WO2019108033A1 - Compound and organic light emitting element comprising same - Google Patents

Abstract

The present specification provides a compound represented by chemical formula 1, and an organic light emitting element comprising the same.

Description

Compounds and organic light emitting devices containing them

This application claims the benefit of Korean Patent Application No. 10-2017-0162877 filed on November 30, 2017 with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound and an organic light emitting device including 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.

The present invention aims to provide a compound having a low driving voltage and a long lifetime.

The present invention also provides an organic light emitting device comprising the compound.

An embodiment of the present specification can provide a compound represented by the following formula (1).

 [Chemical Formula 1]

In formula (1)

X1 and X2 are each independently O or S,

R1 to R3 each independently represent hydrogen; heavy hydrogen; A halogen group; A substituted or unsubstituted silyl group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

a and b are each independently an integer of 0 to 4,

c is an integer of 1 to 4,

When a to c are each independently 2 or more, the substituents in parentheses are the same or different from each other,

At least one of R < 3 > is represented by the following formula (2)

(2)

In formula (2)

L is a substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,

Ar1 and Ar2 each independently represent a substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

n is an integer of 0 to 3,

When n is 2 or more, the substituents in parentheses are the same or different from each other,

Adjacent groups among Ar1, Ar2 and L may combine with each other to form a ring.

In addition, one embodiment of the present disclosure includes 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 compound of Formula 1 have.

The compound according to one embodiment of the present invention can be used as a material of an organic material layer of an organic light emitting device, thereby improving the efficiency of the organic light emitting device, and improving the driving voltage and lifetime.

In addition, the compound according to one embodiment of the present invention can be used as a hole injecting or hole transporting material.

Whenever a component is referred to as " comprising ", it is to be understood that the component may include other components as well, without departing from the scope of the present invention.

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

An embodiment of the present invention provides a compound represented by the above formula (1).

Illustrative examples of such substituents are set forth 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; Cyano; A nitro group; Imide; 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.

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

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

In the present specification, the carbon number of the carbonyl group is not particularly limited, but it is preferably 1 to 40 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 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 , wherein R ₁₀₀ and R ₁₀₁ are the same or different and each independently hydrogen; heavy hydrogen; halogen; Cyano; 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. Specific examples include, but are 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 phosphine oxide group specifically includes a diphenylphosphine oxide group, a dinaphthylphosphine oxide group, and the like, 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 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, But are not limited to, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, But are not limited to, dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl and the like.

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. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another embodiment, the alkenyl group has 2 to 6 carbon atoms. 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 this specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

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, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n Butyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and the like. But is not limited thereto.

In this specification, the amine group is -NH ₂ ; An alkylamine group; N-alkylarylamine groups; An arylamine group; An N-arylheteroarylamine group; An N-alkylheteroarylamine 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 methylamine, dimethylamine, ethylamine, diethylamine, phenylamine, naphthylamine, biphenylamine, anthracenylamine, 9-methyl- , Diphenylamine group, N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group, N-phenylnaphthylamine group, Phenylnaphthylenediamine group, N-phenylphenylenediamine group, N-phenyltriphenylamine group, N-phenylphenanthrenylamine group, N-phenylphenanthrenylamine group, Group, an N-phenanthrenylfluorenylamine group, and an N-biphenylfluorenylamine group, but the present invention is not limited thereto.

In the present specification, the N-alkylarylamine group means an amine group in which N of the amine group is substituted with an alkyl group and an aryl group.

In the present specification, the N-arylheteroarylamine group means an amine group in which N in the amine group is substituted with an aryl group and a heteroaryl group.

In the present specification, the N-alkylheteroarylamine group means an amine group in which N in the amine group is substituted with an alkyl group and a heteroaryl group.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, or a substituted or unsubstituted diarylamine 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. For example, the aryl group in the arylamine group may be selected from the examples of the aryl group described above.

In the present specification, the alkyl group in the alkylamine group, the N-arylalkylamine group, the alkylthio group, the alkylsulfoxy group and the N-alkylheteroarylamine group can be applied to 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 methylsulfoxy group, an ethylsulfoxy group, a propylsulfoxy group, And the like, but the present invention is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group or the like as the monocyclic aryl group, but is not limited thereto. Examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a klycenyl group and a fluorenyl group.

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

When the fluorenyl group is substituted,

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

In the present specification, the heterocyclic group is a heterocyclic group and is a heterocyclic group containing at least one of N, O, S, Si and Se. 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, A benzothiazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline group, a thiazolyl group, a thiazolyl group, a thiazolyl group, 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, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, or a substituted or unsubstituted diheteroarylamine group. The heteroarylamine group having two or more heteroaryl groups may include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group at the same time. For example, the heteroaryl group in the heteroarylamine group may be selected from the examples of the above-mentioned heteroaryl group.

In the present specification, examples of the heteroaryl group in the N-arylheteroarylamine group and the N-alkylheteroarylamine group are the same as the examples of the above-mentioned heteroaryl group.

In the present specification, in the substituted or unsubstituted ring formed by bonding adjacent groups to each other, the "ring" means a substituted or unsubstituted hydrocarbon ring; Or a substituted or unsubstituted heterocycle.

In the 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 this specification, the aromatic 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 an aromatic, aliphatic or aromatic and aliphatic condensed ring, and examples thereof may be selected from the examples of the heterocyclic group except that the heterocyclic group is not monovalent.

In the present specification, the description of the aryl group described above can be applied except that arylene is a divalent group.

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.

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, the explanation on the aryl group described above can be applied except that the aromatic hydrocarbon ring is a divalent group. 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.

In the present specification, an aliphatic heterocyclic ring means an aliphatic ring containing at least one hetero atom.

As used herein, an aromatic heterocyclic ring means an aromatic ring containing at least one heteroatom.

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

In one embodiment of the present disclosure, X 1 and X 2 are each independently 0 or S.

In one embodiment of the present specification, Ar1 and Ar2 each independently represent a substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

Further, in one embodiment of the present specification, Ar1 and Ar2 each independently represent a substituted or unsubstituted silyl group; A substituted or unsubstituted C6 to C30 aryl; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.

In one embodiment of the present invention, Ar1 and Ar2 each independently represent a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted naphthalene group; A substituted or unsubstituted phenanthrene group; A substituted or unsubstituted fluorene group; A substituted or unsubstituted spirobifluorene group; A substituted or unsubstituted dibenzofurane group; A substituted or unsubstituted dibenzothiophene group; Or a substituted or unsubstituted carbazole group.

In one embodiment of the present invention, Ar1 and Ar2 each independently represent a fluorene group substituted with at least one of a phenyl group and a methyl group, an alkyl group substituted or unsubstituted with at least one aryl group, a naphthylene group, a carbazole group, A dibenzofurane group, a dibenzothiophene group, or a phenyl group substituted or unsubstituted with a spirobifluorene group; A biphenyl group substituted or unsubstituted with a silyl group or a carbazole group substituted or unsubstituted with at least one of an alkyl group, a phenyl group, an aryl group or alkyl, substituted or unsubstituted with an aryl group; A terphenyl group substituted or unsubstituted with a phenyl group; A naphthalene group substituted or unsubstituted with a phenyl group; Phenanthrene; A fluorene group substituted or unsubstituted with at least one of a phenyl group and a methyl group; A spirobifluorene group substituted or unsubstituted with a phenyl group; A dibenzofurane group substituted or unsubstituted with a phenyl group or a biphenyl group; A dibenzothiophene group substituted or unsubstituted with a phenyl group or a biphenyl group; Or a carbazol group substituted or unsubstituted with a phenyl group or a biphenyl group.

Further, in one embodiment of the present specification, when n is 0, it is a direct bond.

Further, in one embodiment of the present specification, when n is 2 or more, the substituents in parentheses are the same or different from each other.

Further, in one embodiment of the present specification, L is a substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group.

Further, in one embodiment of the present specification, L is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms; Or a substituted or unsubstituted divalent heterocyclic group having 2 to 30 carbon atoms.

Further, in one embodiment of the present specification, L is any one of the following formulas.

A1 to A3 each independently represent a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

a1 to a3 each represent an integer of 0 to 3,

When a1 to a3 are each independently an integer of 2 or more, the substituents in parentheses are the same or different from each other,

Represents the position to which a substituent is connected.

The ring formed by bonding adjacent groups of Ar1, Ar2 and L to each other is any one of the following formulas.

R5 to R16 each independently represent a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

d is an integer of 0 to 9,

e to h are each independently an integer of 0 to 8,

i is an integer of 0 to 3,

j is an integer of 0 to 6,

When each of e to j is independently an integer of 2 or more, the substituents in the parentheses are the same or different from each other,

Represents the position to which a substituent is connected.

In one embodiment of the present invention, the formula (1) may be represented by any of the following formulas (3) to (6).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

In formulas (3) to (6)

The definitions of R1, R2, R3, X1, X2, a and b are as described above.

According to one embodiment of the present disclosure, the compounds of the present invention are any of the following formulas:

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 compound of Formula 1 have.

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 generating layer, a hole transporting layer, a hole buffering layer, a light emitting layer, and the like 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.

According to one embodiment of the present invention, the organic material layer includes a hole generating layer, a hole transporting layer, a hole buffering layer, or a layer that simultaneously generates and transports holes, and the hole generating layer, the hole transporting layer, the hole blocking layer, At the same time, the layer may contain the compound of formula (1).

According to another embodiment of the present invention, the organic layer may include a light emitting layer, and the light emitting layer may include the compound of Formula 1.

According to another embodiment, the organic light emitting device may be a normal type organic light emitting device in which an anode, one or more organic compound layers, and a cathode are sequentially stacked on a substrate.

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

The organic light emitting device of the present invention may have a laminated structure as described below, but is not particularly limited thereto.

(1) First electrode / hole transporting layer / light emitting layer / second electrode

(2) First electrode / hole injecting layer / hole transporting layer / light emitting layer / second electrode

(3) First electrode / hole injection layer / hole buffer layer / hole transport layer / light emitting layer / second electrode

(4) First electrode / hole transporting layer / light emitting layer / electron transporting layer / second electrode

(5) First electrode / hole transporting layer / light emitting layer / electron transporting layer / electron injecting layer / second electrode

(6) First electrode / hole injecting layer / hole transporting layer / light emitting layer / electron transporting layer / second electrode

(7) First electrode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / second electrode

(8) First electrode / hole injection layer / hole buffer layer / hole transport layer / light emitting layer / electron transport layer / second electrode

(9) First electrode / hole injection layer / hole buffer layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / second electrode

(10) First electrode / hole transporting layer / electron blocking layer / light emitting layer / electron transporting layer / second electrode

(11) First electrode / hole transporting layer / electron suppressing layer / light emitting layer / electron transporting layer / electron injecting layer / second electrode

(12) First electrode / hole injecting layer / hole transporting layer / electron blocking layer / light emitting layer / electron transporting layer / second electrode

(13) First electrode / hole injection layer / hole transport layer / electron suppression layer / light emitting layer / electron transport layer / electron injection layer / second electrode

(14) First electrode / hole transporting layer / light emitting layer / hole blocking layer / electron transporting layer / second electrode

(15) First electrode / hole transporting layer / light emitting layer / hole blocking layer / electron transporting layer / electron injecting layer / second electrode

(16) First electrode / hole injecting layer / hole transporting layer / light emitting layer / hole blocking layer / electron transporting layer / second electrode

(17) First electrode / hole injecting layer / hole transporting layer / light emitting layer / hole blocking layer / electron transporting layer / electron injecting layer / second electrode

The first electrode is an electrode for injecting holes. The material of the first electrode may be a material having a large work function so that injection of holes into the organic material layer can be smoothly performed. 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 hole injection layer may serve to smoothly inject holes from the first electrode into the light emitting layer. The hole injecting layer may include the compound of Formula 1 above. In this case, the hole injection layer may be composed of only the compound of Formula 1, but the compound of Formula 1 may be present in a state mixed or doped with other hole injection layer materials known in the art. The compound of Formula 1 may account for 100% of the hole injection layer, but it may be doped at 0.1 to 50% by weight. The compound of the formula (1) is a derivative having an indenofluorene structure, and has excellent electron-accepting ability, so that power consumption can be improved and the driving voltage can be lowered. The thickness of the hole injection layer may be 1 to 150 nm. If the thickness of the hole injection layer is 1 nm or more, there is an advantage that the hole injection characteristics can be prevented from being lowered. If the thickness is 150 nm or less, the thickness of the hole injection layer is too thick, There is an advantage that it can be prevented from being raised. As the hole injection layer material, a hole injection material known in the art can be used. For example, in the group consisting of CuPc (cupper phthalocyanine), PEDOT (poly (3,4) -ethylenedioxythiophene), PANI (polyaniline) and NPD (N, N-dinaphthyl- Any one or more selected may be used, but the present invention is not limited thereto.

The hole transport layer can play a role of facilitating the transport of holes. The hole transport layer may contain the compound of the above formula (1). In this case, the hole transport layer may be composed of only the compound of Formula 1, but the compound of Formula 1 may be present in a state mixed or doped with other hole transport layer materials known in the art. The compound of Formula 1 may account for 100% of the hole transporting layer, but it may be doped at 0.1 to 50% by weight. As other hole transporting layer materials, hole transporting materials known in the art can be used. For example, the hole-transporting layer may be formed of NPD (N, N-dinaphthyl-N, N'-diphenylbenzidine), TPD (N, N'- s-TAD, and MTDATA (4,4 ', 4 "-tris (N-3-methylphenyl-N-phenylamino) -triphenylamine), but the present invention is not limited thereto. As the hole transport layer material, it is possible to use, as a hole transport layer material, a triazole derivative, an oxadiazole derivative, an imidazole derivative, a polyarylalkane derivative, a pyrazoline derivative and a pyrazolone derivative, a phenylene diamine derivative, an arylamine derivative, Stilbene derivatives, silazane derivatives, polysilane-based compounds, aniline-based copolymers, conductive polymeric oligomers (particularly thiophenol oligomers), and the like.

A hole buffer layer may be additionally provided between the hole injection layer and the hole transport layer. The hole buffer layer may include the compound of Formula 1 and may include hole injection or transport materials known in the art. In the case where the hole buffer layer includes the compound of Formula 1, the hole blocking layer may be composed of only the compound of Formula 1, but the compound of Formula 1 may be mixed or doped with other host materials.

An electron blocking layer may be provided between the hole transporting layer and the light emitting layer, and the compound of Formula 1 or a material known in the art may be used.

The light emitting layer may emit red, green, and / or blue light, and may be formed of a phosphor or a fluorescent material. The light emitting layer material may be those known in the art. As the luminescent host material, CBP (carbazole biphenyl) or mCP (1,3-bis (carbazol-9-yl) may be used.

When the light-emitting layer emits red light, the luminescent dopant may include PIQIR (acac) bis (1-phenylisoquinoline) acetylacetonate iridium, PQIr acac bis (1-phenylquinoline) acetylacetonate iridium, PQIr (tris (1-phenylquinoline) a phosphorescent material such as iridium and PtOEP, or a fluorescent material such as Alq3 (tris (8-hydroxyquinolino) aluminum) may be used. When the light emitting layer emits green light, a fluorescent substance such as Ir (ppy) 3 (fac tris (2-phenylpyridine) iridium) or Alq3 (tris (8-hydroxyquinolino) aluminum) may be used as the luminescent dopant However, it is not limited thereto. In the case where the light emitting layer emits blue light, the light emitting dopant may be a phosphorescent material such as (4,6-F ₂ ppy) ₂ Irpic, a spiro-DPVBi, spiro-6P, distyrylbenzene (DSB), distyrylarylene ), A PFO-based polymer, and a PPV-based polymer may be used, but the present invention is not limited thereto.

A hole blocking layer may be provided between the electron transporting layer and the light emitting layer, and materials known in the art may be used.

The electron transport layer can play a role in facilitating the transport of electrons. Materials known in the art such as Alq3 (tris (8-hydroxyquinolino) aluminum), PBD, TAZ, spiro-PBD, BAlq, SAlq can be used. The thickness of the electron transporting layer may be 1 to 50 nm. Here, when the thickness of the electron transporting layer is 1 nm or more, there is an advantage that the electron transporting property can be prevented from being lowered. When the thickness is 50 nm or less, the thickness of the electron transporting layer is too thick to increase the driving voltage There is an advantage that it can be prevented.

The electron injection layer may serve to smoothly inject electrons. Such as Alq3 (tris (8-hydroxyquinolino) aluminum), PBD, TAZ, spiro-PBD, BAlq or SAlq. Metal compounds include metal halides, and storage can be used, for example, can be used LiQ, LiF, NaF, KF, RbF, CsF, FrF, BeF _2, MgF _2, CaF _2, SrF _2, BaF ₂ and RaF ₂ and the like. The thickness of the electron injection layer may be 1 to 50 nm. If the thickness of the electron injection layer is 1 nm or more, there is an advantage that the electron injection characteristics can be prevented from being degraded. If the thickness is 50 nm or less, the thickness of the electron injection layer is too thick, There is an advantage that it can be prevented from being raised.

The second electrode is an electron injection electrode, and may be a material having a small work function to facilitate injection of electrons 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.

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 compound of the above formula (1).

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, by using a PVD (physical vapor deposition) method such as a sputtering method or an e-beam evaporation method, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the 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.

According to one embodiment of the present disclosure, the first electrode may be an anode and the second electrode may be a cathode.

According to another embodiment, the first electrode may be a cathode and the second electrode may be a cathode.

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. 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.

The embodiments described herein are illustrated by way of example. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Production Example 1

Synthesis of B1

Bromo-1,2-difluorobenzene (18.76 g, 97.20 mmol) and potassium carbonate (37.61, 272.2 mmol) were added to DMF (300 ml) and refluxed with stirring. After completion of the reaction, cool to room temperature and filter. After extraction with water and chlroform at room temperature, the white solid was columned with ethyl acetate and hexane to give the above compound B1 (18.82 g, yield 80%).

MS [M + H] < ⁺ > = 364.21

Synthesis of B2

Compound B2 was synthesized in the same manner as in the synthesis of B1 except that 1-bromo-2,3-difluorobenzene was used instead of 4-bromo-1,2-difluorobenzene.

MS [M + H] < ⁺ > = 364.21

Synthesis of B3

Compound B3 was synthesized in the same manner as in the synthesis of B1 except that 1,2-dichloro-4,5-difluorobenzene was used instead of 4-bromo-1,2-difluorobenzene.

MS [M + H] < ⁺ > = 354.20

Synthesis of B4

Compound B4 was synthesized in the same manner as in the synthesis of B1 except that 1,4-dichloro-2,3-difluorobenzene was used instead of 4-bromo-1,2-difluorobenzene.

MS [M + H] < ⁺ > = 354.20

Production Example 2

Synthesis of C1

4-chlorophenylboronic acid (11.30 g, 72.27 mmol) was added to tetrahydrofuran (300 ml), followed by addition of a 2 M aqueous potassium carbonate solution (150 ml), tetrakis triphenylphosphine (1.59 g, 2 mol%) was added thereto, followed by heating and stirring for 10 hours. After the temperature was lowered to room temperature and the reaction was terminated, the potassium carbonate aqueous solution was removed to separate layers. After removal of the solvent, the white solid was recrystallized from ethyl acetate to give the above compound C1 (23.1 g, yield 85%).

MS [M + H] < ⁺ > = 395.85

Synthesis of C2

Compound C2 was synthesized in the same manner except that 3-chlorophenylboronic acid was used instead of 4-chlorophenylboronic acid in the synthesis of C1.

MS [M + H] < ⁺ > = 395.85

Synthesis of C3

Compound C3 was synthesized in the same manner except that 2-chlorophenylboronic acid was used in place of 4-chlorophenylboronic acid in the synthesis of C1.

MS [M + H] < ⁺ > = 395.85

Synthesis of C4

(25 g, 68.83 mmol), bis (pinacolato) diboron (20.97 g, 82.59 mmol) and potassium acetate (23.65 g, 240.9 mmol) were mixed in a nitrogen atmosphere and dioxane (300 ml) . Bis (dibenzylidineacetone) palladium (1.19 g, 3 mol%) and tricyclohexylphosphine (1.13 g, 6 mol%) were added under reflux and heated and stirred for 3 hours. After completion of the reaction, the temperature was lowered to room temperature and then filtered. The filtrate was poured into water, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate. After distillation under reduced pressure, recrystallization from tetrahydrofuran and ethyl acetate gave Compound C4 (28.23 g, 83%).

MS [M + H] < ⁺ > = 411.28

Synthesis of C5

Synthesis was conducted in the same manner as in the synthesis of C1 except that B2 was used instead of B1 and (4'-chloro- [1,1'-biphenyl] -4-yl) boronic acid was used in place of 4-chlorophenylboronic acid To prepare a compound C5.

MS [M + H] < ⁺ > = 471.95

C6 synthesis

Compound C6 was synthesized by the same method except that B2 was used in place of B1 in the synthesis of C4.

MS [M + H] < ⁺ > = 411.28

Synthesis of D1

The procedure employed for the synthesis of C1 was repeated except that C6 was used instead of B1 and 2-bromo-7-chloro-9,9-dimethyl-9H-fluorene was used instead of 4-chlorophenylboronic acid to obtain Compound D1 .

MS [M + H] < ⁺ > = 512.02

Synthesis of D2

Compound D2 was synthesized in the same manner as in the synthesis of C1 except that C6 was used instead of B1 and 8-bromo-1-chlorobenzo [b, d] furan was used instead of 4-chlorophenylboronic acid.

MS [M + H] < ⁺ > = 485.94

Synthesis of E1

Biphenyl] -4-yl) amine (22.05 g, 68.58 mmol), sodium-t-butoxide (9.05 g, g, 94.14 mol) was added to toluene, and the mixture was heated with stirring, refluxed, and [bis (tri-t-butylphosphine)] palladium (390 mg, 1 mmol%) was added. After the reaction mixture was cooled to room temperature, the reaction mixture was recrystallized from tetrahydrofuran and ethyl acetate to give E1 (25.24 g, 81%).

MS [M + H] < ⁺ > = 464.58

Synthesis of E2

E1 (20 g, 43.41 mmol) was added to acetonitrile (400 ml) and dissolved. Then, perfluorophthanesulfonyl fluoride (15.64 g, 51.77 mmol) was slowly added dropwise at room temperature and stirred at room temperature for 3 hours. After extraction with water and chloroform at room temperature, the white solid was recrystallized from ethyl acetate to give the above compound E2 (27.66 g, yield 86%).

MS [M + H] < ⁺ > = 746.66

Preparation Example 3 (Preparation of compounds 1 to 15)

Synthesis of Compound 1

(13.54 g, 42.12 mmol) and sodium-t-butoxide (5.5 g, 57.81 mol) were dissolved in xylene (15 g, 41.29 mmol) And the mixture was stirred under heating, refluxed, and [bis (tri-t-butylphosphine)] palladium (240 mg, 1 mmol%) was added. After the reaction mixture was cooled to room temperature, the reaction mixture was recrystallized from tetrahydrofuran and ethyl acetate to obtain Compound 1 (18.4 g, 74%).

MS [M + H] < ⁺ > = 604.72

Synthesis of Compound 2

(1, 1'-diphenyl) -4-yl) -9,9-dimethyl-9H -Fluorene-2-amine, the compound 2 was prepared.

MS [M + H] < ⁺ > = 644.79

Synthesis of Compound 3

(1,1'-biphenyl) -2-yl) - (1,1 ', 4' , 1'-terphenyl) -4-amine, the same procedure was repeated to produce Compound 3.

MS [M + H] < ⁺ > = 680.82

Synthesis of Compound 4

In the synthesis of the above compound 1, N - ([1,1'-diphenyl] -4-yl) -9,9-biphenyl-9H -Fluorene-2-amine, the compound 4 was prepared.

MS [M + H] < ⁺ > = 768.93

Synthesis of Compound 5

Compound 5 was prepared by the same method except that B2 was used in place of B1 in the synthesis of Compound 3 above.

MS [M + H] < ⁺ > = 680.82

Synthesis of Compound 6

(1, 1'-biphenyl) -4-yl) - (1, 1'- 1 ', 4', 1'-terphenyl) -4-amine was used in place of 4-amino-2-methylpyridine.

MS [M + H] < ⁺ > = 756.92

Synthesis of Compound 7

Except that C1 was used instead of B1 in the synthesis of the compound 1 and N, 9-diphenyl-9H-carbazol-3-amine was used in place of di [(1,1'-biphenyl- The compound 7 was synthesized by the same method.

MS [M + H] < ⁺ > = 693.82

Synthesis of Compound 8

In the synthesis of Compound 1, C2 was used instead of B1, and N - ([1,1'-diphenyl] -2-yl) -9,9 -Dimethyl-9H-fluorene-2-amine was used in place of 4-fluoro-2-methyl-pyridine.

MS [M + H] < ⁺ > = 720.88

Synthesis of Compound 9

Except that C3 was used in place of B1 in the synthesis of the compound 1 and 4- (naphthalene-1-yl) -N-phenylaniline was used in place of di [(1,1'-biphenyl] To prepare Compound (9).

MS [M + H] < ⁺ > = 654.78

Synthesis of Compound 10

Compound 10 was prepared by the same method except for using C4 instead of B1 and E2 instead of 4-chlorophenylboronic acid in the synthesis of C1.

MS [M + H] < ⁺ > = 730.88

Synthesis of Compound 11

C5 was used in place of B1 in the synthesis of Compound 1, except that N-phenyl- [1,1'-biphenyl] -4-amine was used instead of di [(1,1'- Were synthesized in the same manner as above to give Compound 11.

MS [M + H] < ⁺ > = 680.82

Synthesis of Compound 12

Compound D1 was synthesized in the same manner as Compound 1 except that diphenylamine was used instead of di [(1,1'-biphenyl) -4-yl) amine to prepare Compound 12

MS [M + H] < ⁺ > = 644.79

Synthesis of Compound 13

Synthesis was carried out in the same manner as in the synthesis of the compound 1, except that D2 was used instead of B1 and N-phenyl-1-naphthylamine was used instead of di [(1,1'-biphenyl] -4- 13.

MS [M + H] < ⁺ > = 668.76

Synthesis of Compound 14

Except that B3 was used in place of B1 in the synthesis of Compound 1, and N-phenyl- [1,1'-biphenyl] -4-amine was used instead of di [(1,1'- , The compound 14 was synthesized.

MS [M + H] < ⁺ > = 771.93

Synthesis of Compound (15)

Compound B5 was used instead of B1 in the synthesis of C1, and triphenylamine-4-boronic acid was used in place of 4-chlorophenylboronic acid to prepare compound 15.

MS [M + H] < ⁺ > = 771.93

Example 1

A glass substrate (corning 7059 glass) coated with ITO (indium tin oxide) at a thickness of 1,000 Å was immersed in distilled water containing a dispersing agent and washed with ultrasonic waves. The detergent was a product of Fischer Co. The distilled water was supplied by Millipore Co. Distilled water, which was secondly filtered with a filter of the product, was used. After the ITO was washed for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After the distilled water was washed, ultrasonic washing was performed in the order of isopropyl alcohol, acetone, and methanol solvent, followed by drying.

Hexanitrile hexaazatriphenylene was thermally vacuum deposited on the prepared ITO transparent electrode to a thickness of 500 Å to form a hole injection layer. Compound 1 (900 Å) synthesized in the above Preparation Example 3, which is a hole transporting material, was vacuum-deposited thereon, and then HT2 was vacuum deposited on the HTL to a film thickness of 50 Å to form a hole control layer. A host H1 and a dopant D1 compound (25: 1) were vacuum deposited to a thickness of 300 Å as a compound light emitting layer. Next, an E1 compound (300 Å) was deposited in a 1: 1 ratio with LiQ, followed by thermal vacuum deposition with electron injection and transport layers. Lithium fluoride (LiF) having a thickness of 12 Å and aluminum having a thickness of 2,000 Å were sequentially deposited on the electron transporting layer to form a cathode, thereby preparing an organic light emitting device.

In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the deposition rate of lithium fluoride was 0.2 Å / sec, and the deposition rate of aluminum was 3 to 7 Å / sec.

Example 2

The same experiment was conducted except that Compound 2 was used instead of Compound 1 as the hole transporting layer in Example 1.

Example 3

The same experiment was conducted except that Compound 3 was used instead of Compound 1 as the hole transporting layer in Example 1.

Example 4

The same experiment was carried out except that Compound 4 was used instead of Compound 1 as the hole transporting layer in Example 1 above.

Example 5

The same experiment was conducted except that Compound 12 was used instead of Compound 1 as the hole transporting layer in Example 1 above.

Example 6

The same experiment was conducted except that Compound 14 was used instead of Compound 1 as the hole transporting layer in Example 1 above.

Example 7

The same experiment was conducted except that Compound 15 was used instead of Compound 1 as the hole transporting layer in Example 1.

Comparative Example 1

The same experiment was carried out except that HT1 was used instead of Compound 1 as the hole transporting layer in Example 1 above.

Comparative Example 2

The same experiment was carried out except that HT3 was used instead of Compound 1 as the hole transporting layer in Example 1 above.

Comparative Example 3

The same experiment was conducted except that HT4 was used instead of Compound 1 as the hole transporting layer in Example 1 above.

Comparative Example 4

The same experiment was conducted except that HT3 was used instead of Compound 1 as the hole transporting layer in Example 1, and HT5 was used instead of HT2 as the hole adjusting layer.

Table 1 shows the results of experiments of the organic light emitting devices manufactured using the respective compounds as the hole transporting layer materials as in Examples 1 to 7 and Comparative Examples 1 to 4.

Experimental Example 20 mA / cm 2	Hole transport layer	The hole-	Voltage (V) (@ 20 mA / cm 2 )	Cd / A (@ 20 mA / cm 2 )	The color coordinates (x, y)	Life (T95, h) (@ 20 mA / cm 2 )
Example 1	Compound 1	HT2	3.51	6.71	(0.135, 0.138)	49.0
Example 2	Compound 2	HT2	3.45	6.63	(0.134, 0.137)	50.2
Example 3	Compound 3	HT2	3.41	6.58	(0.135, 0.138)	55.2
Example 4	Compound 4	HT2	3.34	6.82	(0.134, 0.138)	51.2
Example 5	Compound 12	HT2	3.42	6.72	(0.136, 0.139)	48.9
Example 6	Compound 14	HT2	3.31	6.52	(0.135, 0.138)	48.5
Example 7	Compound 15	HT2	3.50	6.69	(0.133, 0.139)	49.1
Comparative Example 1	HT1	HT2	3.82	5.70	(0.134, 0.139)	28.1
Comparative Example 2	HT3	HT2	3.94	5.81	(0.135, 0.138)	21.0
Comparative Example 3	HT4	HT2	3.78	5.66	(0.134, 0.138)	33.0
Comparative Example 4	HT3	HT5	3.88	5.82	(0.136, 0.139)	28.0

Example 8

A glass substrate (corning 7059 glass) coated with ITO (indium tin oxide) at a thickness of 1,000 Å was immersed in distilled water containing a dispersing agent and washed with ultrasonic waves. The detergent was a product of Fischer Co. The distilled water was supplied by Millipore Co. Distilled water, which was secondly filtered with a filter of the product, was used. After the ITO was washed for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After the distilled water was washed, ultrasonic washing was performed in the order of isopropyl alcohol, acetone, and methanol solvent, followed by drying.

Hexanitrile hexaazatriphenylene was thermally vacuum deposited on the prepared ITO transparent electrode to a thickness of 500 Å to form a hole injection layer. HT1 (900 Å), which is a hole transport material, was vacuum deposited on the hole transport layer, and then Compound 1 synthesized in Production Example 3 was vacuum deposited on the hole transport layer to a film thickness of 50 Å to form a hole control layer. A host H1 and a dopant D1 compound (25: 1) were vacuum deposited to a thickness of 300 Å as a compound light emitting layer. Then, an E1 compound (300 ANGSTROM) was sequentially vacuum-deposited by electron injection and transport layer. Lithium fluoride (LiF) having a thickness of 12 Å and aluminum having a thickness of 2,000 Å were sequentially deposited on the electron transporting layer to form a cathode, thereby preparing an organic light emitting device.

In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the deposition rate of lithium fluoride was 0.2 Å / sec, and the deposition rate of aluminum was 3 to 7 Å / sec.

Example 9

The same experiment was conducted except that the compound 3 was used instead of the compound 1 as the hole-adjusting layer in Example 8.

Example 10

The same experiment was carried out as in Example 8 except that Compound 5 was used instead of Compound 1 as the hole-adjusting layer.

Example 11

The same experiment was conducted except that the compound 6 was used instead of the compound 1 as the hole-adjusting layer in Example 8.

Example 12

The same experiment was conducted except that the compound 7 was used instead of the compound 1 as the hole-controlling layer in Example 8.

Example 13

The same experiment was carried out except that Compound 8 was used instead of Compound 1 as the hole-adjusting layer in Example 8.

Example 14

The same experiment was conducted except that Compound 9 was used instead of Compound 1 as the hole-adjusting layer in Example 8.

Example 15

The same experiment was conducted except that the compound 10 was used instead of the compound 1 as the hole-adjusting layer in Example 8.

Example 16

The same experiment was conducted except that the compound 11 was used instead of the compound 1 as the hole-controlling layer in Example 8.

Example 17

The same experiment was conducted except that the compound 13 was used instead of the compound 1 as the hole-adjusting layer in Example 8.

Comparative Example 5

The same experiment was conducted except that HT5 was used instead of Compound 1 as the hole-controlling layer in Example 8. [

Comparative Example 6

In Example 8, HT3 was used instead of HT1 as the hole transport layer, and HT5 was used in place of the compound 1 as the hole control layer.

Comparative Example 7

In the same manner as in Example 8, except that HT6 was used instead of Compound 1 as the hole-controlling layer.

Comparative Example 8

The same experiment was conducted except that HT4 was used instead of HT1 as the hole transport layer in Example 8, and HT6 was used in place of the compound 1 as the hole control layer.

Table 2 shows the results of the organic light emitting device manufactured using the respective compounds as the hole control layer materials as in Examples 8 to 17 and Comparative Examples 5 to 8.

Experimental Example 20 mA / cm 2	Hole transport layer	The hole-	Voltage (V) (@ 20 mA / cm 2 )	Cd / A (@ 20 mA / cm 2 )	The color coordinates (x, y)	Life (T95, h) (@ 20 mA / cm 2 )
Example 8	HT1	Compound 1	3.33	6.89	(0.135, 0.138)	52.0
Example 9	HT1	Compound 3	3.52	6.79	(0.134, 0.138)	48.0
Example 10	HT1	Compound 5	3.44	6.67	(0.134, 0.138)	46.8
Example 11	HT1	Compound 6	3.45	6.58	(0.137, 0.134)	47.1
Example 12	HT1	Compound 7	3.52	6.87	(0.138, 0.138)	42.5
Example 13	HT1	Compound 8	3.38	6.82	(0.135, 0.139)	46.5
Example 14	HT1	Compound 9	3.39	6.81	(0.135, 0.138)	49.7
Example 15	HT1	Compound 10	3.51	6.71	(0.135, 0.139)	50.1
Example 16	HT1	Compound 11	3.45	6.63	(0.134, 0.138)	49.8
Example 17	HT1	Compound 13	3.41	6.58	(0.134, 0.138)	47.4
Comparative Example 5	HT1	HT5	3.82	5.71	(0.134, 0.138)	33.5
Comparative Example 6	HT3	HT5	3.78	5.89	(0.137, 0.135)	28.2
Comparative Example 7	HT1	HT6	3.75	5.91	(0.134, 0.138)	35.1
Comparative Example 8	HT4	HT6	3.70	5.84	(0.135, 0.137)	29.4

The compound represented by the chemical formula according to the present invention can function as a hole transporting and hole controlling in an organic electronic device including an organic light emitting device, and the device according to the present invention exhibits excellent characteristics in terms of efficiency, driving voltage and stability.

Claims (11)

1. A compound represented by the following formula (1):

   [Chemical Formula 1]

   

   In formula (1)

   X1 and X2 are each independently O or S,

   R1 to R3 each independently represent hydrogen; heavy hydrogen; A halogen group; A substituted or unsubstituted silyl group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

   a and b are each independently an integer of 0 to 4,

   c is an integer of 1 to 4,

   When a to c are each independently 2 or more, the substituents in parentheses are the same or different from each other,

   At least one of R < 3 > is represented by the following formula (2)

   (2)

   

   In formula (2)

   L is a substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,

   Ar1 and Ar2 each independently represent a substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

   n is an integer of 0 to 3,

   When n is 2 or more, the substituents in parentheses are the same or different from each other,

   Adjacent groups among Ar1, Ar2 and L may combine with each other to form a ring.
2. The method according to claim 1,

   (1) is represented by any one of the following formulas (3) to (6):

   (3)

   

   [Chemical Formula 4]

   

   [Chemical Formula 5]

   

   [Chemical Formula 6]

   

   In formulas (3) to (6)

   R 1, R 2, R 3, X 1, X 2, a and b are as defined in claim 1,

   And two or more R < 3 > s are the same or different from each other.
3. The method according to claim 1,

   Wherein L is any one of the following formulas:

   

   

   A1 to A3 each independently represent a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

   a1 to a3 each represent an integer of 0 to 3,

   When a1 to a3 are each independently an integer of 2 or more, the substituents in parentheses are the same or different from each other,

   

   Represents the position to which a substituent is connected.
4. The method according to claim 1,

   Ar1 and Ar2 each independently represent a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted naphthalene group; A substituted or unsubstituted phenanthrene group; A substituted or unsubstituted fluorene group; A substituted or unsubstituted spirobifluorene group; A substituted or unsubstituted dibenzofurane group; A substituted or unsubstituted dibenzothiophene group; Or a substituted or unsubstituted carbazole group.
5. The method according to claim 1,

   A ring formed by bonding adjacent groups of Ar1, Ar2 and L to each other is any one of the following formulas:

   

   R5 to R16 each independently represent a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

   d is an integer of 0 to 9,

   e to h are each independently an integer of 0 to 8,

   i is an integer of 0 to 3,

   j is an integer of 0 to 6,

   When d to j are each independently an integer of 2 or more, the substituents in the parentheses are the same or different from each other,

   

   Represents the position to which a substituent is connected.
6. The compound according to claim 1, wherein the compound represented by the formula (1) is selected from the following compounds:

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   
7. A first electrode; A second electrode facing the first electrode; And at least one organic compound layer provided between the first electrode and the second electrode,

   Wherein at least one of the organic material layers comprises a compound according to any one of claims 1 to 6.
8. The method of claim 7,

   Wherein the organic compound layer is made of the compound alone or doped with the compound.
9. The method of claim 7,

   Wherein the organic material layer is a hole injecting layer, a hole transporting layer, an electron transporting layer, or an electron injecting layer.
10. The method of claim 7,

    Wherein the organic material layer is a layer which simultaneously injects holes and transports holes.
11. The method of claim 7,

    Wherein the organic material layer is a light emitting layer.