comparative Example 1-2 EB2 4.23 5.91 (0.136, 0.127)

As shown in Table 1, in the case of an organic light emitting device manufactured using a heterocyclic compound according to one embodiment of the present invention as an electron blocking layer, Comparative Example 1-1, which is a conventional organic light emitting device using EB1 (TCTA) As compared with Comparative Example 1-2 in which phenyl is condensed to the core of the heterocyclic compound according to one embodiment of the present invention, the heterocyclic compound according to one embodiment of the present invention has an electron blocking effect, Exhibits excellent characteristics in terms of driving voltage and / or stability.

As shown in Table 1, it was confirmed that the heterocyclic compound according to one embodiment of the present invention is excellent in electron blocking ability and applicable to organic light emitting devices.

<Experimental Example 2-1>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 1 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as an electron blocking layer .

<Experimental Example 2-2>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 2 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as an electron blocking layer .

<Experimental Example 2-3>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 3 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as an electron blocking layer .

 <Experimental Example 2-4>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 4 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as an electron blocking layer .

<Experimental Example 2-5>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 5 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as an electron blocking layer .

<Experimental Example 2-6>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 6 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as an electron blocking layer .

<Experimental Example 2-7>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 9 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as an electron blocking layer .

<Experimental Example 2-8>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1 except that Compound 10 was used instead of NPB as the hole transport layer in Example 1-1 and EB1 (TCTA) was used as an electron blocking layer Respectively.

<Experimental Example 2-9>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 11 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as an electron blocking layer Respectively.

 <Experimental Example 2-10>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 12 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as an electron blocking layer .

<Experimental Example 2-11>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 13 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as an electron blocking layer .

<Experimental Example 2-12>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 14 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as an electron blocking layer .

<Experimental Example 2-13>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 20 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as an electron blocking layer .

<Experimental Example 2-14>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 21 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as an electron blocking layer .

<Experimental Example 2-15>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 28 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as an electron blocking layer .

<Experimental Example 2-16>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 29 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as an electron blocking layer .

<Experimental Example 2-17>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 36 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as an electron blocking layer .

<Experimental Example 2-18>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 37 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as an electron blocking layer .

<Experimental Example 2-19>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 44 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as an electron blocking layer .

<Experimental Example 2-20>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 45 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as an electron blocking layer Respectively.

<Experimental Example 2-21>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 52 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as the electron blocking layer .

<Experimental Example 2-22>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 53 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as the electron blocking layer .

<Experimental Example 2-23>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 60 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as the electron blocking layer .

<Experimental Example 2-24>

An organic light emitting device was fabricated in the same manner as in Experimental Example 1-1, except that Compound 61 was used instead of NPB as the hole transport layer in Example 1-1, and EB1 (TCTA) was used as the electron blocking layer .

&Lt; Comparative Example 2-1 >

An organic light emitting device was prepared in the same manner as in Experimental Example 2-1, except that HT1 (NPB) was used instead of Compound 1 as the hole transport layer in Experimental Example 2-1.

&Lt; Comparative Example 2-2 &

An organic light emitting device was fabricated in the same manner as in Experimental Example 2-1 except that HT2 (TCTA) was used instead of Compound 1 as the hole transport layer in Experimental Example 2-1.

The results shown in Table 2 were obtained when current was applied to the organic light-emitting devices fabricated in Experimental Examples 2-1 to 2-24 and Comparative Examples 2-1 and 2-2.

compound
(Hole transport layer) Voltage
(V @ 10 mA / cm ² ) efficiency
(cd / A @ 10mA / cm 2) Color coordinates
(x, y) Experimental Example 2-1 Compound 1 4.55 5.35 (0.138, 0.127) EXPERIMENTAL EXAMPLE 2-2 Compound 2 4.52 5.35 (0.139, 0.122) Experimental Example 2-3 Compound 3 4.68 5.36 (0.138, 0.126) Experimental Example 2-4 Compound 4 4.39 5.59 (0.138, 0.127) Experimental Example 2-5 Compound 5 4.45 5.52 (0.137, 0.125) Experimental Examples 2-6 Compound 6 4.76 5.37 (0.136, 0.125) Experimental Example 2-7 Compound 9 4.68 5.31 (0.136, 0.127) Experimental Examples 2-8 Compound 10 4.73 5.35 (0.136, 0.125) Experimental Examples 2-9 Compound 11 4.69 5.34 (0.137, 0.125) Experimental Example 2-10 Compound 12 4.52 5.68 (0.138, 0.125) Experimental Example 2-11 Compound 13 4.54 5.56 (0.136, 0.125) Experimental Examples 2-12 Compound 14 4.46 5.54 (0.137, 0.125) Experimental Example 2-13 Compound 20 4.31 5.61 (0.136, 0.125) Experimental Example 2-14 Compound 21 4.40 5.60 (0.138, 0.126) Experimental Example 2-15 Compound 28 4.33 5.52 (0.137, 0.125) Experimental Example 2-16 Compound 29 4.47 5.61 (0.136, 0.127) Experimental Example 2-17 Compound 36 4.46 5.55 (0.135, 0.127) Experimental Example 2-18 Compound 37 4.34 5.51 (0.138, 0.127) Experimental Example 2-19 Compound 44 4.31 5.69 (0.137, 0.125) Experimental Example 2-20 Compound 45 4.48 5.56 (0.137, 0.125) Experimental Example 2-21 Compound 52 4.36 5.66 (0.137, 0.125) Experimental Example 2-22 Compound 53 4.31 5.58 (0.136, 0.125) Experimental Example 2-23 Compound 60 4.40 5.50 (0.138, 0.126) Experimental Example 2-24 Compound 61 4.33 5.52 (0.137, 0.125) Comparative Example 2-1 HT1 (NPB) 5.56 4.31 (0.136, 0.127) Comparative Example 2-2 HT2 5.21 4.95 (0.136, 0.127)

As shown in Table 2, in the case of an organic light emitting device manufactured using a heterocyclic compound according to one embodiment of the present invention as a hole transport layer, Comparative Example 2-1 using HT1 (NPB) And Comparative Example 2-2 in which phenyl is condensed with the core of the heterocyclic compound according to the present invention exhibits excellent characteristics in terms of efficiency, driving voltage and / or stability of the organic light emitting device.

As shown in Table 1, it was confirmed that the heterocyclic compound according to one embodiment of the present invention is excellent in hole transporting ability and applicable to organic light emitting devices.

As shown in Tables 1 and 2, it was confirmed that the heterocyclic compound according to one embodiment of the present invention is excellent in electron blocking ability as well as hole transporting ability and applicable to organic light emitting devices.

< Comparative Example  3-1>

The compounds prepared in Preparation Examples were subjected to high purity sublimation purification by a conventionally known method, and then a green organic light emitting device was prepared in the following manner.

The glass substrate coated with ITO (ndium tin oxide) with a thickness of 1,000 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. In this case, Fischer Co. was used as a detergent, and distilled water filtered by a filter of Millipore Co. was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

(60 nm) / TCTA (80 nm) / CBP + 10% Ir (ppy) 3 (300 nm) / BCP (10 nm) / Alq3 (30 nm) using CBP as a host on the prepared ITO transparent electrode. / LiF (1 nm) / Al (200 nm) were fabricated in this order to produce an organic EL device.

The structures of m-MTDATA, TCTA, Ir (ppy) 3, CBP and BCP are as follows.

<Experimental Example 3-1>

An organic light emitting device was fabricated in the same manner as in Comparative Example 3-1 except that the compound 1-a-1 was used instead of CBP in the above Comparative Example 3-1.

 <Experimental Example 3-2>

An organic light emitting device was fabricated in the same manner as in Comparative Example 3-1 except that the compound 1-a-4 was used instead of the compound CBP in the above Comparative Example 3-1.

<Experimental Example 3-3>

An organic light emitting device was fabricated in the same manner as in Comparative Example 3-1 except that the compound 1-a-6 was used in place of the compound CBP in Comparative Example 3-1.

<Experimental Example 3-4>

An organic light emitting device was fabricated in the same manner as in Comparative Example 3-1, except that the compound 1-a-7 was used instead of the compound CBP in the above Comparative Example 3-1.

<Experimental Example 3-5>

An organic light emitting device was fabricated in the same manner as in Comparative Example 3-1 except that the compound 1-a-9 was used instead of the compound CBP in the above Comparative Example 3-1.

<Experimental Example 3-6>

An organic light emitting device was fabricated in the same manner as in Comparative Example 3-1 except that the compound 1-a-11 was used instead of the compound CBP in the above Comparative Example 3-1.

<Experimental Example 3-7>

An organic light emitting device was fabricated in the same manner as in Comparative Example 3-1, except that Compound 1-a-13 was used instead of Compound CBP in Comparative Example 3-1.

 <Experimental Example 3-8>

An organic light emitting device was prepared in the same manner as in Comparative Example 3-1, except that the compound 1-a-14 was used instead of the compound CBP in the above Comparative Example 3-1.

<Experimental Example 3-9>

An organic light emitting device was fabricated in the same manner as in Experimental Example 3, except that Compound 7 was used instead of Compound CBP in Comparative Example 3-1.

<Experimental Example 3-10>

An organic light emitting device was fabricated in the same manner as in Comparative Example 3-1, except that Compound 15 was used instead of Compound CBP in Comparative Example 3-1.

<Experimental Example 3-11>

An organic light emitting device was fabricated in the same manner as in Comparative Example 3-1, except that Compound 23 was used instead of Compound CBP in Comparative Example 3-1.

<Experimental Example 3-12>

An organic light emitting device was fabricated in the same manner as in Experimental Example 3, except that Compound 31 was used instead of Compound CBP in Experimental Example 3.

<Experimental Example 3-13>

An organic light emitting device was prepared in the same manner as in Experimental Example 3, except that Compound 39 was used in place of Compound CBP in Experimental Example 3.

<Experimental Example 3-14>

An organic light emitting device was fabricated in the same manner as in Comparative Example 3-1, except that Compound 47 was used instead of Compound CBP in Comparative Example 3-1.

 <Experimental Example 3-15>

An organic light emitting device was fabricated in the same manner as in Comparative Example 3-1, except that Compound 55 was used in place of Compound CBP in Comparative Example 3-1.

<Experimental Example 3-16>

An organic light emitting device was fabricated in the same manner as in Comparative Example 3-1, except that the compound 63 was used instead of the compound CBP in Comparative Example 3-1.

&Lt; Comparative Example 3-2 &

An organic light emitting device was fabricated in the same manner as in Comparative Example 3-1, except that the following GH1 was used in place of CBP in Comparative Example 3-1.

&Lt; Comparative Example 3-3 &

An organic light emitting device was fabricated in the same manner as in Comparative Example 3-1 except that the following GH2 was used in place of CBP in Comparative Example 3-1.

The results shown in Table 3 were obtained when current was applied to the organic light-emitting devices manufactured in Experimental Examples 3-1 to 3-16 and Comparative Examples 3-1 to 3-3.

compound
(Host) Voltage
(V @ 10 mA / cm ² ) efficiency
(cd / A @ 10mA / cm 2) Emission peak
(nm) Comparative Example 3-1 CBP 7.62 31.12 516 Experimental Example 3-1 Compound 1-a-1 6.70 40.43 517 Experimental Example 3-2 Compound 1-a-4 6.72 40.54 516 Experimental Example 3-3 Compound 1-a-6 6.71 40.62 517 Experimental Example 3-4 Compound 1-a-7 6.62 40.55 518 Experimental Example 3-5 Compound 1-a-9 6.70 40.45 517 Experimental Example 3-6 Compound 1-a-11 6.73 40.53 517 Experimental Example 3-7 Compound 1-a-13 6.71 40.42 516 Experimental Examples 3-8 Compound 1-a-14 6.72 40.44 517 Experimental Examples 3-9 Compound 7 6.52 42.08 516 Experimental Example 3-10 Compound 15 6.61 42.72 518 Experimental Example 3-11 Compound 23 6.62 42.70 517 Experimental Examples 3-12 Compound 31 6.63 42.76 516 Experimental Example 3-13 Compound 39 6.60 44.93 517 Experimental Examples 3-14 Compound 47 6.56 45.24 516 Experimental Example 3-15 Compound 55 6.61 44.72 518 Experimental Examples 3-16 Compound 63 6.59 44.65 517 Comparative Example 3-2 GH1 7.12 38.82 516 Comparative Example 3-3 GH2 7.35 36.12 516

As a result of the experiment, the green organic light emitting devices of Experimental Examples 3-1 to 3-16 using the heterocyclic compound according to one embodiment of the present invention as the host material of the light emitting layer were compared with Comparative Example 3-1 using conventional CBP, The organic EL device of Comparative Examples 3-2 and 3-3, which is a derivative in which phenyl is condensed on the core of the heterocyclic compound according to one embodiment of the present invention, exhibits excellent current efficiency and excellent driving voltage.

< Experimental Example  4-1 to 4-8>

The compounds prepared in Preparation Examples were subjected to high purity sublimation purification by a conventionally known method, and red organic light emitting devices were prepared as follows.

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. After the substrate was mounted in a vacuum chamber, the substrate was pressurized to have a pressure of 1 × 10 -6 torr. Then, organic substances were injected onto the ITO using DNTPD (700 Å), α-NPB (300 Å) (100 wt%) was used as host (24 wt%), 24, 32, 40, 48, 56 or 64 as a host, 350 Å), LiF (5 Å), and Al (1,000 Å) in this order and measured at 0.4 mA.

The DNTPD, α-NPB, (piq ) 2 Ir (acac) , and structure of Alq ₃ is as follows.

&Lt; Comparative Example 4-1 >

The organic light emitting device for Comparative Example 4-1 was the same as the organic light emitting device prepared in Example 4-1 except that CBP, which is commonly used as a general phosphorescent host material, Was prepared in the same manner as in Experimental Example 4-1.

The voltage, the current density, the luminance, the color coordinates and the lifetime of the organic light emitting device manufactured according to Experimental Examples 4-1 to 4-8 and Comparative Example 4-1 were measured and the results are shown in Table 4 below. T95 means the time required for the luminance to decrease from the initial luminance (5000 nits) to 95%.

division Host
Dopant Voltage Luminance
(V) CIEx
(cd / m ² ) CIEy T95 (hr) Experimental Example 4-1 8 [(piq) ₂ Ir (acac)] 4.3 1860 0.670 0.329 465 Experimental Example 4-2 16 [(piq) ₂ Ir (acac)] 4.2 1850 0.674 0.325 415 Experimental Example 4-3 24 [(piq) ₂ Ir (acac)] 4.1 1900 0.672 0.327 440 Experimental Example 4-4 32 [(piq) ₂ Ir (acac)] 4.3 1840 0.673 0.335 435 Experimental Example 4-5 40 [(piq) ₂ Ir (acac)] 4.0 1790 0.675 0.333 405 Experimental Example 4-6 48 [(piq) ₂ Ir (acac)] 4.2 1810 0.670 0.339 420 Experimental Examples 4-7 56 [(piq) ₂ Ir (acac)] 4.3 1970 0.671 0.338 445 Experimental Examples 4-8 64 [(piq) ₂ Ir (acac)] 4.3 1860 0.668 0.329 465 Comparative Example 4-1 CBP [(piq) ₂ Ir (acac)] 6.5 1220 0.679 0.339 235

As shown in Table 4, the red color of Experimental Examples 4-1 to 4-8 using the heterocyclic compounds 8, 16, 24, 32, 40, 48, 56 and 64 as the host material of the light- It was confirmed that the organic light emitting device exhibited superior performance in terms of current efficiency, driving voltage and lifetime than the red organic light emitting device of Comparative Example 4-1 using CBP.

While the present invention has been described with reference to the preferred embodiments (the electron blocking layer, the hole transporting layer, and the light emitting layer), the present invention is not limited thereto and various modifications may be made within the scope of the claims and the detailed description of the invention And it is also within the scope of the invention.

1: substrate
2: anode
3: Hole injection layer
4: hole transport layer
5: light emitting layer
6: electron transport layer
7: cathode

Claims (23)

A heterocyclic compound represented by the following formula (2) or (3):
(2)

(3)

In formulas (2) and (3)
X is O, S or NR,
R1 and R2 are each hydrogen or combine to form a 5-membered fused ring,
R1 'and R2' are each hydrogen or combine to form a 5-membered condensed ring,
a is an integer of 1 to 3,
b is an integer of 1 to 6,
c is an integer of 1 to 6,
d is an integer of 1 to 4,
When c is 2 or more, plural R &lt; 9 &gt; are the same or different from each other,
R is an arylamine group substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms; An alkyl group having 1 to 30 carbon atoms, a phosphine oxide group substituted with an aryl group having 6 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with a heteroaryl group having 2 to 30 carbon atoms ; A phosphine oxide group substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms; Or a heterocyclic group having 2 to 30 carbon atoms which is substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms,
R9 is hydrogen; A nitrile group; An aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms substituted with an aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, An aryl group having 6 to 30 carbon atoms; A heterocyclic group having 2 to 30 carbon atoms which is substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms; An arylamine group; Or a phosphine oxide group substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms,
R3 to R6 are the same or different from each other, and each independently hydrogen; Or an aryl group having 6 to 30 carbon atoms, and R7, R8 and R10 are hydrogen. delete The method according to claim 1,
The heterocyclic compound represented by the above formula (2) or (3) is a heterocyclic compound represented by the following formula (4) or (5)
[Chemical Formula 4]

[Chemical Formula 5]

In the general formulas (4) and (5)
X, a, b, d, R, R1 ', R2' and R1 to R10 are the same as defined in claim 1. The method according to claim 1,
The heterocyclic compound represented by the above formula (2) or (3) is a heterocyclic compound represented by the following formula (6) or (7)
[Chemical Formula 6]

(7)

In the above formulas (6) and (7)
X, a, b, d, R, R1 ', R2' and R1 to R10 are the same as defined in claim 1. The method according to claim 1,
Wherein the heterocyclic compound represented by the formula (2) or (3) is represented by any one of the following formulas (8) to (11)
[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

In formulas (8) to (11)
a to d, X, R1 ', R2' and R1 to R10 are as defined in claim 1. The method according to claim 1,
And X is S or O. The method according to claim 1,
X is NR,
And R is the same as defined in claim 1. The method according to claim 1,
Wherein the heterocyclic compound represented by Formula 2 or 3 is represented by any one of the following Formulas 1-a-1 to 1-a-24:

In the general formulas (1-a-1) to (1-a-24), R is the same as defined in claim 1. The method according to claim 1,
Wherein the heterocyclic compound represented by Formula 2 or 3 is represented by any one of the following Formulas 1-b-1 to 1-b-48:

In the general formulas (1-b-1) to (b-48), R and R9 are the same as defined in claim 1. delete The method according to claim 1,
R9 is hydrogen; A nitrile group; A phenyl group substituted or unsubstituted with an alkyl group having 1 to 30 carbon atoms, a phosphine oxide group substituted with an aryl group having 6 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 2 to 30 carbon atoms; A naphthalene group; Phenanthrene; Triphenylene; A fluorenyl group substituted or unsubstituted with an alkyl group having 1 to 30 carbon atoms; A carbazolyl group substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms; A pyridine group substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms; A pyrimidine group substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms; A triazine group substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms; A benzimidazole group substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms; 1,10-phenanthroline group; An arylphosphine group having 6 to 30 carbon atoms; Or an arylamine group substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms. The method according to claim 1,
R9 is a fluorenyl group substituted or unsubstituted with an alkyl group having 1 to 30 carbon atoms; An arylphosphine group having 6 to 30 carbon atoms; And a heterocyclic compound which is any one of the following substituents:

,

,

,

,

,

,

,

,

,

,

,

,

In the substituent,
e is an integer of 1 to 4,
f, g, i and 1 are each an integer of 1 to 7,
h is an integer of 1 to 4,
j and k are each an integer of 1 to 9,
L1 is a direct bond; An arylene group; Or a divalent heterocyclic group,
R11 to R27 are the same or different from each other, and each independently hydrogen; Or aryl having from 6 to 30 carbon atoms. The method of claim 12,
L1 is a direct bond; A phenylene group; Or a divalent carbazole group. delete delete The heterocyclic compound according to claim 1, wherein the compound of formula (2) or (3) is selected from the following formulas:

The heterocyclic compound according to claim 1, wherein the compound of formula (2) or (3) is selected from the following formulas:

The heterocyclic compound according to claim 1, wherein the compound of formula (2) or (3) is selected from the following formulas:

A first electrode; A second electrode facing the first electrode; And at least one organic layer including a light emitting layer provided between the first electrode and the second electrode,
Wherein at least one of the organic material layers comprises the heterocyclic compound according to any one of claims 1, 3 to 9, 11 to 13, and 16 to 18. The method of claim 19,
The organic material layer includes an electron transport layer, an electron injection layer, a layer that simultaneously performs electron transport and electron injection, a light emitting layer, a hole transport layer, a hole injection layer, or a layer simultaneously transporting holes and injecting holes,
Wherein the electron transporting layer, the electron injecting layer, the layer that simultaneously transports electrons and injects electrons, the light emitting layer, the hole transporting layer, the hole injecting layer, or the layer that simultaneously transports holes and injects holes comprises the heterocyclic compound. The method of claim 19,
Wherein the organic material layer comprises a hole transporting layer, and the hole transporting layer comprises the heterocyclic compound. The method of claim 19,
Wherein the organic material layer comprises an electron blocking layer, and the electron blocking layer comprises the heterocyclic compound. The method of claim 19,
Wherein the light emitting layer comprises the heterocyclic compound as a host.

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