WO2019240471A1 - Heterocyclic compound and organic light-emitting device comprising same - Google Patents

Abstract

The present specification relates to a heterocyclic compound of chemical formula 1, an organic light-emitting device comprising same, and a preparation method therefor.

Description

Heterocyclic compound and organic light emitting device comprising the same

The present invention claims the benefit of the filing date of Korean Patent No. 10-2018-0066879 filed to the Korean Intellectual Property Office on June 11, 2018, the entire contents of which are incorporated herein.

The present specification relates to a heterocyclic compound 유기 organic light emitting device including the same.

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. The organic material layer is often made of a multi-layered structure composed of different materials to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer, and excitons are formed when the injected holes and the electrons meet each other. When it falls back to the ground, it glows.

There is a continuing need for the development of new materials for such organic light emitting devices.

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

An exemplary embodiment of the present specification provides a heterocyclic compound represented by Formula 1 below.

[Formula 1]

In Chemical Formula 1,

X ₁ to X ₇ is N or CR ₁ , at least one of X ₁ to X ₇ is N,

Y ₁ to Y ₇ is N or CR 2, and at least one of Y ₁ to Y ₇ is N,

R1 is hydrogen or -L _n -Ar,

R2 is hydrogen,

L is a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted monocyclic having 3 to 30 carbon atoms Heteroarylene group,

Ar is hydrogen; heavy hydrogen; Nitrile group; Halogen group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted silyl group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted amine group; Substituted or unsubstituted aryl group; A pyridine group unsubstituted or substituted with an aryl group; Pyrimidine groups unsubstituted or substituted with aryl groups; Triazine group unsubstituted or substituted with an aryl group or a heteroaryl group; Pyridazine groups unsubstituted or substituted with an aryl group; Benzoimidazole group unsubstituted or substituted with an alkyl group; Imidazole group; Dibenzofuran group; Dibenzothiophene group; Or a phenanthroline group,

n is an integer of 1 to 3, and when n is 2 or more, L is the same as or different from each other.

Another embodiment of the present specification provides a first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including one or two or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes a heterocyclic compound of Chemical Formula 1. To provide.

The heterocyclic compound according to the exemplary embodiment of the present specification may be used as a material of the organic material layer of the organic light emitting device, and by using the same, it is possible to improve efficiency, low driving voltage, and / or lifespan characteristics in the organic light emitting device.

1 illustrates an organic light emitting device according to an exemplary embodiment of the present specification.

2 illustrates an organic light emitting device according to an exemplary embodiment of the present specification.

[Description of the code]

1: substrate

2: first electrode

3: organic material layer

4: second electrode

5: hole injection layer

6: hole transport layer

7: electron suppression layer

8: light emitting layer

9: hole blocking layer

10: electron injection and transport layer

Hereinafter, this specification is demonstrated in detail.

The present specification provides a heterocyclic compound represented by Chemical Formula 1.

The heterocyclic compound of the present specification is characterized in that it has a ring structure in which a 6-membered ring including N or more is condensed.

In general, the electron mobility of a compound depends on the orientation on the 3D structure of the molecule, and when it is a more horizontal structure, the electron mobility is enhanced.

According to an exemplary embodiment of the present specification, the heterocyclic compound represented by Chemical Formula 1 in which one -L _n -Ar is substituted is stronger than the compound in which two -L1-Ar1 is substituted, and thus the horizontal structural tendency of the molecule is strong. There is an advantage that the mobility is increased.

Accordingly, when the heterocyclic compound represented by Chemical Formula 1 is used in an organic light emitting device, the driving voltage is low, and high efficiency and long life are effective (see APPLIED PHYSICS LETTERS 95, 243303 (2009)).

In the present specification, when a part "includes" a certain component, this means that it may further include other components, without excluding other components unless specifically stated otherwise.

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

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

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

As used herein, the term "substituted or unsubstituted" is deuterium; Nitrile group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted aryl group; And it is substituted with one or two or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group, or two or more of the substituents exemplified above are substituted with a substituent, or means that do not have any substituents. For example, "a substituent to which two or more substituents are linked" may be an aryl group substituted with an aryl group, an aryl group substituted with a heteroaryl group, a heterocyclic group substituted with an aryl group, an aryl group substituted with an alkyl group, and the like.

In the present specification, the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 30.

In the present specification, specifically, the silyl group includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like. However, the present invention is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.

When the aryl group is a monocyclic aryl group, carbon number is not particularly limited, but is preferably 6 to 30 carbon atoms.

Carbon number is not particularly limited when the aryl group is a polycyclic aryl group. It is preferable that it is C10-30.

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, may be a polycyclic aryl group. The arylamine group including two or more aryl groups may simultaneously include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group. 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 heteroaryl group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like. The carbon number is not particularly limited, but is preferably 2 to 30 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic.

In the present specification, the arylene group is the same as the definition of an aryl group except that it is divalent.

In the present specification, the heteroarylene group is the same as the definition of the heteroaryl group, except that it is divalent.

In one embodiment of the present specification, Chemical Formula 1 may be represented by the following Chemical Formula 2.

[Formula 2]

In Formula 2, the definitions of X _1, X _2, X ₄ to X _7, Y ₁ to Y _7, L, Ar, and n are the same as defined in Formula 1.

According to an exemplary embodiment of the present specification, any one or more of X ₁ to X ₇ is N, the rest is CR1.

According to an exemplary embodiment of the present specification, any one of X ₁ to X ₇ is N, the rest is CR1.

According to an exemplary embodiment of the present specification, any one or more of the Y ₁ to Y ₇ is N, the rest is CR1.

According to an exemplary embodiment of the present specification, any one of the Y ₁ to Y ₇ is N, the rest is CR1.

According to an exemplary embodiment of the present specification, X ₁ is N, X ₂ to X ₇ are CR 1.

According to an exemplary embodiment of the present specification, X ₂ is N, X _1, and X ₃ to X ₇ are CR 1.

According to an exemplary embodiment of the present specification, X ₃ is N, X _1, X _2, and X ₄ to X ₇ are CR 1.

According to an exemplary embodiment of the present specification, X ₄ is N, X ₁ to X _3, and X ₅ to X ₇ are CR 1.

According to an exemplary embodiment of the present specification, X ₅ is N, X ₁ to X _4, X ₆ and X ₇ are CR 1.

According to an exemplary embodiment of the present specification, X ₆ is N, X ₁ to X _5, and X ₇ are CR 1.

According to an exemplary embodiment of the present specification, X ₇ is N, X ₁ to X ₆ are CR ₁ .

According to an exemplary embodiment of the present specification, Y ₁ is N, Y ₂ to Y ₇ are CR ₂ .

According to an exemplary embodiment of the present specification, Y ₂ is N, Y _1, and Y ₃ to Y ₇ are CR 2.

According to an exemplary embodiment of the present specification, Y ₃ is N, Y _1, Y _2, and Y ₄ to Y ₇ are CR 2.

According to an exemplary embodiment of the present specification, Y ₄ is N, Y ₁ to Y _3, and Y ₅ to Y ₇ are CR 2.

According to an exemplary embodiment of the present specification, Y ₅ is N, Y ₁ to Y _4, Y ₆ and Y ₇ are CR 2.

According to an exemplary embodiment of the present specification, Y ₆ is N, Y ₁ to Y _5, and Y ₇ are CR 2.

According to an exemplary embodiment of the present specification, Y ₇ is N, Y ₁ to Y ₆ are CR 2.

In one embodiment of the present specification, Chemical Formula 1 may be represented by any one of the following Chemical Formulas 3 to 9.

For Formula 3 to 9, _wherein, the definition of L, n and Ar are as defined in formula (I).

In one embodiment of the present specification, Chemical Formula 1 may be represented by the following Chemical Formula 1-1.

[Formula 1-1]

In Chemical Formula 1-1, X ₁ to X _7, and Y ₁ to Y ₇ are as defined above,

Z ₁ to Z ₃ are the same as or different from each other, and each independently N or CH ₂ ,

At least one of Z ₁ to Z ₃ is N,

L ₁₀₁ is a direct bond, a substituted or unsubstituted arylene group, or a heteroarylene group,

Ar ₁₀₁ and Ar ₁₀₂ are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted silyl group, substituted or Unsubstituted phosphine oxide group, substituted or unsubstituted amine group, substituted or unsubstituted aryl group, or substituted or unsubstituted heteroaryl group,

m is an integer of 1 to 2, and when m is 2, L ₁₀₁ is the same as or different from each other.

In one embodiment of the present specification, Chemical Formula 1 may be represented by the following Chemical Formula 1-2.

[Formula 1-2]

In Chemical Formula 1-2, X ₁ to X _7, and Y ₁ to Y ₇ are as defined above,

R ₃ is a substituted or unsubstituted phosphine oxide group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

o is an integer from 0 to 3, and when o is 2 or more, R ₃ is the same as or different from each other.

According to an exemplary embodiment of the present specification, R ₁ and R ₂ is hydrogen.

According to an exemplary embodiment of the present specification, R ₃ is a phosphine oxide group substituted with an aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted C 3 to 30 carbon atoms. Is a heteroaryl group.

According to an exemplary embodiment of the present specification, R ₃ is a phosphine oxide group substituted with an aryl group having 6 to 30 carbon atoms; An aryl group having 6 to 30 carbon atoms unsubstituted or substituted with an aryl group or a heteroaryl group; Or a heteroaryl group including any one or more of N, O, and S unsubstituted or substituted with an aryl group or a heteroaryl group.

According to an exemplary embodiment of the present disclosure, wherein R ₃ is a phenanthrene group; Phosphine oxide groups; Phenanthroline group; Pyridazine groups; Or benzimidazole group,

The phenanthrene group; Phosphine oxide groups; Phenanthroline group; Pyridazine groups; Or the benzimidazole group is unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group containing any one or more of N, O and S having 3 to 30 carbon atoms.

According to an exemplary embodiment of the present disclosure, wherein R ₃ is a phenanthrene group; Phosphine oxide groups; Phenanthroline group; Pyridazine groups; Or benzimidazole group,

The phenanthrene group; Phosphine oxide groups; Phenanthroline group; Pyridazine groups; Or the benzimidazole group is methyl group, ethyl group, propyl group, butyl group, terbutyl group, phenyl group, biphenyl group, terphenyl group, naphthyl group, anthracene group, phenanthrene group, pyrene group, triphenylene group, pyridine group, pyrimi It is unsubstituted or substituted by a dine group, a triazine group, a carbazole group, a dibenzofuran group, or a dibenzothiophene group.

According to an exemplary embodiment of the present disclosure, wherein R ₃ is a phenanthrene group; Phosphine oxide groups substituted with aryl groups; Phenanthroline group; Pyridazine groups unsubstituted or substituted with an aryl group; Or a benzimidazole group unsubstituted or substituted with an alkyl group.

According to an exemplary embodiment of the present disclosure, wherein R ₃ is a phosphine oxide group substituted with a phenyl group; Phenanthroline group; Pyridazine groups unsubstituted or substituted with a phenyl group or a naphthyl group; Or a benzimidazole group unsubstituted or substituted with a methyl group.

According to an exemplary embodiment of the present specification, L is one or more of a direct bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a substituted or unsubstituted C 3 to 30 N, O, and S Heteroarylene group.

According to an exemplary embodiment of the present specification, L is a direct bond; An arylene group having 6 to 30 carbon atoms or at least one of N, O, and S having 3 to 30 carbon atoms is a heteroarylene group.

According to an exemplary embodiment of the present specification, L is a direct bond, a phenylene group, a divalent biphenyl group, a divalent terphenyl group, a naphthylene group, an anthracenylene group, a phenanthrenylene group, or a divalent pyrene group.

According to an exemplary embodiment of the present specification, L is a direct bond, a phenylene group, a naphthylene group, or a divalent pyrene group.

According to an exemplary embodiment of the present specification, L ₁₀₁ is a direct bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a substituted or unsubstituted C 3 to 30 of any one of N, O, and S Is a heteroarylene group.

According to an exemplary embodiment of the present specification, the L ₁₀₁ is a direct bond; An arylene group having 6 to 30 carbon atoms or at least one of N, O, and S having 3 to 30 carbon atoms is a heteroarylene group.

According to an exemplary embodiment of the present specification, L ₁₀₁ is a direct bond, a phenylene group, a divalent biphenyl group, a divalent terphenyl group, a naphthylene group, an anthracenylene group, a phenanthrenylene group, or a divalent pyrene group.

According to an exemplary embodiment of the present specification, L ₁₀₁ is a direct bond, a phenylene group, or a naphthylene group.

According to an exemplary embodiment of the present specification, Ar is hydrogen, deuterium, a nitrile group, an alkyl group, a phosphine oxide group unsubstituted or substituted with an aryl group, a silyl group substituted with an alkyl group, an aryl group unsubstituted or substituted with a nitrile group, A heteroaryl group unsubstituted or substituted with an alkyl group, or a heteroaryl group unsubstituted or substituted with an aryl group.

According to an exemplary embodiment of the present specification, Ar is hydrogen, deuterium, a nitrile group, an alkyl group, a phosphine oxide group unsubstituted or substituted with an aryl group, a silyl group substituted with an alkyl group, an aryl group unsubstituted or substituted with a nitrile group, A heteroaryl group unsubstituted or substituted with an alkyl group, or a heteroaryl group unsubstituted or substituted with an aryl group.

According to an exemplary embodiment of the present specification, Ar is a phosphine oxide group unsubstituted or substituted with an aryl group having 6 to 30 carbon atoms; An aryl group having 6 to 30 carbon atoms unsubstituted or substituted with a nitrile group; Or a C3-C30 heteroaryl group unsubstituted or substituted with a C1-C10 alkyl group or a C6-C30 aryl group.

According to an exemplary embodiment of the present specification, Ar is a phenyl group, biphenyl group, terphenyl group, naphthyl group, fluoranthene group, pyrene group, triphenylene group, phosphine oxide group, quinoline group, quinazoline group, pyridine group, pyri Midine group, triazine group, pyridazine group, benzoimidazole group, imidazole group, dibenzofuran group, dibenzothiophene group, or phenanthroline group,

Examples of Ar are a group consisting of deuterium, a nitrile group, a fluoro group, a chloro group, a bromo group, an iodo group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a heteroaryl group having 3 to 30 carbon atoms. It may be substituted or unsubstituted with one or more selected from.

According to an exemplary embodiment of the present specification, Ar is a phenyl group unsubstituted or substituted with a nitrile group; A biphenyl group unsubstituted or substituted with a nitrile group; Terphenyl group; Phosphine oxide groups substituted with a phenyl group or a naphthyl group; A quinazoline group unsubstituted or substituted with a phenyl group; Pyridazine groups unsubstituted or substituted with phenyl groups; Benzoimidazole group unsubstituted or substituted with a methyl group; Fluoranthene group; Pyridine group; And a triazine group unsubstituted or substituted with a phenyl group, a benzonitrile group or a pyridine group.

According to an exemplary embodiment of the present specification, Ar ₁₀₁ and Ar ₁₀₂ are the same as or different from each other, and each independently, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted carbon atom having 3 to 30 carbon atoms. Heteroaryl group.

According to an exemplary embodiment of the present specification, Ar ₁₀₁ and Ar ₁₀₂ are the same as or different from each other, and each independently an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 3 to 30 carbon atoms,

The aryl group having 6 to 30 carbon atoms, or the heteroaryl group having 3 to 30 carbon atoms is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a halogen group, a nitrile group, an alkyl group, an aryl group, or a heteroaryl group.

According to an exemplary embodiment of the present specification, Ar ₁₀₁ and Ar ₁₀₂ are the same as or different from each other, and each independently, a phenyl group, a biphenyl group, a naphthyl group, a pyridine group, a pyrimidine group, or a triazine group,

The phenyl group, biphenyl group, naphthyl group, pyridine group, pyrimidine group, or triazine group is a nitrile group, phenyl group, biphenyl group, terphenyl group, naphthyl group, anthracene group, pyrene group, phenanthrene group, triphenylene group, phenanthrol It may be substituted or unsubstituted with any one or more substituents selected from the group consisting of a lean group, a pyridine group, a pyrimidine group, a dibenzofuran group, and a dibenzothiophene group.

According to an exemplary embodiment of the present specification, Ar ₁₀₁ and Ar ₁₀₂ are the same as or different from each other, and each independently, a phenyl group, a biphenyl group, a naphthyl group, or a pyridine group,

The phenyl group, biphenyl group, naphthyl group, or pyridine group includes nitrile group, phenyl group, biphenyl group, naphthyl group, pyrene group, phenanthrene group, phenanthroline group, pyridine group, pyrimidine group, dibenzofuran group, and dibenzo It may be substituted or unsubstituted with any one or more substituents selected from the group consisting of thiophene groups.

According to yet an embodiment of the present disclosure, the heterocyclic compound of Formula 1 may be represented by any one of the following structural formula.

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The organic light emitting device of the present invention may be manufactured by a conventional method and material for manufacturing an organic light emitting device, except that at least one organic material layer is formed using the above-described compound.

In addition, the organic light emitting display device according to the present invention includes a first electrode; A second electrode provided to face the first electrode; And one or two or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include a heterocyclic compound represented by Chemical Formula 1.

According to an exemplary embodiment of the present invention, the organic material layer includes an electron injection layer, an electron transport layer, or an electron injection and transport layer, and the electron injection layer, the electron transport layer, or the electron injection and transport layer is a hetero ring of Formula 1 Compound.

According to an exemplary embodiment of the present invention, the electron injection layer, the electron transport layer, or the electron injection and transport layer may include a heterocyclic compound of Formula 1 and additional compounds.

According to the exemplary embodiment of the present invention, the electron injection layer, the electron transport layer, or the electron injection and transport layer may include the heterocyclic compound of Formula 1, and may further use a metal complex.

According to the exemplary embodiment of the present invention, the electron injection layer, the electron transport layer, or the electron injection and transport layer may include the heterocyclic compound of Formula 1, and may further use a lithium complex.

According to the exemplary embodiment of the present invention, the electron injection layer, the electron transport layer, or the electron injection and transport layer using the heterocyclic compound and the lithium quinoline-8- oleate of the formula (1) in a weight ratio of 1: 1 to 2: 1 do.

According to an exemplary embodiment of the present invention, the organic material layer includes a hole injection layer, a hole transport layer, or a hole injection and transport layer, the hole injection layer, a hole transport layer, or a hole injection and transport layer is a heterocyclic compound of Formula 1 It includes.

According to an exemplary embodiment of the present invention, the organic material layer includes a light emitting layer, and the light emitting layer includes a heterocyclic compound of Chemical Formula 1.

1 illustrates a structure of an organic light emitting device in which a first electrode 2, an organic material layer 3, and a second electrode 4 are sequentially stacked on a substrate 1. The heterocyclic compound of Formula 1 is included in the organic material layer 3.

2 shows a first electrode 2, a hole injection layer 5, a hole transport layer 6, an electron suppression layer 7, a light emitting layer 8, a hole blocking layer 9, an electron injection and the like on a substrate 1. The structure of the organic light emitting element in which the transport layer 10 and the second electrode 4 are sequentially stacked is illustrated. The heterocyclic compound of Formula 1 may preferably be included in the hole blocking layer 9 or the electron injection and transport layer 10.

However, the structure of the organic light emitting device according to the exemplary embodiment of the present specification is not limited to FIGS. 1 and 2, and may be any one of the following structures.

(1) Anode / hole transport layer / light emitting layer / electron transport layer / cathode

(2) Anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

(3) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

(4) Anode / hole transport layer / hole control layer / light emitting layer / electron transport layer / electron injection layer / cathode

(5) Anode / hole injection layer / hole transport layer / hole control layer / light emitting layer / electron transport layer / electron injection layer / cathode

(6) Anode / hole transport layer / light emitting layer / electron control layer / electron transport layer / cathode

(7) Anode / hole transport layer / light emitting layer / electron control layer / electron transport layer / electron injection layer / cathode

(8) Anode / hole injection layer / hole transport layer / light emitting layer / electron control layer / electron transport layer / cathode

(9) Anode / hole injection layer / hole transport layer / light emitting layer / electron control layer / electron transport layer / electron injection layer / cathode

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

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

In an exemplary embodiment of the present invention, the organic material layer including the heterocyclic compound of Formula 1 may include at least one of an electron injection layer, an electron transport layer, a layer for simultaneously injecting and transporting electrons, and at least one of the layers. The layer may include the heterocyclic compound of Formula 1 above.

As the anode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); ZnO: Al or SnO ₂ : Combination of metals and oxides such as Sb; Conductive polymers such as poly (3-methyl compound), poly [3,4- (ethylene-1,2-dioxy) compound] (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.

It is preferable that the cathode material is 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; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

The hole injection material is a material capable of well injecting holes from the anode at a low voltage, and the highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene-based organics, quinacridone-based organics, and perylene-based Organic compounds, anthraquinones and polyaniline and poly-compounds of conductive polymers, and the like, but are not limited thereto.

As the hole transporting material, a material capable of transporting holes from the anode or the hole injection layer to be transferred to the light emitting layer is suitable. Specific examples thereof include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable. Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq ₃ ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; 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 containing compound. Specifically, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and the heterocyclic compounds include heterocyclic compounds, dibenzofuran derivatives, and ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

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

The organic light emitting device of the present specification may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer is formed using the heterocyclic compound.

Dopant materials include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, and include pyrene, anthracene, chrysene, and periplanthene having an arylamino group, and a styrylamine compound may be substituted or unsubstituted. At least one arylvinyl group is substituted with the arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.

The hole blocking layer is a layer which blocks the cathode from reaching the hole, and may generally be formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes, and the like, but are not limited thereto.

The organic light emitting device according to the present specification may be a top emission type, a bottom emission type, or a double side emission type according to a material used.

According to an exemplary embodiment of the present specification, the heterocyclic compound of Formula 1 may be prepared according to the following reaction scheme, but is not limited thereto. In the following schemes, the type and number of substituents can synthesize various kinds of intermediates as those skilled in the art appropriately select known starting materials. Reaction type and reaction conditions may be used those known in the art.

Production Example  1. Synthesis of Compound E1

Compound 8- (4,4,5,5-tetramethyl-1,3,2-dioxaboron-2-yl) -5,8'-biquinoline (10.0 g, 26.2 mmol) and 2-chloro- Dissolve 4,6-diphenyl-1,3,5-triazine (7.4 g, 27.5 mmol) completely in tetrahydrofuran (100 ml), add potassium carbonate (14.4 g, 104.6 mmol) in 43 ml of water, and add Tetrakistriphenyl-phosphinepalladium (907 mg, 0.79 mmol) was added thereto, and the mixture was heated and stirred for 7 hours. After the temperature was lowered to room temperature and the reaction was terminated, the white carbonate was filtered by removing the potassium carbonate solution. The filtered white solid was washed twice with tetrahydrofuran and ethyl acetate each to prepare Compound E1 (10.2 g, yield 80%).

MS [M + H] ⁺ = 488

Production Example  2. Synthesis of Compound E2

In Preparation Example 1, 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-tri instead of 2-chloro-4,6-diphenyl-1,3,5-triazine Except for using azine, the compound E2 was prepared in the same manner as in Preparation Example 1.

MS [M + H] ⁺ = 564

Production Example  3. Synthesis of Compound E3

2- (6-bropoppyridin-3-yl) -4,6-diphenyl-1,3, instead of 2-chloro-4,6-diphenyl-1,3,5-triazine in Preparation Example 1 Compound E3 was prepared in the same manner as in Preparation Example 1, except that 5-triazine was used.

MS [M + H] ⁺ = 565

Production Example  4. Synthesis of Compound E4

2-chloro-4- (3- (dibenzo [b, d] furan-2-yl) phenyl instead of 2-chloro-4,6-diphenyl-1,3,5-triazine in Preparation Example 1 Compound E4 was prepared in the same manner as in Preparation Example 1, except that) -6-phenyl-1,3,5-triazine was used.

MS [M + H] ⁺ = 654

Production Example  5. Synthesis of Compound E5

Except for using 3- (4-bromophenyl) -5- (naphthalen-2-yl) pyridazine instead of 2-chloro-4,6-diphenyl-1,3,5-triazine in Preparation Example 1 Compound E5 was prepared in the same manner as in Preparation Example 1.

MS [M + H] ⁺ = 537

Production Example  6. Synthesis of Compound E6

2- (3-bromophenyl) -4-phenyl-6- (4- (pyridin-4-yl) instead of 2-chloro-4,6-diphenyl-1,3,5-triazine in Preparation Example 1 Compound E6 was prepared in the same manner as in Preparation Example 1, except that 1) phenyl) -1,3,5-triazine was used.

MS [M + H] ⁺ = 641

Production Example  7. Synthesis of Compound E7

2- (4-bromonaphthalen-1-yl) -4,6-diphenyl-1,3, instead of 2-chloro-4,6-diphenyl-1,3,5-triazine in Preparation Example 1 Compound E7 was prepared in the same manner as in Preparation Example 1, except that 5-triazine was used.

MS [M + H] ⁺ = 614

Production Example  8. Synthesis of Compound E8

In Preparation Example 1, 2- (5-bromopyridin-2-yl) -4,6-diphenyl-1,3, instead of 2-chloro-4,6-diphenyl-1,3,5-triazine Compound E8 was prepared in the same manner as in Preparation Example 1, except that 5-triazine was used.

MS [M + H] ⁺ = 641

Production Example  9. Synthesis of Compound E9

3- (4- (4-bromophenyl) -6-phenyl-1,3,5-triazine instead of 2-chloro-4,6-diphenyl-1,3,5-triazine in Preparation Example 1 Compound E9 was prepared in the same manner as in Preparation Example 1, except that 2-yl) benzonitrile was used.

MS [M + H] ⁺ = 589

Production Example  10. Synthesis of Compound E10

3- (3- (4-bromo-6-phenyl-1,3,5-triazine-2 instead of 2-chloro-4,6-diphenyl-1,3,5-triazine in Preparation Example 1 Compound E10 was prepared in the same manner as in Preparation Example 1, except that -yl) phenyl) -1,10-phenanthroline was used.

MS [M + H] ⁺ = 666

Production Example  11.Synthesis of Compound E11

The same method as in Preparation Example 1, except that (3-bromophenyl) diphenylphosphine oxide was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine in Preparation Example 1. Compound E11 was prepared.

MS [M + H] ⁺ = 533

Production Example  12. Synthesis of Compound E12

In Example 1, 1- (4-bromophenyl) -2-ethyl-1H-benzo [d] imidazole was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine. Except for preparing the compound E12 in the same manner as in Preparation Example 1.

MS [M + H] ⁺ = 477

Proper combination of the formulas described in the examples herein and the intermediates on the basis of common technical knowledge, it is possible to prepare all of the heterocyclic compounds of Formula 1 described herein.

Example  1-1

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and ultrasonically cleaned. In this case, Fischer Co. was used as a detergent, and distilled water was filtered secondly as a filter of Millipore Co. as a distilled water. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After washing the distilled water, ultrasonic washing with a solvent of isopropyl alcohol, acetone, methanol, dried and transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.

The compound of the following compound HI1 and the following compound HI2 was thermally vacuum-deposited to a thickness of 100 kPa so that the ratio of 98: 2 (molar ratio) was formed on the ITO transparent electrode as the anode thus prepared to form a hole injection layer. Compound (1150.) Represented by the following formula HT1 was vacuum deposited on the hole injection layer to form a hole transport layer. Subsequently, the electron suppression layer was formed by vacuum depositing a compound of EB1 on the hole transport layer with a film thickness of 50 GPa. Subsequently, the light emitting layer was formed by vacuum depositing the compound represented by the following formula BH and the compound represented by the following formula BD at a weight ratio of 50: 1 on the electron suppressing layer with a film thickness of 200 kPa. A hole blocking layer was formed by vacuum depositing a compound represented by the following formula HB1 with a film thickness of 50 kPa on the light emitting layer. Subsequently, the compound of Preparation Example 1 and the compound represented by the following formula LiQ were vacuum-deposited on the hole blocking layer in a weight ratio of 1: 1 to form an electron injection and transport layer at a thickness of 30 kPa. Lithium fluoride (LiF) and aluminum were deposited on the electron injection and transport layer sequentially to a thickness of 12 Å and 1,000 Å to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7Å / sec, the lithium fluoride of the cathode was maintained at 0.3Å / sec, the deposition rate of aluminum was 2Å / sec, the vacuum degree during deposition is 2x10 ^-7 ~ The organic light emitting device was manufactured by maintaining 5 × 10 ⁻⁶ torr.

Example  1-2 to Example  1-8

An organic light emitting diode was manufactured according to the same method as Example 1-1 except for using the compound shown in Table 1 instead of the compound E1.

Comparative example  1-1 to 1-4

An organic light-emitting device was manufactured in the same manner as in Example 1-1, except for using the compound shown in Table 1 below instead of the compound of Preparation Example 1. The compounds of ET1, ET2, ET3, and ET4 used in Table 1 below are as follows.

When the current was applied to the organic light emitting device manufactured by Examples 1-1 to 1-8, and Comparative Examples 1-1 to 1-4, voltage, efficiency, color coordinates and lifetime were measured, and the results were as follows. It is shown in [Table 1]. T95 means the time it takes for the luminance to decrease to 95% from the initial luminance of 1600 nits.

	Compound (electron injection and transport layer)	Voltage (V @ 20mA / cm 2 )	Efficiency (cd / A @ 20mA / cm 2 )	Color coordinates (x, y)	T95 (hr)
Example 1-1	Compound E1	4.21	6.34	(0.141, 0.046)	255
Example 1-2	Compound E2	4.32	6.52	(0.142, 0.045)	285
Example 1-3	Compound E5	4.22	6.86	(0.143, 0.047)	275
Example 1-4	Compound E6	4.34	6.85	(0.143, 0.046)	260
Example 1-5	Compound E9	4.17	6.79	(0.144, 0.044)	275
Example 1-6	Compound E10	4.28	6.44	(0.141, 0.047)	255
Example 1-7	Compound E11	4.39	6.60	(0.142, 0.047)	278
Example 1-8	Compound E12	4.21	6.43	(0.143, 0.046)	268
Comparative Example 1-1	ET 1	4.53	5.78	(0.145, 0.049)	187
Comparative Example 1-2	ET 2	5.77	5.12	(0.148, 0.051)	61
Comparative Example 1-3	ET 3	5.51	5.49	(0.146, 0.053)	86
Comparative Example 1-4	ET 4	4.78	5.84	(0.143, 0.047)	103

As shown in Table 1, the organic light emitting device manufactured by using the compound of the present invention as an electron injection and transport layer exhibits excellent characteristics in terms of efficiency, driving voltage and / or stability of the organic light emitting device. Like the ET1 core The biquinoline compound and the substituted compound showed lower voltage, higher efficiency and longer life than the organic light emitting device manufactured by using the electron transport layer.

In the case of Comparative Examples 1-2 and 1-4 using a compound whose core is not a biquinoline compound or a non-biquinoline compound substituted at the 1,4 position, and Comparative Examples 1-3 using a compound in which R 2 is not hydrogen In comparison with Examples 1-1 to 1-8, it was confirmed that the service life significantly decreased and had a high voltage.

Although the preferred embodiment of the present invention (electron injection and transport layer) has been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention. It also belongs to the scope of the invention.

Claims (8)

1. Heterocyclic compounds represented by the formula (1):

   [Formula 1]

   

   In Chemical Formula 1,

   X ₁ to X ₇ is N or CR ₁ , at least one of X ₁ to X ₇ is N,

   Y ₁ to Y ₇ is N or CR ₂ , at least one of Y ₁ to Y ₇ is N,

   R1 is hydrogen or -L _n -Ar,

   R2 is hydrogen,

   L is a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted monocyclic having 3 to 30 carbon atoms Heteroarylene group,

   Ar is hydrogen; heavy hydrogen; Nitrile group; Halogen group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted silyl group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted amine group; Substituted or unsubstituted aryl group; A pyridine group unsubstituted or substituted with an aryl group; Pyrimidine groups unsubstituted or substituted with aryl groups; Triazine group unsubstituted or substituted with an aryl group or a heteroaryl group; Pyridazine groups unsubstituted or substituted with an aryl group; Benzoimidazole group unsubstituted or substituted with an alkyl group; Imidazole group; Dibenzofuran group; Dibenzothiophene group; Or a phenanthroline group,

   n is an integer of 1 to 3, and when n is 2 or more, L is the same as or different from each other.
2. The heterocyclic compound according to claim 1, wherein Formula 1 is represented by Formula 2:

   [Formula 2]

   

   In Formula 2, the definitions of X _1, X _2, X ₄ to X _7, Y ₁ to Y _7, L, Ar, and n are the same as defined in Formula 1.
3. The heterocyclic compound according to claim 1, wherein Formula 1 is represented by any one of Formulas 3 to 9:

   
4. The heteroaryl of claim 1, wherein L is a direct bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl including any one or more of N, O, and S having 3 to 30 carbon atoms. Heterocyclic compound which is a rene group.
5. The method of claim 1, wherein Ar is a phosphine oxide group unsubstituted or substituted with an aryl group having 6 to 30 carbon atoms; An aryl group having 6 to 30 carbon atoms unsubstituted or substituted with a nitrile group; A pyridine group unsubstituted or substituted with an aryl group; Pyrimidine groups unsubstituted or substituted with aryl groups; Triazine group unsubstituted or substituted with an aryl group or a heteroaryl group; Pyridazine groups unsubstituted or substituted with an aryl group; Benzoimidazole group unsubstituted or substituted with an alkyl group; Imidazole group; Dibenzofuran group; Dibenzothiophene group; Or a phenanthroline group.
6. [Correction under Rule 91 26.07.2019]
   The heterocyclic compound according to claim 1, wherein Formula 1 is represented by any one of the following structural formulas:
   

   

   
   

   

   
   

   

   
   

   

   
   

   

   
   

   

   
   

   

   
   

   

   
   

   

   
   

   

   
   

   

   
   

   

   
   

   

   
   

   

   
   

   

   
   

   

   
   

   
7. A first electrode; A second electrode provided to face the first electrode; And one or two or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include the heterocyclic compound according to any one of claims 1 to 6. Phosphorescent organic light-emitting device.
8. The organic light emitting device of claim 7, wherein the organic material layer comprises an electron injection layer, an electron transport layer, an electron injection and transport layer, and the electron injection layer, the electron transport layer, the electron injection and transport layer comprises the heterocyclic compound.

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