KR101984081B1 - Hetero-cyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

[0001] HETERO-CYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME [0002]

This application claims the benefit of Korean Patent Application No. 10-2015-0166708, filed on November 26, 2015, to the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

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

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layer structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out.

Development of new materials for such organic light emitting devices has been continuously required.

International Patent Application Publication No. 2003-012890

The present invention provides a heterocyclic compound and an organic light emitting device including the heterocyclic compound.

According to one embodiment of the present invention, there is provided a heterocyclic compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

L ₁ and L ₂ are the same or different and are each independently a direct bond; A substituted or unsubstituted cyclopentadienylene group; A substituted or unsubstituted furanyl group; A substituted or unsubstituted phenylene group; A substituted or unsubstituted naphthylene group; A substituted or unsubstituted terphenylene group; A substituted or unsubstituted anthrylene group; A substituted or unsubstituted biphenylene group; A substituted or unsubstituted phenanthrylene group; A substituted or unsubstituted fluorenylene group; A substituted or unsubstituted spirobifluorenylene group; A substituted or unsubstituted dibenzofuranylene group; A substituted or unsubstituted dihydrophenanthrenylene group; A substituted or unsubstituted triphenylene group; A substituted or unsubstituted phenylene group-naphthylene group; And a structure represented by the following formula (2)

 (2)

In Formula 2,

R ₁ to R ₆ are the same or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted C6 to C30 aryl; And a substituted or unsubstituted C2-C30 heteroaryl group,

Two of R &_lt; ₁ > to R &_lt; ₆ >

a, b, c, d, e and f are the same or different and each is an integer of 1 to 4,

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

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

When c is 2 or more, the R < ₃ > s are the same or different from each other,

When d is 2 or more, R < ₄ > are the same or different from each other,

When e is 2 or more, R ₅ are the same or different from each other,

When f is 2 or more, the R < ₆ >

Ar ₁ and Ar ₂ are the same or different and each is a phenyl group substituted with a nitrile group; A biphenyl group substituted with a nitrile group; A substituted or unsubstituted pyrenyl group; A substituted or unsubstituted pyridazinyl group; A substituted or unsubstituted pyrazinyl group; A substituted or unsubstituted 1,2,3-triazinyl group; A substituted or unsubstituted 1,2,4-triazinyl group; A substituted or unsubstituted quinolinyl group; A substituted or unsubstituted isoquinolinyl group; A substituted or unsubstituted phenanthryl group; A substituted or unsubstituted phenanthridyl group; A substituted or unsubstituted phenanthrolinyl group; A substituted or unsubstituted benzoquinolinyl group; A substituted or unsubstituted benzoisoquinolinyl group; A substituted or unsubstituted fluoranthenyl group; A substituted or unsubstituted quinoxalinyl group; A substituted or unsubstituted thienolinyl group; A substituted or unsubstituted benzosynolinyl group; A substituted or unsubstituted quinazolinyl group; A substituted or unsubstituted phosphine oxide group; And a structure represented by the following formula (3)

Provided that when L ₁ is a direct bond, Ar ₁ is not a substituted or unsubstituted pyrenyl group, and when L ₂ is a direct bond, Ar ₂ is not a substituted or unsubstituted pyrenyl group,

(3)

In Formula 3,

X ₁ to X ₁₂ are the same or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted C6 to C30 aryl; And a substituted or unsubstituted C2-C30 heteroaryl group, or two adjacent X ₁ to X ₁₂ are connected to each other to form a substituted or unsubstituted monocyclic or polycyclic hydrocarbon ring or substituted or unsubstituted C 6 -C 30 hydrocarbon ring Or an unsubstituted monocyclic or polycyclic heterocyclic ring having 2 to 30 carbon atoms,

Any one of X ₁ to X ₁₂ is connected to the formula (1) via L ₁ or L ₂ .

According to an embodiment of the present invention, there is also provided a plasma display panel comprising: a first electrode; A second electrode facing the first electrode; And at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers includes the above-described heterocyclic compound.

The compound according to one embodiment of the present disclosure can be used as a material of an organic material layer of an organic light emitting device and by using it, it is possible to improve the efficiency, the driving voltage and / or the lifetime characteristics of the organic light emitting device.

1 shows an organic light emitting device 10 according to an embodiment of the present invention.
2 shows an organic light emitting element 11 according to another embodiment of the present invention.
Fig. 3 shows the MS spectrum of Compound 1 prepared by Preparation Example 1. Fig.

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

The present invention provides a compound represented by the above formula (1).

In this specification, when a part is referred to as " including " an element, it is to be understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise.

In this specification, when a member is located on another member, it includes not only the case where the member is in contact with the other member but also the case where another member exists between the two members.

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

Examples of substituents in the present specification are described below, but are not limited thereto.

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

As used herein, the term " substituted or unsubstituted " A halogen group; Knit Reel; A nitro group; Imide; An amide group; Carbonyl group; An ester group; A hydroxy 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 amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group, or that at least two of the substituents exemplified above are substituted with a substituent to which they are linked, or have no substituent. For example, " a substituent to which at least two 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. Means that at least two of the substituents exemplified above are substituted or unsubstituted with a substituent connected thereto. For example, " a substituent to which at least two 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.

는 다른 치환기 또는 결합부에 결합되는 부위를 의미한다.In the present specification,

Quot; refers to a moiety bonded to another substituent or bond.

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

In the present specification, the number of carbon atoms in the imide group is not particularly limited, but is preferably 1 to 30 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 substituted with hydrogen, an alkyl group having 1 to 30 carbon atoms, a straight chain, a branched chain or a cyclic alkyl group having 6 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the carbon number of the carbonyl group is not particularly limited, but it is preferably 1 to 30 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 an ester group oxygen in a straight chain, branched chain or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 30 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 30. 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, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like.

In the present specification, the cycloalkyl group is not particularly limited, but is preferably a group having 3 to 30 carbon atoms. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, 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 30 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 this specification, the amine group is -NH ₂ ; An alkylamine group; An aralkylamine group; An arylamine group; And a heteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, 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.

In the present specification, the alkyl group in the alkylamine, the aralkylamine, 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, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. 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 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 may be -BR ₁₀₀ R ₁₀₁ R ₁₀₂ , wherein R ₁₀₀ , R ₁₀₁ and R ₁₀₂ are the same or different and each independently hydrogen; heavy hydrogen; halogen; Nitrile group; A substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; A substituted or unsubstituted, straight or branched chain alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; And a substituted or unsubstituted monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 30 carbon atoms. Specific examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group, and the like, but are not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. And preferably 10 to 30 carbon atoms. Specific examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a klycenyl group and a fluorenyl group.

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

,

,

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 aryl group in the aryloxy group, the arylthioxy group, the arylsulfoxy group and the 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 this specification, the heteroaryl group in the present specification includes one or more non-carbon atoms and hetero atoms, and specifically, the hetero atom may be an atom selected from the group consisting of O, N, Se and S, . The number of carbon atoms is not particularly limited, but is preferably 2 to 30 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furanyl group, a pyrrolyl 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, a pyrazinopyrazinyl group, a pyrazinopyrazinyl group, a pyrazinopyranyl group, a pyrazinylpyridazinyl group, a pyrazinylpyridazinyl group, a pyrazinylpyridazinyl group, a pyrazinylpyridazinyl group, A benzothiazolyl group, a benzothiazolyl group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline group (such as a benzothiazolyl group, a benzothiazolyl group, phenanthroline, thiazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group and dibenzofuranyl group, but not limited thereto.

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

In the present specification, the heterocyclic group may be monocyclic or polycyclic, and may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and examples thereof may be selected from the above heteroaryl groups.

In the present specification, an arylene group means a divalent group having two bonding positions in an aryl group. The description of the aryl group described above can be applied except that each of these is 2 groups.

또는

일 수 있으나, 이에 한정되는 것은 아니다.In the present specification, in the case of a phenylene group-naphthylene group, it means that a naphthylene group is connected to a phenylene group to form a divalent linkage group,

or

But is not limited thereto.

In the present specification, the hydrocarbon ring may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and may be selected from the examples of the cycloalkyl group or the aryl group except the univalent hydrocarbon ring.

In the present specification, an adamantyl ring may be monocyclic or polycyclic and may be selected from the examples of the aryl group except that it is not monovalent.

In the present specification, the hetero ring includes one or more non-carbon atoms and hetero atoms. Specifically, the hetero atom may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like. The heterocyclic ring may be monocyclic or polycyclic, and may be aromatic, aliphatic or aromatic and aliphatic condensed rings, and may be selected from the examples of the heteroaryl group except that it is not monovalent.

According to one embodiment of the present invention, in Formula 1, L ₁ and L ₂ are the same or different and are each independently a direct bond; Cyclopentadienylene group; A furanylene group; A phenyl group; Naphthylene group; A terphenylrenylene group; Anthrylene group; Biphenyllylene groups; Phenanthrylene group; A fluorenylene group substituted with methyl or phenyl; A spirobifluorenylene group; Dibenzofuranyl group; Dihydrophenanthrenylene group; Triphenylenylene group; A phenylene group-naphthylene group; And a structure represented by the following formula (2).

(2)

In the above formula (2), the definitions of R ₁ to R ₆ , a, b, c, d, e and f are the same as described above.

According to one embodiment of the present invention, in Formula 2, R ₁ to R ₆ are hydrogen, and two of R ₁ to R ₆ are linked to Formula (1).

According to one embodiment of the present invention, Ar ₁ and Ar ₂ are the same or different and each is a phenyl group substituted with a nitrile group; A biphenyl group substituted with a nitrile group; Pyrenyl; A pyridazinyl group; A pyrazinyl group; 1,2,3-triazinyl group; A 1,2,4-triazinyl group; A quinolinyl group; An isoquinolinyl group; A phenanthryl group; Phenanthridil; A phenanthrolinyl group; Benzoquinolinyl group; Benzoisoquinolinyl group; A fluoranthenyl group; A quinoxalinyl group; Cinnolinyl group; Benzoinorhinyl group; A quinazolinyl group; A phosphine oxide group substituted with a phenyl group, a biphenyl group, a naphthyl group or a phenanthryl group; And a structure represented by the following formula (3)

Provided that when L ₁ is a direct bond, Ar ₁ is not a pyrenyl group, and when L ₂ is a direct bond, Ar ₂ is not a pyrenyl group,

(3)

In the general formula (3), the definitions of X ₁ to X ₁₂ are the same as those described above.

According to one embodiment of the present invention, in Formula 3, X ₁ to X ₁₂ are hydrogen, or two adjacent X ₁ to X ₁₂ are connected to each other to form a substituted or unsubstituted monocyclic ring having 6 to 20 carbon atoms Or a substituted or unsubstituted monocyclic or polycyclic heterocyclic ring having 2 to 20 carbon atoms, and any of X ₁ to X ₁₂ is linked to the formula (1) via L ₁ or L ₂ .

According to one embodiment of the present invention, in Formula 3, two of adjacent X ₁ to X ₁₂ are connected to form a substituted or unsubstituted monocyclic or polycyclic hydrocarbon ring having 6 to 10 carbon atoms, or a substituted or unsubstituted Form a monocyclic or polycyclic heterocyclic ring having 2 to 10 carbon atoms.

According to one embodiment of the present invention, the adjacent two of X ₁ to X ₁₂ are connected to each other to form a substituted or unsubstituted benzene ring.

According to one embodiment of the present invention, the adjacent two of X ₁ to X ₁₂ are bonded to each other to form a benzene ring.

According to one embodiment of the present invention, the structure represented by Formula 3 may be represented by any one of the following Formulas 3-1 to 3-8.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Chemical Formula 3-4]

[Formula 3-5]

[Chemical Formula 3-6]

[Chemical Formula 3-7]

[Chemical Formula 3-8]

In the above formulas (3-1) to (3-8)

The definitions of X ₁ to X ₁₂ are the same as those of the above formula (3)

Y ₁ to Y ₄ are the same or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted C6 to C30 aryl; And a substituted or unsubstituted C 2 -C 30 heteroaryl group, or a substituted or unsubstituted C 6 -C 30 monocyclic ring or a substituted or unsubstituted monocyclic or polycyclic group, wherein X ₁ to X ₁₂ and two adjacent ones of Y ₁ to Y ₄ are connected to each other to form a A substituted or unsubstituted monocyclic or polycyclic hydrocarbon ring or a substituted or unsubstituted monocyclic or polycyclic heterocyclic ring having 2 to 30 carbon atoms,

Any one of X ₁ to X ₁₂ and Y ₁ to Y ₄ is linked to the formula (1) through L ₁ or L ₂ .

According to one embodiment of the present invention, in the formulas (3-1) to (3-8), X ₁ to X ₁₂ and Y ₁ to Y ₄ are hydrogen, and X ₁ to X ₁₂ and Y ₁ to Y ₄ one is connected to the general formula (1) through L ₁ or L _2.

According to one embodiment of the present invention, the heterocyclic compound represented by Formula 1 may be any one selected from the following Compounds 1 to 98.

According to one embodiment of the present disclosure, there is provided a liquid crystal display comprising: a first electrode; A second electrode facing the first electrode; And at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers includes the above-described 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, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transporting layer, and an electron injecting layer as organic layers. However, the structure of the organic light emitting device is not limited thereto and may include fewer or more organic layers.

For example, the structure of the organic light emitting device of the present invention may have a structure as shown in FIGS. 1 and 2, but the present invention is not limited thereto.

1 illustrates a structure of an organic light emitting diode 10 in which a first electrode 30, a light emitting layer 40, and a second electrode 50 are sequentially stacked on a substrate 20. 1 is an exemplary structure of an organic light emitting diode according to an embodiment of the present invention, and may further include another organic layer.

2, a first electrode 30, a hole injection layer 60, a hole transport layer 70, a light emitting layer 40, a hole blocking layer 80, an electron transport layer 90, The structure of the organic light emitting device in which the injecting layer 100 and the second electrode 50 are sequentially laminated is illustrated. 2 is an exemplary structure according to an embodiment of the present invention, and may further include another organic layer.

According to one embodiment of the present invention, the organic material layer includes a hole blocking layer, and the hole blocking layer includes a heterocyclic compound represented by the general formula (1).

According to an embodiment of the present invention, the organic material layer includes an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes the heterocyclic compound represented by the formula (1).

According to one embodiment of the present invention, the organic material layer includes an electron transporting layer, an electron injecting layer, or a layer simultaneously performing electron transporting and electron injection, and the electron transporting layer, the electron injecting layer, And a heterocyclic compound represented by the above formula (1).

According to an embodiment of the present invention, the organic material layer may further include at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

The organic light emitting device of the present invention is manufactured by materials and methods known in the art except that one or more of the organic layers include the heterocyclic compound of the present specification, that is, the heterocyclic compound represented by the above formula (1) .

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.

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 metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation Forming a first electrode, forming an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer, and an electron transporting layer on the first electrode, and depositing a material usable as a second electrode 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 first electrode material on a substrate. The heterocyclic compound represented by Formula 1 may be formed into an organic layer by a solution coating method as well as a vacuum deposition method in the production of an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, 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.

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

According to another embodiment of the present invention, 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, LiO ₂ / Al, and Mg / Ag, but are not limited thereto.

As the hole injecting material, the hole injecting layer has a function of injecting holes from an electrode and a hole injecting material, and has a hole injecting effect in the anode, and an excellent hole injecting effect in a light emitting layer or a light emitting material , The migration of excitons generated in the light emitting layer to the electron injection layer or the electron injection material, and also the ability to form thin films 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 of the light emitting layer 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 high 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 may be 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 heterocyclic compound include carbazole derivatives, dibenzofuran derivatives, Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include an aromatic amine derivative, a styrylamine compound, a boron complex, a fluoranthene compound, and a metal complex. 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 of the electron transporting layer is a layer that transports electrons from the electron injecting layer to the electron transporting layer and transports electrons from the cathode to the light emitting layer. This large material 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.

According to one embodiment of the present invention, the heterocyclic compound represented by Formula 1 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.

Production Example 1. Preparation of Compound 1

The compound 1-A (31.08 g, 93.98 mmol) and the compound 1-B (7.0 g, 46.99 mmol) were dissolved in dioxane (200 mL), followed by the addition of 2M aqueous tribasic potassium phosphate solution (120 mL) and bis (dibenzylideneacetone) palladium (1.36 g, 3 mol%) and tricyclohexylphosphane (1.32 g, 6 mol%) were added thereto, and the mixture was refluxed for 1 hour and 30 minutes. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was purified by soxhlet with chloroform and the resulting solid was filtered. The resulting solid was dried to give Compound 1 (11.4 g, 50%). MS: [M + H] < ⁺ > = 487

Production Example 2. Preparation of Compound 3

Compound 3 (9.8 g, 43%) was prepared in the same manner as in Production Example 1 except that Compound 3-A (31.08 g, 93.98 mmol) was used instead of Compound 1-A in Production Example 1. MS: [M + H] < ⁺ > = 487

Production Example 3. Preparation of Compound 6

Compound 6 (17.1 g, 62%) was prepared in the same manner as in Production Example 1, except that Compound 6-A (35.8 g, 93.98 mmol) was used in place of Compound 1-A in Production Example 1. MS: [M + H] < ⁺ > = 587

Production Example 4. Preparation of Compound 7

Compound 7 (13.5 g, 49%) was prepared in the same manner as in Production Example 1 except that Compound 7-A (35.7 g, 93.98 mmol) was used instead of Compound 1-A in Production Example 1. MS: [M + H] < ⁺ > = 585

Production Example 5. Preparation of Compound 1-C

The compound 1-B (30.0 g, 201.4 mmol) and 4-chlorophenyl boronic acid (63.0 g, 402.8 mmol) were dissolved in dioxane (500 mL), 2M potassium carbonate (300 mL) Phosphino palladium (9.3 g, 8.1 mmol) was added and the mixture was refluxed for 12 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized from chloroform, and the resulting solid was filtered. The resulting solid was dried to give Compound 1-C (497. g, 82%). MS: [M + H] < ⁺ > = 301

Production Example 6. Preparation of Compound 8

(20 g, 66.4 mmol), compound 1-C (10 g, 33.2 mmol), dichloro (1,3-bis (diphenylphosphino) propane) ) propane) nickel (1.8 g, 3.3 mmol) and cesium carbonate (21.6 g, 66.4 mmol) were placed in dioxane and refluxed for 5 hours. After completion of the reaction, the resulting solid was filtered and dissolved in CHCl ₃ and recrystallized to obtain Compound 8 (18.5 g, yield 67%; MS: [M + H] + = 833).

Production Example 7. Preparation of Compound 10

Compound 10 (12.6 g, 55%) was prepared in the same manner as in Production Example 1 except that Compound 10-A (31.08 g, 93.98 mmol) was used in place of Compound 1-A in Production Example 1. MS: [M + H] < ⁺ > = 487

Production Example 8. Preparation of Compound 15

Compound 15 (11.2 g, 39%) was prepared in the same manner as in Production Example 1 except that Compound 15-A (37.05 g, 93.98 mmol) was used instead of Compound 1-A in Production Example 1. MS: [M + H] < ⁺ > = 613

Production Example 9. Preparation of Compound 21

Compound 21 (12.9 g, 43%) was prepared in the same manner as in Production Example 1 except that Compound 21-A (30.5 g, 93.98 mmol) was used in place of Compound 1-A in Production Example 1. MS: [M + H] < ⁺ > = 637

Preparation 10. Preparation of Compound 22

Compound 22-A (30.5 g, 93.98 mmol) was used in place of Compound 1-A in Production Example 1, and Compound 1-C (14.15 g, 46.99 mmol) (15.2 g, 51%). MS: [M + H] < ⁺ > = 633

Preparation Example 11. Preparation of Compound 26

Compound 26 (10.3 g, 47%) was prepared in the same manner as in Production Example 1 except that Compound 26-A (30.18 g, 93.98 mmol) was used instead of Compound 1-A in Production Example 1. MS: [M + H] < ⁺ > = 467

Production Example 12. Preparation of Compound 1-D

Compound 1-D (44.5 g, 76%) was prepared in the same manner as in Production Example 5 except that phenanthren-3-ylboronic acid (44.7 g, 201.4 mmol) was used instead of (4-chlorophenyl) boronic acid in Production Example 5 . MS: [M + H] < ⁺ > = 291

Preparation Example 13. Preparation of Compound 50

Except that Compound 50-A (23.7 g, 46.99 mmol) was used in place of Compound 1-A in Production Example 1 and Compound 1-D (13.7 g, 46.99 mmol) was used in place of Compound 1-B, Compound 50 (23.5 g, 79%). MS: [M + H] < ⁺ > = 633

Example 1

A glass substrate coated with ITO (indium tin oxide) having a thickness of 500 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. At this time, Fischer Co. product 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.

The following compound [HI-A] was thermally vacuum deposited on the ITO transparent electrode prepared above to a thickness of 600 Å to form a hole injection layer. The compound [HAT] (50 ANGSTROM) and the following compound [HT-A] (600 ANGSTROM) were sequentially vacuum-deposited on the hole injection layer to form a hole transport layer.

Subsequently, the following compounds [BH] and [BD] were vacuum deposited on the hole transport layer at a weight ratio of 25: 1 at a thickness of 200 ANGSTROM to form a light emitting layer. [Compound 1] and the following 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 350 Å. Lithium fluoride (LiF) and aluminum having a thickness of 1,000 Å were sequentially deposited on the electron injecting and transporting layer to form a cathode. The deposition rate of the organic material was maintained at 0.4 to 0.9 A / sec, the lithium fluoride at the cathode was maintained at a deposition rate of 0.3 A / sec, and the deposition rate of aluminum was maintained at 2 A / sec. by keeping the ^-7 to 5 × 10 ^-8 torr, an organic light emitting device was produced.

Example 2

An organic light emitting device was fabricated in the same manner as in [Example 1] except that [Compound 3] was used in place of [Compound 1] in [Example 1].

Example 3

An organic light emitting device was fabricated in the same manner as in [Example 1], except that [Compound 6] was used in place of [Compound 1] in [Example 1].

Example 4

An organic light emitting device was fabricated in the same manner as in [Example 1] except that [Compound 7] was used in place of [Compound 1] in [Example 1].

Example 5

An organic light emitting device was fabricated in the same manner as in [Example 1] except that [Compound 8] was used in place of [Compound 1] in [Example 1].

Example 6

An organic light emitting device was prepared in the same manner as in [Example 1] except that [Compound 10] was used instead of [Compound 1] in [Example 1].

Example 7

An organic light emitting device was fabricated in the same manner as in [Example 1] except that [Compound 15] was used instead of [Compound 1] in [Example 1].

Example 8

An organic light emitting device was fabricated in the same manner as in [Example 1] except that [Compound 21] was used in place of [Compound 1] of [Example 1].

Example 9

An organic light emitting device was fabricated in the same manner as in [Example 1] except that [Compound 22] was used in place of [Compound 1] in [Example 1].

Example 10

An organic light emitting device was fabricated in the same manner as in [Example 1] except that [Compound 26] was used in place of [Compound 1] in [Example 1].

Example 11

An organic luminescent device was fabricated in the same manner as in [Example 1], except that [Compound 50] was used in place of [Compound 1] in [Example 1].

Comparative Example 1

An organic light emitting device was fabricated in the same manner as in [Example 1] except that Alq ₃ was used in place of [Compound 1] in [Example 1].

Voltage (V) Efficiency (cd / A) The color coordinates (x, y) Life span (h)
T ₉₀ at 20 mA / cm ² Example 1 4.32 7.35 (0.143, 0.108) 130 Example 2 4.29 7.27 (0.143, 0.109) 142 Example 3 4.38 6.92 (0.142, 0.108) 260 Example 4 4.40 7.04 (0.143, 0.108) 190 Example 5 4.16 8.01 (0.141, 0.107) 122 Example 6 4.37 7.19 (0.143, 0.108) 128 Example 7 3.92 6.79 (0.141, 0.108) 213 Example 8 4.12 7.46 (0.142, 0.109) 125 Example 9 4.53 6.81 (0.143, 0.108) 270 Example 10 4.01 7.66 (0.140, 0.107) 110 Example 11 4.11 8.12 (0.142, 0.108) 240 Comparative Example 1 5.51 3.87 (0.143, 0.109) 101

From the results of the above table, the compound represented by the formula (1) according to the present invention can be used for an organic layer capable of simultaneously injecting electrons and transporting electrons of an organic light emitting device. And it is easy to control the lifetime and efficiency by controlling the substituent.

In particular, the compound represented by formula (1) according to the present invention can be used in combination with an n-type dopant when used in an organic layer capable of electron injection and electron transport.

10, 11: Organic light emitting device
20: substrate
30: first electrode
40: light emitting layer
50: second electrode
60: Hole injection layer
70: hole transport layer
80: hole blocking layer
90: electron transport layer
100: electron injection layer

Claims (8)

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

In Formula 1,
L ₁ and L ₂ are the same or different and are each independently a direct bond; Cyclopentadienylene group; A furanylene group; A phenylene group; Naphthylene group; A terphenylrenylene group; Anthrylene group; Biphenyllylene groups; Phenanthrylene group; A fluorenylene group substituted or unsubstituted with an alkyl group or an aryl group; A spirobifluorenylene group; Dibenzofuranyl group; Dihydrophenanthrenylene group; Triphenylenylene group; Pyrrolylene group; A phenylene group-naphthylene group; And a structure represented by the following formula (2)
(2)

In Formula 2,
R ₁ to R ₆ are the same or different and are each independently hydrogen,
Two of R &_lt; ₁ > to R &_lt; ₆ >
a, b, c, d, e and f are each 4,
Ar ₁ and Ar ₂ are the same or different and each is a phenyl group substituted with a nitrile group; A biphenyl group substituted with a nitrile group; Pyrenyl; A pyridazinyl group; A pyrazinyl group; 1,2,3-triazinyl group; A 1,2,4-triazinyl group; A quinolinyl group; An isoquinolinyl group; A phenanthryl group; Phenanthridil; A phenanthrolinyl group; Benzoquinolinyl group; Benzoisoquinolinyl group; A fluoranthenyl group; A quinoxalinyl group; Cinnolinyl group; Benzoinonyl group; A dibenzosynolyl group; A pyrazinyl group; A quinazolinyl group; A phosphine oxide group substituted or unsubstituted with a phenyl group, a naphthyl group, a phenanthrene group, or a biphenyl group; And a structure represented by the following formula (3)
Provided that when L ₁ is a direct bond, Ar ₁ is not a pyrenyl group, and when L ₂ is a direct bond, Ar ₂ is not a pyrenyl group,
(3)

In Formula 3,
X ₁ to X ₁₂ are each hydrogen or two adjacent ones of X ₁ to X ₁₂ are connected to each other to form a monocyclic or polycyclic hydrocarbon ring having 6 to 30 carbon atoms,
Any one of X ₁ to X ₁₂ is connected to the formula (1) via L ₁ or L ₂ . The heterocyclic compound according to claim 1, wherein two adjacent X ₁ to X ₁₂ are connected to each other to form a benzene ring. The method according to claim 1,
Wherein the structure represented by the formula (3) is represented by any one of the following formulas (3-1) to (3-8):
[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Chemical Formula 3-4]

[Formula 3-5]

[Chemical Formula 3-6]

[Chemical Formula 3-7]

[Chemical Formula 3-8]

In the above formulas (3-1) to (3-8)
The definitions of X ₁ to X ₁₂ are the same as those of the above formula (3)
Y ₁ to Y ₄ are each hydrogen, or two adjacent ones of X ₁ to X ₁₂ and Y ₁ to Y ₄ are connected to each other to form a monocyclic or polycyclic hydrocarbon ring having 6 to 30 carbon atoms,
Any one of X ₁ to X ₁₂ and Y ₁ to Y ₄ is linked to the formula (1) through L ₁ or L ₂ . The heterocyclic compound according to claim 1, wherein the heterocyclic compound represented by the formula (1) is any one selected from the following compounds 1 to 98:

A first electrode; A second electrode facing the first electrode; And at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers comprises the heterocyclic compound of any one of claims 1 to 4, device. The organic light emitting diode according to claim 5, wherein the organic layer includes a hole blocking layer, and the hole blocking layer comprises the heterocyclic compound. 6. The organic electroluminescent device according to claim 5, wherein the organic material layer comprises an electron transporting layer, an electron injecting layer, or a layer simultaneously performing electron transporting and electron injection, wherein the electron transporting layer, And an organic light emitting layer. [6] The organic light emitting device according to claim 5, wherein the organic layer further comprises one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer.

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