KR102172580B1 - Heterocyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

The present specification relates to a heterocyclic compound of Formula 1 and an organic light emitting device including the same.

Description

Heterocyclic compound and organic light-emitting device including the same TECHNICAL FIELD [0002] HETEROCYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME

This specification claims the benefit of the filing date of Korean Patent Application No. 10-2018-0017478 filed with the Korean Intellectual Property Office on February 13, 2018, the entire contents of which are incorporated herein.

The present specification relates to a heterocyclic compound and an organic light emitting device formed using the heterocyclic compound.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic light emitting device using the organic light emitting phenomenon has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device.For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of such an organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It glows when it falls back to the ground.

Development of a new material for the organic light emitting device as described above is continuously required.

US Patent Application Publication No. 2004-0251816

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

According to an exemplary embodiment of the present specification provides a heterocyclic compound represented by the following formula (1).

[Formula 1]

In Formula 1

X is O or S,

A1 and A2 are the same as or different from each other, and each independently a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted trialkylsilyl group, a substituted or unsubstituted triarylsilyl group, a substituted Or an unsubstituted dialkylarylsilyl group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or an aliphatic substituted or unsubstituted by bonding adjacent substituents to each other To form a ring, a substituted or unsubstituted aromatic ring, or a substituted or unsubstituted hetero ring,

L1 and L2 are the same as or different from each other, and each independently a direct bond or an arylene group,

R1 and R2 are the same as or different from each other, and each independently hydrogen, deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

a is an integer from 0 to 3,

b is 0 or 1,

n is an integer from 0 to 2,

m is an integer from 0 to 4,

a+m≤4 and

b+n≤2,

When a is plural, R1 is the same as or different from each other,

When m is plural, -(L1-A1) is the same as or different from each other,

When n is plural, -(L2-A2) is the same as or different from each other.

Finally, the present specification includes a first electrode; A second electrode provided opposite to the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the heterocyclic compound.

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

More specifically, the compound according to an exemplary embodiment of the present invention has a structure having high electron-accepting capacity, has delayed fluorescence characteristics, and can maintain an appropriate deposition temperature when fabricating an organic light-emitting device. In addition, high purity can be achieved by a sublimation purification method, and contamination is not caused to a deposition apparatus or an organic light emitting device when manufacturing an organic light emitting device.

1 shows an organic light emitting device according to an exemplary embodiment of the present specification.
2 shows an organic light-emitting device according to an exemplary embodiment of the present specification.

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

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

In the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

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

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

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

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Nitrile group; Halogen group; Boron group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted carbonyl group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group, substituted with one or two or more substituents selected from the group consisting of, or two or more of the substituents exemplified above are substituted with a connected substituent, or no substituent. For example, the "substituent to which two or more substituents are connected" 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 a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., but are limited thereto. It is not.

In the present specification, the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it 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, the number of carbon atoms is not particularly limited, but it is preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it has 10 to 30 carbon atoms. Specifically, the polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a triphenyl group, a pyrenyl group, a phenalenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but are limited thereto. no.

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

,

,

,

,

및

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

,

,

,

,

And

Etc. However, it is not limited thereto.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group containing two or more aryl groups may include 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 aryl group in the aryloxy group, the N-arylalkylamine group, and the N-arylheteroarylamine group is the same as the example of the aryl group described above. Specifically, the aryloxy group includes a phenoxy group, p-tolyloxy group, m-tolyloxy group, 3,5-dimethyl-phenoxy group, 2,4,6-trimethylphenoxy group, p-tert-butylphenoxy group, 3- Biphenyloxy group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthryloxy group , 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenanthryloxy group, and 9-phenanthryloxy group.

In the present specification, the heteroaryl group includes one or more atoms and heteroatoms other than carbon, and specifically, the heteroatom may include one or more atoms selected from the group consisting of O, N, Se, and S. The number of carbon atoms is not particularly limited, but is preferably 2 to 30 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include thiophene group, furanyl group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, tria Zolyl group, acridyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, p Nanthrolinyl group (phenanthroline), isoxazolyl group, thiadiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, but are not limited thereto.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroarylamine group including 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 heteroaryl group described above.

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

In the present specification, the arylene is the same as the example of the aryl group described above except that it is divalent.

According to an exemplary embodiment of the present specification, Formula 1 is represented by any one of the following Formulas 2 and 3.

[Formula 2]

[Formula 3]

In Formulas 2 and 3, the definitions of X, A1, A2, L1, L2, R1, R2, a, b, m and n are as defined in Formula 1,

The A11 to A14 are the same as the definition of A1,

The L11 to L14 are the same as the definition of L1,

A21 and A22 are the same as the definition of A2,

L21 and L22 are the same as the definition of L2.

According to an exemplary embodiment of the present specification, Chemical Formula 1 may be represented by any one of the compounds of Chemical Formulas 4 to 11.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

In Formulas 4 and 11, the definition of X is as defined in Formula 1,

The A11 to A14 are the same as the definition of A1,

The L11 to L14 are the same as the definition of L1,

A21 and A22 are the same as the definition of A2,

L21 and L22 are the same as the definition of L2.

According to an exemplary embodiment of the present specification, m+n≥1.

According to an exemplary embodiment of the present specification, A1, A2, A11 to A14, A21, and A22 are the same as or different from each other, and a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted It is an arylamine group.

According to an exemplary embodiment of the present specification, A1, A2, A11 to A14, A21, and A22 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted carbon number It is a 3 to 30 heteroaryl group, or a substituted or unsubstituted arylamine group.

According to an exemplary embodiment of the present specification, A1, A2, A11 to A14, A21, and A22 are the same as or different from each other, and each independently deuterium, nitrile group, halogen group, aryl group, heteroaryl group, silyl group, boron It is an aryl group unsubstituted or substituted with a substituent selected from a group, an alkenyl group, a carbonyl group, a phosphine oxide group, and an amine group.

According to an exemplary embodiment of the present specification, A1, A2, A11 to A14, A21, and A22 are the same as or different from each other, and each independently an aryl group unsubstituted or substituted with an alkyl group.

According to an exemplary embodiment of the present specification, A1, A2, A11 to A14, A21, and A22 are the same as or different from each other, and each independently an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with an alkyl group or an aryl group.

According to an exemplary embodiment of the present specification, A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, and each independently substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms It is a C6-C30 aryl group.

According to an exemplary embodiment of the present specification, A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, and each independently a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a terbutyl group, a pen Substituted or furnished with a tyl group, hexyl group, cyclohexyl group, phenyl group, naphthyl group, biphenyl group, terphenyl group, quarterphenyl group, phenanthrene group, anthracene group, pyrene group, triphenylene group, fluorene group, or spirobifluorene group It is a ring C6-C30 aryl group.

According to an exemplary embodiment of the present specification, A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and the substituted or unsubstituted The aryl group having 6 to 30 carbon atoms is a phenyl group; Naphthyl group; Biphenyl group; Terphenyl group; Quarter phenyl group; Phenanthrene group; Anthracene group; Pyren group; Triphenylene group; Fluorene group; And spirobifluorene group, but is not limited thereto.

According to an exemplary embodiment of the present specification, A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, and each independently a nitrile group, a halogen group, an alkyl group, an aryl group, a heteroaryl group, a silyl group, and boron. It is a heteroaryl group unsubstituted or substituted with a substituent selected from a group, an alkenyl group, a carbonyl group, a phosphine oxide group, and an amine group.

According to an exemplary embodiment of the present specification, A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, and each independently a nitrile group, a halogen group, an alkyl group, an aryl group, a heteroaryl group, a silyl group, and boron. It is a C3-C30 heteroaryl group containing one or more of N, O, and S unsubstituted or substituted with a substituent selected from a group, an alkenyl group, a carbonyl group, a phosphine oxide group, and an amine group.

According to an exemplary embodiment of the present specification, A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, and each independently substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms It is a monocyclic or polycyclic heteroaryl group containing one or more of N, O, and S,

The monocyclic or polycyclic heteroaryl group is a pyrrole group, pyridine group, pyrimidine group, triadine group, carbazole group, imidazole group, pyrrole group, quinazole group, quinoline group, furan group, benzofuran group, dibenzofuran group, benzo Naphthofuran group, thiophene group, benzothiophene group, dibenzothiophene group, and benzonaphthothiophene group may be selected from, but is not limited thereto.

According to an exemplary embodiment of the present specification, A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, and each independently a carbazole group, a dibenzofuran group, or a dibenzothiophene group,

The carbazole group, dibenzofuran group, or dibenzothiophene group may be unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, A1, A2, A11 to A14, A21, and A22 are the same as or different from each other, and each independently deuterium, nitrile group, halogen group, aryl group, heteroaryl group, silyl group, boron It is an arylamine group unsubstituted or substituted with a substituent selected from a group, an alkenyl group, a carbonyl group, a phosphine oxide group, and an amine group.

According to an exemplary embodiment of the present specification, A1, A2, A11 to A14, A21, and A22 are the same as or different from each other, and each independently deuterium, nitrile group, halogen group, aryl group, or heteroaryl group substituted or unsubstituted It is an arylamine group.

According to an exemplary embodiment of the present specification, A1, A2, A11 to A14, A21, and A22 are the same as or different from each other, and each independently substituted with an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms, or It is an unsubstituted arylamine group.

According to an exemplary embodiment of the present specification, A1, A2, A11 to A14, A21 and A22 are the same as or different from each other, and each independently a monocyclic aryl group having 6 to 30 carbon atoms, a polycyclic aryl group having 6 to 30 carbon atoms , A monocyclic heteroaryl group having 6 to 30 carbon atoms, or an arylamine group unsubstituted or substituted with a polycyclic heteroaryl group having 3 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, A1, A2, A11 to A14, A21, and A22 are the same as or different from each other, and each independently a methyl group, a terbutyl group, or a phenyl group unsubstituted or substituted with a carbazole group; Naphthyl group; A carbazole group unsubstituted or substituted with a phenyl group or a terbutyl group; Dibenzofuran group; Dibenzothiophene group; Diphenylfluorene group; Dimethylfluorene group; Spirobifluorene; Or a diphenylamine group.

According to an exemplary embodiment of the present specification, L1, L2, L11 to L14, L21 and L22 are the same as or different from each other, and are each independently a direct bond or an arylene group having 6 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, L1, L2, L11 to L14, L21, and L22 are the same as or different from each other, and each independently a divalent phenyl group, a divalent biphenylene group, a divalent terphenylene group, and a divalent phenyl group. It is a nanthrene group, a divalent anthracene group, or a divalent triphenylene group.

According to an exemplary embodiment of the present specification, L1, L2, L11 to L14, L21, and L22 are the same as or different from each other, and each independently a direct bond or a phenylene group.

According to an exemplary embodiment of the present specification, m is 1 and n is 0.

According to an exemplary embodiment of the present specification, m is 2 and n is 0.

According to an exemplary embodiment of the present specification, m is 4 and n is 0.

According to an exemplary embodiment of the present specification, n is 1 and m is 0.

According to an exemplary embodiment of the present specification, n is 2 and m is 0.

According to another exemplary embodiment of the present specification, the heterocyclic compound of Formula 1 may be represented by any one selected from the following structural formulas.

In addition, the organic light emitting device according to the present invention includes a first electrode; A second electrode provided opposite to the first electrode; And 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 the heterocyclic compound.

The organic light-emitting device of the present invention may be manufactured by a conventional method and material of an organic light-emitting device, except that one or more organic material layers are formed by using the above-described compound.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection 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 material layers. In addition, the organic material layer may include at least one of an electron transport layer, an electron injection layer, and a layer that simultaneously transports electrons and injects electrons, and at least one of the layers may include the compound.

The organic material layer including the heterocyclic compound of Formula 1 may have a multilayer structure including a hole injection layer, a hole transport layer, an emission layer, an electron transport layer, etc., but is not limited thereto and may have a single layer structure. In addition, the organic material layer is made of a variety of polymer materials, and is used in a smaller number of solvent processes, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be made in layers.

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

1 illustrates a structure of an organic light-emitting device in which a first electrode 2, an organic material layer 3, a light emitting layer 4, and a second electrode 5 are sequentially stacked on a substrate 1.

2, a first electrode 2, a hole injection layer 6, a hole transport layer 7, an electron blocking layer 8, a light emitting layer 4, a hole blocking layer 9, an electron injection and transport layer 10, and The structure of an organic light-emitting device in which the second electrodes 5 are sequentially stacked is illustrated. Preferably, the heterocyclic compound of Formula 1 is included in the light emitting layer.

1 and 2 illustrate an organic light emitting device and are not limited thereto.

In the specification of the present invention, the organic light emitting device includes a structure in which a first electrode/a light emitting layer/a second electrode are sequentially stacked.

In the specification of the present invention, the organic light-emitting device includes a structure in which a first electrode/hole transport layer/electron-suppression layer/emission layer/second electrode are sequentially stacked.

In the specification of the present invention, the organic light emitting device includes a structure in which a first electrode/hole injection layer/hole transport layer/light emitting layer/second electrode are sequentially stacked.

In the specification of the present invention, the organic light emitting device includes a structure in which a first electrode/hole injection layer/hole transport layer/light emitting layer/electron injection and transport layer/second electrode are sequentially stacked.

In the specification of the present invention, the organic light emitting device includes a structure in which a first electrode/hole injection layer/hole transport layer/electron suppression layer/light emitting layer/electron injection and transport layer/second electrode are sequentially stacked.

In the specification of the present invention, the organic light emitting device includes a structure in which a first electrode / a hole injection layer / a hole transport layer / an electron suppression layer / a light emitting layer / a hole suppression layer / an electron injection and transport layer / a second electrode are sequentially stacked.

In an exemplary embodiment of the present invention, the organic light-emitting device may include an emission layer, and the heterocyclic compound of Formula 1 may be included in the emission layer.

In an exemplary embodiment of the present invention, the organic light-emitting device includes the heterocyclic compound of Formula 1 as a dopant of the light-emitting layer in the light-emitting layer.

In one embodiment of the present invention, the organic light emitting device includes an organic compound in the light emitting layer as a host of the light emitting layer.

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

In an exemplary embodiment of the present invention, the organic light-emitting device includes an N-containing heterocyclic compound in the light-emitting layer as a host of the light-emitting layer.

In an exemplary embodiment of the present invention, the organic light emitting device includes a carbazole compound in the light emitting layer as a host of the light emitting layer.

In an exemplary embodiment of the present invention, the organic light-emitting device includes a carbazole-based compound in the emission layer as a host of the emission layer.

In an exemplary embodiment of the present invention, the organic light-emitting device includes a host and a dopant in an emission layer in a weight ratio of 90:10 to 10:90.

In an exemplary embodiment of the present invention, the organic light-emitting device includes a host and a dopant in an emission layer in a weight ratio of 80:20 to 50:50.

In an exemplary embodiment of the present invention, the organic light-emitting device includes a host and a dopant in an emission layer in a weight ratio of 80:20 to 60:40.

In an exemplary embodiment of the present invention, the organic light emitting device includes an electron injection layer, an electron transport layer, or a hole blocking layer, and the heterocyclic compound of Formula 1 is added to the electron injection layer, the electron transport layer, or the hole blocking layer. Can include.

In an exemplary embodiment of the present invention, the organic light emitting device includes a hole injection layer, a hole transport layer, or an electron blocking layer, and the heterocyclic compound of Formula 1 is added to the hole injection layer, the hole transport layer, or the electron blocking layer. Can include.

For example, the organic light-emitting device according to the present invention uses a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, and uses a metal or conductive metal oxide or alloy thereof on a substrate. A material that can be used as a cathode after forming an anode by depositing a hole injection layer, a hole transport layer, a light emitting layer, an organic material layer including an electron transport layer, and an organic material layer including the heterocyclic compound of Formula 1 thereon. Can be prepared by evaporating. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

As the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of a metal and an oxide such as ZnO:Al or SnO ₂ :Sb; Poly(3-methyl compound), poly[3,4-(ethylene-1,2-dioxy) compound] (PEDT), conductive polymers such as polypyrrole and polyaniline, 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; There are multi-layered materials such as LiF/Al or LiO ₂ /Al, 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 it is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrine, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Of organic matter, anthraquinone, and conductive polymers of a series of polyaniline and poly compounds, but are not limited thereto.

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

The light-emitting material is a material capable of emitting light in a visible light region by transporting and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole, and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The emission layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocyclic compounds include heterocyclic compounds, dibenzofuran derivatives, and ladder type 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.

For example, the organic light emitting device of the present specification may be manufactured by sequentially laminating an anode, an organic material layer, and a cathode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, an anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. And, after forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, it can be produced by depositing a material that can be used as a cathode thereon. In addition to such a method, an organic light-emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the emission layer.As an electron transport material, a material capable of receiving electrons from the cathode and transferring them to the emission layer, and a material having high mobility for electrons is suitable. Do. Specific examples include the Al complex of 8-hydroxyquinoline; Complexes including Alq3; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials that have a low work function and are followed by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium, and samarium, and in each case an aluminum layer or a silver layer follows.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, has an excellent electron injection effect on the light emitting layer or light emitting material, and injects holes of excitons generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, preorenylidene methane, anthrone, etc. Complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include lithium 8-hydroxyquinolinato, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is not limited to this.

The hole blocking layer is a layer that prevents holes from reaching the cathode, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes, etc., 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-sided emission type depending on the material used.

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

According to an exemplary embodiment of the present specification, the compound of Formula 1 may be prepared according to the following reaction scheme, but is not limited thereto. In the following reaction scheme, various types of intermediates can be synthesized according to the type and number of substituents appropriately selecting a known starting material by a person skilled in the art. As for the reaction type and reaction conditions, those known in the art may be used.

When the preparation formula described in the examples of the present specification and the intermediates are appropriately combined based on common technical knowledge, all of the compounds of Formula 1 described in the present specification can be prepared.

< Manufacturing example >

The compound represented by Formula 1 can be prepared from the process of forming a ring by introducing various types of benzene into halide-substituted benzene as follows. After the introduction of cyanide, the compounds were finally synthesized by introducing carbazole, heteroaryl, and aryl.

Manufacturing example 1-1: Synthesis of compound 1-A

(2-hydroxyphenyl) boronic acid 30g (217.5mmol), 1,3,5-tribromo-2,4,6-trifluorobenzene 217.5mmol, tetrahydrofuran 200mL and water 100mL were mixed and then 60 ℃ Heated to. Potassium carbonate (652.5 mmol) and tetrakistriphenylphosphine palladium (1 mmol) were added, and the mixture was stirred for 3 hours in a reflux state. After the reaction, the organic layer was extracted from the reaction solution returned to room temperature, and then recrystallized twice with chloroform and hexane to obtain 74.7 g of compound 1-A (yield 90%).

MS[M+H]+ = 381

Manufacturing example 1-2: synthesis of compound 1-B

1-A 50g (130.9mmol), potassium carbonate 262mmol, DMF 300mL were mixed, heated at 60°C for 1 hour, and stirred for 1 hour in reflux state. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with TFC and ethanol to obtain 38.8 g of compound 1-B (yield 82%).

MS[M+H]+ = 361

Manufacturing example 1-3: Synthesis of Compound 1-C

1-B 35g (96.7mmol), cupacyanide 386mmol, DMF 300mL were mixed and stirred at 100°C for 4 hours. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with TFC and ethanol to obtain 18.7 g of compound 1-C (yield 76%).

MS[M+H]+ = 255

Manufacturing example 1-4: Synthesis of compound 1-D

1-C 15g (59mmol), 5-phenyl-5,12-dihydroindolo[3,2-a]carbazole 59mmol, potassium carbonate 118mmol, and DMF 100mL were mixed and stirred at 80°C for 1 hour. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with TFC and ethanol to obtain 28 g of compound 1-D (yield 84%).

MS[M+H]+ = 567

Manufacturing example 1-5: synthesis of compound 1

1-C 15g (59mmol), 9-H-carbazole 118mmol, potassium carbonate 236mmol, and DMF 100mL were mixed and stirred at 100°C for 2 hours. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with TFC and ethanol to obtain 26.2 g of compound 1 (yield 81%).

MS[M+H]+ = 549

Manufacturing example 1-6: synthesis of compound 2

1-D 15g (26.5mmol), 9-H-carbazole 26.5mmol, potassium carbonate 118mmol, and DMF 100mL were mixed and stirred at 100°C for 1 hour. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with TFC and ethanol to obtain 15.7 g of compound 2 (yield 83%).

MS[M+H]+ = 714

Manufacturing example 2-1: Synthesis of compound 2-A

2-bromophenol 37.6 g (217.5 mmol), (perfluorophenyl) boronic acid 217.5 mmol, tetrahydrofuran 200 mL, and water 100 mL were mixed and heated to 60°C. Potassium carbonate (652.5 mmol) and tetrakistriphenylphosphine palladium (1 mmol) were added, and the mixture was stirred for 3 hours in a reflux state. After the reaction, the organic layer was extracted from the reaction solution returned to room temperature, and then recrystallized twice with chloroform and hexane to obtain 51.5 g of compound 2-A (yield 91%).

MS[M+H]+ = 261

Manufacturing example 2-2: Synthesis of compound 2-B

1-A 34g (130.9mmol) and DMF 300mL were mixed, and 130.9mmol of NBS was added at 0°C, followed by stirring for 1 hour. After the reaction, the reaction solution was reverse-precipitated in an aqueous sodium thiosulfate solution to obtain a solid, and then recrystallized twice with TFC and hexane to obtain 48.1 g of compound 2-B (yield 88%).

MS[M+H]+ = 416

Manufacturing example 2-3: Synthesis of compound 2-C

2-B 40g (95.7mmol), potassium carbonate 192mmol, DMF 300mL were mixed, heated at 60°C for 1 hour, and stirred for 1 hour in reflux state. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with TFC and ethanol to obtain 30.8 g of compound 2-C (yield 81%).

MS[M+H]+ = 396

Manufacturing example 2-4: Synthesis of compound 2-D

2-C 25g (62.8mmol), cupacyanide 125.6mmol, and DMF 200mL were mixed and stirred at 100°C for 4 hours. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with TFC and ethanol to obtain 13.3 g of compound 2-D (yield 73%).

MS[M+H]+ = 291

Manufacturing example 2-5: Synthesis of compound 3

2-D 12g (41.3mmol), 9-H-carbazole 165.4mmol, potassium carbonate 330.8mmol, and DMF 100mL were mixed and stirred at 100°C for 2 hours. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with TFC and ethanol to obtain 28 g of compound 3 (yield 77%).

MS[M+H]+ = 879

Manufacturing example 2-6: Synthesis of compound 4

2-D 12g (41.3mmol), 3,6-dimethyl-9-H-carbazole 165.4mmol, potassium carbonate 330.8mmol, and DMF 100mL were mixed and stirred at 100°C for 2 hours. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with TFC and ethanol to obtain 30.7 g of compound 4 (yield 75%).

MS[M+H]+ = 991

Manufacturing example 3-1: Synthesis of compound 3-A

(2-mercamtophenyl) boronic acid 33.5g (217.5mmol), 1,3,5-tribromo-2,4,6-trifluorobenzene 217.5mmol, tetrahydrofuran 200mL and water 100mL were mixed and 60 Heated to °C. Potassium carbonate (652.5 mmol) and tetrakistriphenylphosphine palladium (1 mmol) were added, and the mixture was stirred for 3 hours in a reflux state. After the reaction, the organic layer was extracted from the reaction solution returned to room temperature, and then recrystallized twice with chloroform and hexane to obtain 77 g of compound 3-A (yield 89%).

MS[M+H]+ = 396

Manufacturing example 3-2: Synthesis of compound 3-B

52g (130.9mmol) of 3-A, 262mmol of potassium carbonate, and 300mL of DMF were mixed, heated to 60°C for 1 hour, and stirred for 1 hour in reflux state. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with TFC and ethanol to obtain 39.6 g of compound 3-B (yield 80%).

MS[M+H]+ = 376

Manufacturing example 3-3: Synthesis of compound 3-C

3-B 36.5g (96.7mmol), cupacyanide 386mmol, DMF 300mL were mixed and stirred at 100°C for 4 hours. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with TFC and ethanol to obtain 19.8 g of compound 3-C (yield 76%).

MS[M+H]+ = 271

Manufacturing example 3-4: Synthesis of compound 3-D

3-C 15.9g (59mmol), 5-phenyl-5,12-dihydroindolo[3,2-a]carbazole 59mmol, potassium carbonate 118mmol, and DMF 100mL were mixed and stirred at 80°C for 1 hour. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with TFC and ethanol to obtain 27.8 g of compound 3-D (yield 81%).

MS[M+H]+ = 583

Manufacturing example 3-5: Synthesis of compound 5

3-C 15.9g (59mmol), 9-H-carbazole 118mmol, potassium carbonate 236mmol, and DMF 100mL were mixed and stirred at 100°C for 2 hours. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with TFC and ethanol to obtain 27.6 g of compound 5 (yield 83%).

MS[M+H]+ = 565

Manufacturing example 3-6: Synthesis of compound 6

3-D 15.4g (26.5mmol), 9-H-carbazole 26.5mmol, potassium carbonate 118mmol, and DMF 100mL were mixed and stirred at 100°C for 1 hour. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with TFC and ethanol to obtain 15.6 g of compound 6 (yield 81%).

MS[M+H]+ = 730

Materials of specific examples were synthesized by introducing various types of substituents using the same reaction as in the above scheme.

< Example >

In the present embodiment, the compound represented by Formula 1 according to the exemplary embodiment of the present specification is included in the emission layer together with a host material (m-CBP) having a triplet value of 2.5 eV or more to manufacture an organic light emitting device, and Evaluated.

[ Comparative example One]

A glass substrate coated with a thin film of ITO (indium tin oxide) to a thickness of 1,000Å was put in distilled water dissolved in a detergent and washed with ultrasonic waves. In this case, Fischer Co. product was used as a detergent, and distilled water secondarily filtered with a filter made by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator. Each thin film was stacked on the thus prepared ITO transparent electrode by vacuum evaporation with a vacuum degree of 5.0 占10 ^-4 Pa. First, hexaazatriphenylene (HAT) was thermally vacuum deposited to a thickness of 500Å on ITO to form a hole injection layer.

A hole transport layer was formed by vacuum deposition of the following compound 4-4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB) (300Å), which is a material that transports holes on the hole injection layer. I did.

Compound N-([1,1'-bisphenyl]-4-yl)-N-(4-(11-([1,1'-biphenyl]-4-yl) with a film thickness of 100Å on the hole transport layer )-11H-benzo[a]carbazole-5-yl)phenyl)-[1,1'-biphenyl]-4-amine (EB1) (100Å) was vacuum deposited to form an electron blocking layer.

Subsequently, m-CBP and compound 4CzIPN were vacuum-deposited on the electron blocking layer at a weight ratio of 70:30 with a thickness of 300 Å as follows to form an emission layer.

A hole blocking layer was formed by vacuum depositing compound HB1 on the emission layer with a thickness of 100 Å.

Compound ET1 and compound LiQ (Lithium Quinolate) were vacuum-deposited at a weight ratio of 1:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 300Å. Lithium fluoride (LiF) at a thickness of 12 Å and aluminum at a thickness of 2,000 Å were sequentially deposited on the electron injection and transport layer to form a negative electrode.

Was maintained at the deposition rate was 0.4 ~ 0.7Å / sec for organic material in the above process, the lithium fluoride of the cathode was 0.3Å / sec, aluminum is deposited at a rate of 2Å / sec, the degree of vacuum upon deposition ⅹ10 2 ^-7 By maintaining ~ 5 x10 ^-6 torr, an organic light emitting device was manufactured.

[Experimental Examples 1 to 6]

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that the compound of Table 1 below was used instead of the compound 4CzIPN in Comparative Example 1.

[Comparative Examples 2 and 3]

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that compounds of the following T1 to T2 were used instead of the compound 4CzIPN in Comparative Example 1.

When a current was applied to the organic light-emitting devices manufactured according to Experimental Examples 1 to 6 and Comparative Examples 1 to 3, the results shown in Table 1 were obtained.

division compound
(Luminescent layer) Voltage
(V@10mA/cm ² ) efficiency
(cd/A@10mA/cm ² ) Color coordinates
(x,y) Comparative Example 1 4CzIPN 4.4 16 (0.33, 0.62) Experimental Example 1 Compound 1 4.0 23 (0.34, 0.64) Experimental Example 2 Compound 2 4.1 22 (0.33, 0.65) Experimental Example 3 Compound 3 4.1 23 (0.33, 0.66) Experimental Example 4 Compound 4 4.0 23 (0.33, 0.65) Experimental Example 5 Compound 5 3.9 22 (0.32, 0.64) Experimental Example 6 Compound 6 3.9 23 (0.33, 0.64) Comparative Example 2 T1 4.8 One (0.21, 0.25) Comparative Example 3 T2 4.7 2 (0.27, 0.28)

As shown in Table 1, the devices of Experimental Examples 1 to 6 using the compound having the structure of Chemical Formula 1 as a core had a lower voltage and increased efficiency than those using 4CzIPN. In addition, Comparative Example 2 And when comparing the device of Comparative Example 3 with the Example of the present application, it was found that the characteristics of the structure of the present Examples were improved both in terms of voltage and efficiency than when the position of the carbazole substituted with the nitrile group was different.

As shown in the results of Table 1, it was confirmed that the compound according to the present invention has excellent light-emitting ability and high color purity, so that it can be applied to a delayed fluorescent organic light-emitting device.

1: substrate
2: first electrode
3: organic material layer
4: light-emitting layer
5: second electrode
6: hole injection layer
7: hole transport layer
8: Electron layer
9: hole block
10: electron injection and transport layer

Claims (9)

Heterocyclic compound represented by the following Formula 1:
[Formula 1]

In Formula 1
X is O or S,
A1 and A2 are the same as or different from each other, and each independently a carbazole group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms; Or an indolocarbazole group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms,
L1 and L2 are the same as or different from each other, and each independently a direct bond or an arylene group,
R1 and R2 are hydrogen,
a is an integer from 0 to 4,
b is 0 to 2,
n is an integer from 0 to 2,
m is an integer from 0 to 4,
a+m≤4 and
b+n≤2,
When m is plural, -(L1-A1) is the same as or different from each other,
When n is plural, -(L2-A2) is the same as or different from each other. The heterocyclic compound of claim 1, wherein the formula 1 is represented by any one of the following formulas 2 and 3:
[Formula 2]

[Formula 3]

In Formulas 2 and 3, the definitions of X, A1, A2, L1, L2, R1, R2, a, b, m and n are as defined in Formula 1,
A11 to A14 are the same as the definition of A1,
L11 to L14 are the same as the definition of L1,
A21 and A22 are the same as the definition of A2,
L21 and L22 are the same as the definition of L2. delete The heterocyclic compound of claim 1, wherein L1 and L2 are the same as or different from each other, and each independently a direct bond or an arylene group having 6 to 30 carbon atoms. The heterocyclic compound according to claim 1, wherein Formula 1 is any one selected from the following compounds:

A first electrode; A second electrode provided opposite to the first electrode; And 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 is the heterocyclic compound of any one of claims 1, 2, 4 and 5 The organic light emitting device comprising a. The organic light-emitting device of claim 6, wherein the organic material layer includes an emission layer, and the emission layer includes the heterocyclic compound. The organic light-emitting device of claim 6, wherein the organic material layer includes a hole injection layer, a hole transport layer, or an electron blocking layer, and the hole injection layer, a hole transport layer, or an electron blocking layer includes the heterocyclic compound. The organic light-emitting device of claim 6, wherein the organic material layer includes an electron injection layer, an electron transport layer, or a hole blocking layer, and the electron injection layer, the electron transport layer, or the hole blocking layer includes the heterocyclic compound.

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