KR20240059572A - Compound and organic light emitting device comprising the same - Google Patents

Abstract

This specification relates to the compound of Formula 1 and an organic light-emitting device containing the same.

Description

Compound and organic light-emitting device containing the same {COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME}

This application claims the benefit of the filing date of Korean Patent Application No. 10-2022-0139484 filed with the Korea Intellectual Property Office on October 26, 2022, the entire contents of which are incorporated herein by reference.

This specification relates to compounds and organic light-emitting devices containing the same.

In this specification, an organic light-emitting device is a light-emitting device using an organic semiconductor material and requires exchange of holes and/or electrons between an electrode and an organic semiconductor material. Organic light-emitting devices can be broadly divided into two types according to their operating principles as follows. First, excitons are formed in the organic layer by photons flowing into the device from an external light source, these excitons are separated into electrons and holes, and these electrons and holes are transferred to different electrodes and used as current sources (voltage sources). It is a type of light emitting device. The second type is a light-emitting device that applies voltage or current to two or more electrodes to inject holes and/or electrons into the organic semiconductor material layer forming the interface with the electrodes, and operates by the injected electrons and holes.

In general, organic luminescence refers to a phenomenon that converts electrical energy into light energy using organic materials. Organic light-emitting devices that utilize the organic light-emitting phenomenon usually have a structure including an anode, a cathode, and an organic material layer between them. Here, the organic material layer is often composed of a multi-layer structure composed of different materials to increase the efficiency and stability of the organic light-emitting device. For example, it consists of a hole injection layer, a hole transport layer, a light-emitting layer, an electron suppression layer, an electron transport layer, and an electron injection layer. You can lose. In the structure of this organic light-emitting device, when a voltage is applied between two electrodes, holes are injected from the anode and electrons from the cathode into the organic material layer. When the injected holes and electrons meet, an exciton is formed, and this exciton When it falls back to the ground state, it glows. These organic light-emitting devices are known to have characteristics such as self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, and high contrast.

Materials used as organic layers in organic light-emitting devices can be classified into light-emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron suppression materials, electron transport materials, and electron injection materials, depending on their function. Depending on the color of light emitting, there are blue, green, and red light emitting materials, and yellow and orange light emitting materials needed to realize better natural colors.

Additionally, in order to increase color purity and increase luminous efficiency through energy transfer, a host/dopant system can be used as a luminescent material. The principle is that when a small amount of dopant, which has a smaller energy band gap and higher luminous efficiency than the host that mainly constitutes the light-emitting layer, is mixed into the light-emitting layer, excitons generated in the host are transported to the dopant, producing highly efficient light. At this time, since the wavelength of the host moves to the wavelength of the dopant, light of the desired wavelength can be obtained depending on the type of dopant used.

In order to fully demonstrate the excellent characteristics of the above-described organic light-emitting device, the materials that make up the organic layer within the device, such as hole injection material, hole transport material, light-emitting material, electron suppressor material, electron transport material, and electron injection material, must be stable and efficient materials. As this is supported by , the development of new materials continues to be required.

International Patent Publication No. 2017-126443

Disclosed herein are compounds and organic light-emitting devices containing the same.

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

[Formula 1]

In Formula 1,

A is a heteroaryl group containing a 6-membered ring containing N substituted with a substituted or unsubstituted aryl group,

B is a heteroaryl group containing a 6-membered ring containing N substituted with a substituted or unsubstituted aryl group,

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

One of Q1 and Q2 is an aryl group having 6 to 30 carbon atoms, and the other is hydrogen or an aryl group having 6 to 30 carbon atoms,

When one of Q1 and Q2 is hydrogen, the remainder is one or more substituents selected from deuterium, nitro group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, and substituted or unsubstituted heteroaryl group. It is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms,

When both Q1 and Q2 are aryl groups having 6 to 30 carbon atoms, the aryl group having 6 to 30 carbon atoms is deuterium, nitrile group, nitro group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, and substituted Or, it is substituted or unsubstituted with one or more substituents selected from unsubstituted heteroaryl groups.

The compound of the present invention can be used as a material for the organic layer of an organic light-emitting device. When manufacturing an organic light-emitting device including the compound of the present invention, an organic light-emitting device with high efficiency, low voltage, and long lifespan characteristics can be obtained, and when the compound of the present invention is included in the electron transport layer of the organic light-emitting device, intramolecular Due to its high polarity, the effect of electron transfer is high, making it possible to manufacture organic light-emitting devices with long-life characteristics.

The compound of the present invention has two or more substituted heterocycles containing an N-containing 6-membered ring with electron transport properties, and is adjacent to the ortho position of phenyl, resulting in structural distortion, so that the electron transport ability can be adjusted in various ways. there is.

1 and 2 show examples of organic light-emitting devices according to the present invention.

Hereinafter, this specification will be described in more detail.

In this specification, when a part “includes” a certain component, this means that it may further include other components rather than excluding other components, unless specifically stated to the contrary.

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

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

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

As used herein, the term “substituted or unsubstituted” refers to deuterium; halogen group; Cyano group (-CN); silyl group; boron group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; and substituted or unsubstituted heterocyclic groups, or is substituted with a substituent in which two or more of the above-exemplified substituents are linked, or does not have any substituents. For example, “a substituent group in which two or more substituents are connected” may be a biphenyl group. That is, the biphenyl group may be an aryl group, or it may be interpreted as a substituent in which two phenyl groups are connected.

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

In this specification, examples of the halogen group include fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

In the present specification, the silyl group is deuterium; Substituted or unsubstituted alkyl group; Alternatively, it may be substituted or unsubstituted with a substituted or unsubstituted aryl group. The silyl group specifically includes, but is not limited to, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, and phenylsilyl group. No.

In the present specification, the boron group is deuterium; Substituted or unsubstituted alkyl group; Alternatively, it may be substituted or unsubstituted with a substituted or unsubstituted aryl group. The boron group specifically includes, but is not limited to, trimethyl boron group, triethyl boron group, t-butyldimethyl boron group, triphenyl boron group, and phenyl boron group.

In the present specification, the alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60. According to one embodiment, the carbon number of the alkyl group is 1 to 30. According to another embodiment, the carbon number of the alkyl group is 1 to 20. According to another embodiment, the carbon number of the alkyl group is 1 to 10. Specific examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, and octyl groups.

In the present specification, the amine group is -NH ₂ ; Alkylamine group; N-alkylarylamine group; Arylamine group; N-arylheteroarylamine group; It may be selected from the group consisting of N-alkylheteroarylamine group and heteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of amine groups include methylamine groups; dimethylamine group; ethylamine group; diethylamine group; phenylamine group; Naphthylamine group; Biphenylamine group; Anthracenylamine group; 9-methylanthracenylamine group; Diphenylamine group; Ditolylamine group; N-phenyltolylamine group; Triphenylamine group; N-phenylbiphenylamine group; N-phenylnaphthylamine group; N-biphenylnaphthylamine group; N-naphthylfluorenylamine group; N-phenylphenanthrenylamine group; N-biphenylphenanthrenylamine group; N-phenylfluorenylamine group; N-phenylterphenylamine group; N-phenanthrenylfluorenylamine group; N-biphenylfluorenylamine group, etc., but is not limited thereto.

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

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

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

In this specification, the alkyl groups in the alkylamine group, N-arylalkylamine group, alkylthioxy group, alkylsulfoxy group, and N-alkylheteroarylamine group are the same as examples of the alkyl groups described above. Specifically, the alkylthioxy group includes methylthioxy group; ethylthioxy group; tert-butylthioxy group; hexylthioxy group; Octylthioxy groups, etc., and examples of alkylsulfoxy groups include mesyl; ethyl sulfoxy group; Propyl alcohol oxygen group; Butyl sulfoxy group, etc., but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to another embodiment, the carbon number of the cycloalkyl group is 3 to 6. Specifically, it includes cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc., but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, such as a phenyl group, biphenyl group, or terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, triphenylene group, chrysenyl group, fluorenyl group, etc., but is not limited thereto.

In the present specification, the heteroaryl group is a cyclic group containing one or more of N, O, P, S, Si, and Se as heteroatoms, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. According to one embodiment, the carbon number of the heterocyclic group is 2 to 30. Examples of heterocyclic groups include pyridine group, pyrrole group, pyrimidine group, pyridazinyl group, furan group, thiophene group, imidazole group, pyrazole group, dibenzofuran group, dibenzothiophene group, carbazole group, etc. However, it is not limited to these.

In the present specification, the arylene group is the same as defined for the aryl group, except that it is a divalent group.

In the present specification, the heteroarylene group is the same as defined for the heteroaryl group, except that it is a divalent group.

In this specification, Formula 1 is Formula 1-1 or 1-2 below.

[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2, A, B, L, Q1, and Q2 are as defined in Formula 1.

In this specification, Formula 1 is Formula 1-3 below.

[Formula 1-3]

In Formula 1-3, A, B, and L are as defined in Formula 1,

R1 and R2 are the same or different from each other, and are each independently hydrogen, deuterium, nitrile group, nitro group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted heteroaryl group. Or, it combines with an adjacent group to form a substituted or unsubstituted ring,

a and b are integers from 1 to 5,

When a is 2 or more, R1 is the same or different,

When b is 2 or more, R2 is the same or different.

In this specification, Formula 1 is Formula 1-4 below.

[Formula 1-4]

In Formula 1-4, L, Q1, and Q2 are as defined in Formula 1,

One of X1 to X3 is N, and the others are N or CR, respectively,

R is deuterium, nitrile group, nitro group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted heteroaryl group,

One of X4 to X8 is N, and the others are N or CR1, respectively,

R1 is deuterium, nitrile group, nitro group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted heteroaryl group, or is substituted or unsubstituted by combining with adjacent substituents. forms a ring

According to an exemplary embodiment of the present specification, A is pyridine, pyrimidine, triazine, quinoline, quinazoline, or quinoxaline,

The pyridine, pyrimidine, triazine, quinoline, quinazoline, or quinoxaline are each independently substituted with deuterium, nitrile group, nitro group, halogen group, or substituted or unsubstituted aryl group with substituted or unsubstituted alkyl group.

According to an exemplary embodiment of the present specification, B is pyridine, pyrimidine, or triazine, and the pyridine, pyrimidine, or triazine are each independently deuterium, nitrile group, nitro group, halogen group, or substituted or unsubstituted. It is substituted with a substituted alkyl group or with an unsubstituted aryl group.

According to an exemplary embodiment of the present specification, R1 and R2 are the same as or different from each other, and are each independently hydrogen, deuterium, nitrile group, nitro group, halogen group, alkyl group having 1 to 10 carbon atoms, and aryl group having 6 to 30 carbon atoms. group, or a heteroaryl group having 3 to 30 carbon atoms, or is combined with an adjacent group to form a substituted or unsubstituted benzene ring.

According to an exemplary embodiment of the present specification, R1 and R2 are the same as or different from each other, and are each independently hydrogen, deuterium, nitrile group, nitro group, F, Cl, methyl group, ethyl group, propyl group, terbutyl group, phenyl group. , a naphthyl group, anthracene group, biphenyl group, carbazole group, dibenzofuran group, or dibenzothiophene group, or is combined with an adjacent group to form a benzene ring.

According to an exemplary embodiment of the present specification, A is a triazine substituted with an aryl group, a pyrimidine substituted with an aryl group, a pyridine substituted with an aryl group, or a quinazole group substituted with an aryl group.

According to an exemplary embodiment of the present specification, A is a triazine, pyrimidine, pyridine, or quinazole group, and the substituents are substituted with deuterium or with an unsubstituted aryl group having 6 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, B is a triazine substituted with an aryl group, a pyrimidine substituted with an aryl group, a pyridine substituted with an aryl group, or a quinazole group substituted with an aryl group.

According to an exemplary embodiment of the present specification, B is a triazine, pyrimidine, pyridine, or quinazole group, and the substituents are substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms that is unsubstituted or substituted with deuterium.

According to an exemplary embodiment of the present specification, L is a direct bond, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, L is a direct bond, or an arylene group having 6 to 30 carbon atoms unsubstituted or substituted with deuterium.

According to an exemplary embodiment of the present specification, L is a direct bond, a phenyl group substituted or unsubstituted with deuterium, or a divalent naphthalene group substituted or unsubstituted with deuterium.

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

According to an exemplary embodiment of the present specification, one of Q1 and Q2 is an aryl group having 6 to 30 carbon atoms, and the other is hydrogen or an aryl group having 6 to 30 carbon atoms,

When one of Q1 and Q2 is hydrogen, the remainder is an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with one or more substituents selected from deuterium, nitro group, halogen group, alkyl group, aryl group, and heteroaryl group,

When both Q1 and Q2 are aryl groups having 6 to 30 carbon atoms, the aryl group having 6 to 30 carbon atoms is substituted with one or more substituents selected from deuterium, nitrile group, nitro group, halogen group, alkyl group, aryl group, and heteroaryl group. or unsubstituted.

According to an exemplary embodiment of the present specification, when one of Q1 and Q2 is hydrogen, the other is a phenyl group, naphthyl group, phenanthrene group, fluoranthene group, or phenanthrene group, and the substituent is deuterium, nitro group, F , an alkyl group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, or a heteroaryl group with 3 to 30 carbon atoms that is unsubstituted or substituted with deuterium and an alkyl group with 1 to 10 carbon atoms. It's a relief.

According to an exemplary embodiment of the present specification, when Q1 and Q2 are a phenyl group, naphthyl group, phenanthrene group, fluoranthene group, or phenanthrene group, the substituent is deuterium, nitro group, nitrile group, F, and has 1 to 10 carbon atoms. is substituted or unsubstituted with an alkyl group, a haloalkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, or a heteroaryl group with 3 to 30 carbon atoms that is substituted or unsubstituted with deuterium and an alkyl group with 1 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, when Q1 and Q2 are a phenyl group, a naphthyl group, a phenanthrene group, a fluoranthene group, or a phenanthrene group, the substituent is a deuterium group, a nitrile group, F, a methyl group, or a methyl group substituted with F. , terbutyl group, dibenzofuran group, dibenzothiophene group, adamantyl group, nitro group, carbazole group substituted or unsubstituted with deuterium, benzothiazole group, benzoxazole group, or benz substituted or unsubstituted with ethyl group. It is substituted or unsubstituted with an imidazole group.

According to an exemplary embodiment of the present specification, when one of Q1 and Q2 is hydrogen and the other is a phenyl group, naphthyl group, phenanthrene group, fluoranthene group, or phenanthrene group, the substituent is deuterium, F, methyl group, F-substituted methyl group, terbutyl group, dibenzofuran group, dibenzothiophene group, adamantyl group, nitro group, deuterium-substituted or unsubstituted carbazole group, benzothiazole group, benzoxazole group, or ethyl group. Or, it is substituted or unsubstituted with an unsubstituted benzimidazole group.

According to an exemplary embodiment of the present specification, when Q1 and Q2 are a phenyl group, a naphthyl group, a phenanthrene group, a fluoranthene group, or a phenanthrene group, the phenyl group is a deuterium group, a nitrile group, F, a methyl group, or a methyl group substituted with F. , terbutyl group, dibenzofuran group, dibenzothiophene group, adamantyl group, nitro group, carbazole group substituted or unsubstituted with deuterium, benzothiazole group, benzoxazole group, or benz substituted or unsubstituted with ethyl group. Substituted or unsubstituted with an imidazole group,

The naphthyl group, phenanthrene group, fluoranthene group, and phenanthrene group are unsubstituted.

According to an exemplary embodiment of the present specification, when one of Q1 and Q2 is hydrogen and the other is a phenyl group, naphthyl group, phenanthrene group, fluoranthene group, or phenanthrene group, the phenyl group is deuterium, F, methyl group, F-substituted methyl group, terbutyl group, dibenzofuran group, dibenzothiophene group, adamantyl group, nitro group, deuterium-substituted or unsubstituted carbazole group, benzothiazole group, benzoxazole group, or ethyl group. or substituted or unsubstituted with an unsubstituted benzimidazole group,

The naphthyl group, phenanthrene group, fluoranthene group, and phenanthrene group are unsubstituted.

According to an exemplary embodiment of the present specification, Formula 1 is one of the structural formulas below.

Substituents of the compound of Formula 1 may be combined by methods known in the art, and the type, position, or number of substituents may be changed according to techniques known in the art.

In addition, by introducing various substituents into the core structure of the above structure, it is possible to synthesize compounds having the unique properties of the introduced substituents. For example, by introducing substituents mainly used in hole injection layer materials, hole transport materials, light emitting layer materials, and electron transport layer materials used in the manufacture of organic light-emitting devices into the core structure, a material that satisfies the conditions required for each organic material layer can be synthesized. You can.

Additionally, the organic light emitting device according to the present invention includes a first electrode; a second electrode provided opposite the first electrode; And an organic light-emitting device comprising at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer contains the above-described compound.

The organic light emitting device of the present invention can be manufactured using conventional organic light emitting device manufacturing methods and materials, except that one or more organic material layers are formed using the above-described compounds.

The compound may be formed into an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution application method refers to spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, or may have a multi-layer 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 layer that simultaneously performs hole injection and hole transport, a light-emitting layer, an electron transport layer, an electron injection layer, etc. as an organic material layer. However, the structure of the organic light emitting device is not limited to this and may include fewer or more organic material layers.

In the organic light emitting device of the present invention, the organic material layer may include one or more of an electron transport layer, an electron injection layer, and an electron injection and transport layer, and one or more of the layers includes the compound of Formula 1.

In another organic light emitting device, the organic material layer may include an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes the compound of Formula 1.

In the organic light emitting device of the present invention, the electron injection and transport layer includes the compound of Formula 1 and a metal complex.

In the organic light emitting device of the present invention, the organic material layer may include one or more layers among a hole injection layer, a hole transport layer, and a layer that performs both hole injection and hole transport, and one or more of the layers contains the compound of Formula 1. Includes.

In another organic light emitting device, the organic material layer may include a hole injection layer or a hole transport layer, and the hole transport layer or the hole injection layer may include the compound of Formula 1.

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

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

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

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

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

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

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

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

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

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

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

(10) Anode/hole transport layer/electron suppression layer/light emitting layer/electron transport layer/cathode

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

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

(13) Anode/hole injection layer/hole transport layer/electron suppression layer/light-emitting layer/electron transport layer/electron injection layer/cathode

(14) Anode/hole transport layer/light emitting layer/hole suppression layer/electron transport layer/cathode

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

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

(17) Anode/hole injection layer/hole transport layer/light-emitting layer/hole suppression layer/electron transport layer/electron injection layer/cathode

(18) Anode/hole injection layer/hole transport layer/electron suppression layer/light emitting layer/hole blocking layer/electron injection and transport layer/cathode

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

Figure 1 illustrates the structure of an organic light-emitting device in which an anode 2, an organic material layer 3, and a cathode 4 are sequentially stacked on a substrate 1. In this structure, the compound of Formula 1 may be included in the organic layer 3.

In Figure 2, an anode (2), a hole injection layer (5), a hole transport layer (6), a light emitting layer (7), an electron injection and transport layer (8), and a cathode (4) are sequentially stacked on a substrate (1). The structure of the light emitting device is illustrated. In this structure, the compound of Formula 1 is included in the electron injection and transport layer (8).

For example, the organic light emitting device according to the present invention deposits a metal, a conductive metal oxide, or an alloy thereof on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. An anode is formed by depositing an anode on which a hole injection layer, a hole transport layer, a layer that simultaneously performs hole transport and hole injection, a light emitting layer, an electron transport layer, an electron injection layer, and a group consisting of a layer that performs both electron transport and electron injection are selected. It can be manufactured by forming an organic material layer containing one or more selected layers and then depositing a material that can be used as a cathode thereon. In addition to this method, an organic light-emitting device can also be made by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate.

The organic material layer may have a multi-layer structure including a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer, but is not limited to this and may have a single-layer structure. In addition, the organic material layer uses a variety of polymer materials to form a smaller number of layers by using a solvent process rather than a deposition method, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be manufactured in layers.

The anode is an electrode that injects holes, and the anode material is generally preferably a material with a large work function to facilitate hole injection into the organic layer. Specific examples of anode materials 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); Combination of metal and oxide such as ZnO:Al or SnO ₂ :Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline are included, but are not limited to these.

The cathode is an electrode that injects electrons, and the cathode material is preferably a material with a low work function to facilitate electron injection into the organic layer. Specific examples of cathode materials include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; There are, but are not limited to, multi-layered materials such as LiF/Al or LiO ₂ /Al.

The hole injection layer is a layer that serves to facilitate the injection of holes from the anode to the light emitting layer, and the hole injection material is a material that can well inject holes from the anode at a low voltage. HOMO (highest occupied) of the hole injection material It is preferable that the molecular orbital is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of hole injection materials include metal porphyrine, oligothiophene, arylamine-based organic material, hexanitrilehexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. organic substances, anthraquinone, polyaniline, and polythiophene series conductive polymers, etc., but are not limited to these. The thickness of the hole injection layer may be 1 to 150 nm. If the thickness of the hole injection layer is 1 nm or more, there is an advantage in preventing the hole injection characteristics from deteriorating, and if it is 150 nm or less, the thickness of the hole injection layer is so thick that the driving voltage is increased to improve the movement of holes. There is an advantage to preventing this.

According to an exemplary embodiment of the present specification, the hole injection layer includes, but is not limited to, a compound represented by the following formula HI-1.

[Formula HI-1]

In the formula HI-1,

R300 to R308 are the same or different from each other, and are each independently hydrogen; heavy hydrogen; Nitrile group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted amine group; Substituted or unsubstituted aryl group; Or it is a substituted or unsubstituted heteroaryl group, or combines with an adjacent group to form a substituted or unsubstituted ring,

r301 and r302 are each integers from 1 to 4,

r303 and r304 are each integers from 1 to 3,

When r301 is 2 or more, R301 is the same or different from each other,

When r302 is 2 or more, R302 is the same or different from each other,

When r303 is 2 or more, R303 is the same or different from each other,

When r304 is 2 or more, R304 is the same as or different from each other.

According to the provisional status of this specification, R301 to R304 are hydrogen.

According to the provisional status of the present specification, R300 is a substituted or unsubstituted aryl group.

According to the provisional status of the present specification, R300 is a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

According to the provisional status of the present specification, R300 is a phenyl group.

According to an exemplary embodiment of the present specification, R305 to R308 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

According to an exemplary embodiment of the present specification, R305 to R308 are the same as or different from each other, and are each independently a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; Or it is a monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms that is substituted or unsubstituted with a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, R305 to R308 are the same as or different from each other, and are each independently a phenyl group; Or it is a carbazole group substituted or unsubstituted with a phenyl group.

According to an exemplary embodiment of the present specification, the formula HI-1 is represented by the following compound.

The hole transport layer may play a role in facilitating the transport of holes. The hole transport material is a material that can transport holes from the anode or hole injection layer and transfer them to the light emitting layer, and a material with high mobility for holes is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers with both conjugated and non-conjugated portions, but are not limited to these.

According to an exemplary embodiment of the present specification, the hole transport layer includes a compound represented by the following formula HT-1, but is not limited thereto.

[Formula HT-1]

In the formula HT-1,

At least one of X'1 to X'6 is N, and the remainder is CH,

R309 to R314 are the same or different from each other, and are each independently hydrogen; heavy hydrogen; Nitrile group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted amine group; Substituted or unsubstituted aryl group; Or it is a substituted or unsubstituted heteroaryl group, or it combines with adjacent groups to form a substituted or unsubstituted ring.

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

According to an exemplary embodiment of the present specification, R309 to R314 are nitrile groups.

According to an exemplary embodiment of the present specification, the formula HT-1 is represented by the following compound.

According to an exemplary embodiment of the present specification, the hole transport layer includes a compound represented by the following chemical formula HT-2, but is not limited thereto.

[Formula HT-2]

In the formula HT-2,

R400 to R402 are the same or different from each other, and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted amine group; Substituted or unsubstituted heteroaryl group; and any one selected from the group consisting of combinations thereof, or by combining with adjacent groups to form a substituted or unsubstituted ring,

L402 are the same or different from each other, and each independently represents a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.

According to an exemplary embodiment of the present specification, R400 to R402 are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group; Substituted or unsubstituted amine group; Substituted or unsubstituted heteroaryl group; and any one selected from the group consisting of combinations thereof.

According to an exemplary embodiment of the present specification, R400 and R401 are the same or different from each other and are each independently a substituted or unsubstituted aryl group, or are combined with adjacent groups to form an aromatic hydrocarbon ring substituted with an alkyl group.

According to an exemplary embodiment of the present specification, R400 and R401 are the same or different from each other, and are each independently a phenyl group or a diphenylfluorene group.

According to an exemplary embodiment of the present specification, R402 is a carbazole group substituted or unsubstituted with a phenyl group.

According to an exemplary embodiment of the present specification, the formula HT-2 is selected from the following compounds.

An electron blocking layer may be provided between the hole transport layer and the light emitting layer. The electron suppressing layer may be made of the spiro compound described above or a material known in the art.

The light-emitting layer may emit red, green, or blue light and may be made of a phosphorescent material or a fluorescent material. The light-emitting material is a material capable of emitting light in the visible range by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and is preferably a material with good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV) series polymer; Spiro compounds; Polyfluorene, rubrene, etc., but are not limited to these.

Host materials for the light-emitting layer include condensed aromatic ring derivatives or heterocycle-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocyclic ring-containing compounds include carbazole derivatives, dibenzofuran derivatives, and ladder-type compounds. These include, but are not limited to, furan compounds and pyrimidine derivatives.

An organic light-emitting device according to an exemplary embodiment of the present specification includes a light-emitting layer, and the light-emitting layer includes a compound represented by the following formula H as a host material.

[Formula H]

In the formula H,

L21 and L22 are the same or different from each other and are each independently directly bonded; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

R21 to R28 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Ar21 and Ar22 are the same or different from each other, and are each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

In an exemplary embodiment of the present specification, R21 to R28 are the same as or different from each other, and are each independently hydrogen or deuterium.

In an exemplary embodiment of the present specification, Ar21 and Ar22 are different from each other.

In an exemplary embodiment of the present specification, Ar21 and Ar22 are the same or different from each other, and each independently represents a substituted or unsubstituted aryl group.

In an exemplary embodiment of the present specification, Ar21 and Ar22 are naphthyl groups.

In an exemplary embodiment of the present specification, L21 and L22 are the same or different from each other and are each independently directly bonded; Substituted or unsubstituted phenylene group; Substituted or unsubstituted biphenylene group; Substituted or unsubstituted naphthylene group; A substituted or unsubstituted divalent dibenzofuran group; Or it is a substituted or unsubstituted dibenzothiophene group.

In one embodiment of the present specification, the formula H is represented by the following compound.

When the light-emitting layer emits red light, the light-emitting dopants include PIQIr(acac)(bis(1-phenylquinoline)acetylacetonateiridium), PQIr(acac)(bis(1-phenylquinoline)acetylacetonate iridium), and PQIr(tris(1-phenylquinoline)iridium). ), phosphorescent materials such as PtOEP (octaethylporphyrin platinum), or fluorescent materials such as Alq ₃ (tris(8-hydroxyquinolino)aluminum) may be used, but are not limited to these. If the light-emitting layer emits green light, a phosphor such as Ir(ppy) ₃ (fac tris(2-phenylpyridine)iridium) or a fluorescent material such as Alq3 (tris(8-hydroxyquinolino)aluminum) can be used as the light-emitting dopant. However, it is not limited to this. When the light-emitting layer emits blue light, the light-emitting dopant may be a phosphorescent material such as (4,6-F2ppy) ₂ Irpic, spiro-DPVBi, spiro-6P, distylbenzene (DSB), distrylarylene (DSA), Fluorescent materials such as PFO-based polymers and PPV-based polymers may be used, but are not limited to these.

According to an exemplary embodiment of the present specification, the dopant includes, but is not limited to, a compound represented by the following formula D-1.

[Formula D-1]

In Formula D-1,

T1 to T6 are the same or different from each other, and are each independently hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

t5 and t6 are each integers from 1 to 4,

When t5 is 2 or more, the 2 or more T5 are the same or different from each other,

When the t6 is 2 or more, the 2 or more T6s are the same or different from each other.

According to an exemplary embodiment of the present specification, T1 to T6 are the same as or different from each other, and are each independently hydrogen; A substituted or unsubstituted straight-chain or branched alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; Or it is a substituted or unsubstituted monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, T1 to T6 are the same as or different from each other, and are each independently hydrogen; A straight or branched alkyl group having 1 to 30 carbon atoms; a nitrile group, or a monocyclic or polycyclic aryl group having 6 to 30 carbon atoms substituted or unsubstituted with a straight-chain or branched alkyl group having 1 to 30 carbon atoms; Or it is a monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, T1 to T6 are the same as or different from each other, and are each independently hydrogen; isopropyl group; A phenyl group substituted with a methyl group; Or it is a dibenzofuran group.

According to an exemplary embodiment of the present specification, Formula D-1 is represented by the following compound.

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

The electron transport layer may play a role in facilitating the transport of electrons. The electron transport material is a material that can easily inject electrons from the cathode and transfer them to the light-emitting layer, and a material with high mobility for electrons is suitable. Specific examples include Al complex of 8-hydroxyquinoline; Complex containing Alq ₃ ; organic radical compounds; Hydroxyflavone-metal complexes, etc., but are not limited to these. The thickness of the electron transport layer may be 1 to 50 nm. If the thickness of the electron transport layer is 1 nm or more, there is an advantage in preventing the electron transport characteristics from deteriorating, and if it is 50 nm or less, the thickness of the electron transport layer is too thick to prevent the driving voltage from increasing to improve the movement of electrons. There are benefits to this.

The electron injection layer may serve to facilitate injection of electrons. The electron injection material has the ability to transport electrons, has an excellent electron injection effect from the cathode, a light emitting layer or a light emitting material, prevents movement of excitons generated in the light emitting layer to the hole injection layer, and also has an excellent electron injection effect from the cathode to the light emitting layer or light emitting material. , Compounds with excellent thin film forming ability are preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc. and their derivatives, metals. These include, but are not limited to, complex compounds and nitrogen-containing five-membered ring derivatives.

The electron injection and transport layer may serve to simultaneously inject and transport electrons. The layer can be formed using an electron transport material and an electron injection material.

Examples of the metal complex compounds include 8-hydroxyquinolinato lithium, 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-naphtolato) aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato) gallium, etc. It is not limited to this.

The hole blocking layer is a layer that prevents holes from reaching the cathode, and can generally be formed under the same conditions as the hole injection layer. Specifically, it includes oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complex, etc., but is not limited thereto.

The organic light emitting device according to the present invention may be a front emitting type, a back emitting type, or a double-sided emitting type depending on the material used.

The organic light emitting device of the present invention can be manufactured using conventional organic light emitting device manufacturing methods and materials, except that one or more organic material layers are formed using the above-described compounds.

The method for producing the compound of Formula 1 and the production of organic light-emitting devices using the same will be described in detail in the examples below. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

In the following reaction formula, various types of intermediates can be synthesized by appropriately selecting starting materials known to those skilled in the art regarding the type and number of substituents. Reaction types and reaction conditions known in the art can be used.

The method for producing the compound of Formula 1 and the production of organic light-emitting devices using the same will be described in detail in the examples below. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

In the following reaction formula, various types of intermediates can be synthesized by appropriately selecting starting materials known to those skilled in the art regarding the type and number of substituents. Reaction types and reaction conditions known in the art can be used.

Q1, Q2, A and B are as defined in Formula 1 above.

By appropriately combining the production formulas described in the Examples of this specification and the intermediates based on common technical knowledge, all of the compounds of Formula 1 described in this specification can be prepared.

[Synthesis example]

Synthesis Example 1: Synthesis of Compound 1

Step 1) Synthesis of Compound 1-a

In a nitrogen atmosphere, 1-bromo-4-chloro-2-iodobenzene (50 g, 157.6 mmol) and phenylboronic acid (19.2 g, 157.6 mmol) were added to 1000 ml of tetrahydrofuran, stirred and refluxed. Afterwards, sodium carbonate (50.1 g, 472.7 mmol) was dissolved in 50 ml of water, stirred sufficiently, and then tetrakistriphenyl-phosphinopalladium (5.5 g, 4.7 mmol) was added. After reacting for 1 hour, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in 843 mL of 20 times toluene, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with toluene and ethyl acetate to prepare white solid compound 1-a (35.8 g, 85%, MS: [M+H]+ = 268.6).

Step 2) Synthesis of Compound 1-b

Compound 1-a (50 g, 186.9 mmol) and (2-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)boronic acid (66 g, 186.9 mmol) in a nitrogen atmosphere. was added to 1000 ml of tetrahydrofuran, stirred and refluxed. Afterwards, potassium carbonate (77.5 g, 560.6 mmol) was dissolved in 77 ml of water, stirred sufficiently, and then tetrakistriphenyl-phosphinopalladium (6.5 g, 5.6 mmol) was added. After reacting for 1 hour, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in 1854 mL of 20 times toluene, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with toluene and ethyl acetate to prepare white solid compound 1-b (64.9 g, 70%, MS: [M+H]+ = 497.3).

Step 3) Synthesis of Compound 1-c

In a nitrogen atmosphere, compound 1-b (50 g, 100.8 mmol) and bis(pinacolato)diboron (25.6 g, 100.8 mmol) were added to 1000 ml of 1,4-dioxane, stirred and refluxed. Afterwards, potassium acetate (64.2 g, 302.4 mmol) was added, stirred sufficiently, and then palladium dibenzylidene acetone palladium (1.7 g, 3 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, the organic layer was filtered to remove salts, and the filtered organic layer was distilled. This was again dissolved in 592 mL of 10 times chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethanol to prepare white solid compound 1-c (29.6 g, 50%, MS: [M+H]+ = 588.5).

Step 4) Synthesis of Compound 1

In a nitrogen atmosphere, compound 1-c (50 g, 85.1 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (22.8 g, 85.1 mmol) were added to 1000 ml of tetrahydrofuran and stirred. It refluxed. Afterwards, potassium carbonate (35.3 g, 255.3 mmol) was dissolved in 35 ml of water, stirred sufficiently, and then tetrakistriphenyl-phosphinopalladium (2.9 g, 2.6 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in 1179 mL of 20 times toluene, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with toluene and ethyl acetate to prepare white solid Compound 1 (45.4 g, 77%, MS: [M+H]+ = 693.8).

Synthesis Example 2: Synthesis of Compound 2

In Synthesis Example 1, compound 2 (MS[M+H] ⁺ = 743.9) was prepared in the same manner as that of compound 1, except that phenylboronic acid was changed to naphthalen-1-ylboronic acid. .

Synthesis Example 3: Synthesis of Compound 3

In Synthesis Example 1, Compound 3 (MS[M+H] ⁺ = 743.9) was prepared in the same manner as that of Compound 1, except that phenylboronic acid was changed to naphthalen-2-ylboronic acid. .

Synthesis Example 4: Synthesis of Compound 4

In Synthesis Example 1, Compound 4 (MS[M+H] ⁺ = 793.9) was prepared using the same method as that of Compound 1, except that phenylboronic acid was changed to phenanthrene-9-ylboronic acid. did.

Synthesis Example 5: Synthesis of Compound 5

In Synthesis Example 1, (2-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)boronic acid and 2-chloro-4,6-diphenyl-1,3,5 -Compound 1, except that triazine was changed to (2-(4,6-diphenylpyrimidin-2-yl)phenyl)boronic acid and 2-chloro-4,6-diphenylpyrimidine. Compound 5 (MS[M+H] ⁺ = 691.9) was prepared using the same manufacturing method.

Synthesis Example 6: Synthesis of Compound 6

In Synthesis Example 1, phenylboronic acid, (2-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)boronic acid and 2-chloro-4,6-diphenyl-1 , 3,5-triazine is combined with fluoranthen-8-ylboronic acid, (2-(2,6-diphenylpyrimidin-4-yl)phenyl)boronic acid and 4-chloro-2,6-diphenylpyri. Compound 6 (MS[M+H] ⁺ = 815.4) was prepared in the same manner as that of compound 1, except that it was changed to midine.

Synthesis Example 7: Synthesis of Compound 7

In Synthesis Example 1, compound 7 (MS[M+H] ⁺ = 698.3) was prepared using the same manufacturing method as that of compound 4, except that phenylboronic acid was changed to (phenyl-d5)boronic acid. did.

Synthesis Example 8: Synthesis of Compound 8

In Synthesis Example 1, phenylboronic acid and 2-chloro-4,6-diphenyl-1,3,5-triazine were reacted with naphthalen-2-ylboronic acid and 2-chloro-4-phenyl-6-(phenyl-d5 Compound 8 (MS[M+H] ⁺ = 748.3) was prepared in the same manner as that of Compound 1, except that it was changed to )-1,3,5-triazine.

Synthesis Example 9: Synthesis of Compound 9

In Synthesis Example 1, the same method for preparing Compound 1 was used, except that 1-bromo-4-chloro-2-iodobenzene was changed to 4-bromo-1-chloro-2-iodobenzene. Compound 9 (MS[M+H] ⁺ = 693.3) was prepared using the preparation method.

Synthesis Example 10: Synthesis of Compound 10

In Synthesis Example 1, 1-bromo-4-chloro-2-iodobenzene and boronic acid were reacted with 4-bromo-1-chloro-2-iodobenzene and (4-(adamantan-1-yl) Compound 10 (MS[M+H] ⁺ = 827.4) was prepared using the same manufacturing method as that of Compound 1, except that it was changed to boronic acid.

Synthesis Example 11: Synthesis of Compound 11

In Synthesis Example 1, 1-bromo-4-chloro-2-iodobenzene, (2-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)boronic acid and 2 -Chloro-4,6-diphenyl-1,3,5-triazine is 4-bromo-1-chloro-2-iodobenzene, (2-(4,6-diphenylpyrimidin-2-yl ) phenyl) boronic acid and 2-chloro-4- (dibenzo [b, d] thiophen-4-yl) -6-phenyl-1,3,5-triazine, except that they are used as compounds. Compound 11 (MS[M+H] ⁺ = 798.3) was prepared using the same preparation method as that of 1.

Synthesis Example 12: Synthesis of Compound 12

In Synthesis Example 1, 1-bromo-4-chloro-2-iodobenzene, phenylboronic acid and 2-chloro-4,6-diphenyl-1,3,5-triazine were reacted with 4-bromo-1. -Compound 1, except that it was changed to chloro-2-iodobenzene, (3-(9H-carbazol-9-yl)phenyl)boronic acid, and 2-chloro-4,6-diphenylpyrimidine. Compound 12 (MS[M+H] ⁺ = 857.3) was prepared using the same manufacturing method as that of .

Synthesis Example 13: Synthesis of Compound 13

In Synthesis Example 1, 2-chloro-4,6-diphenyl-1,3,5-triazine is converted to 2-(2-chlorophenyl)-4,6-diphenyl-1,3,5-triazine. Compound 13 (MS[M+H] ⁺ =769.3) was prepared using the same preparation method as that of Compound 1, except that it was used in modification.

Synthesis Example 14: Synthesis of Compound 14

In Synthesis Example 1, 1-bromo-4-chloro-2-iodobenzene, (2-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)boronic acid and 2 -Chloro-4,6-diphenyl-1,3,5-triazine is combined with 1-bromo-4-chloro-2,3-diiodobenzene, (2-(4-phenylquinazolin-2-yl) The same method for preparing compound 1 was used, except that it was changed to phenyl)boronic acid and 9-(4-chloro-6-phenyl-1,3,5-triazin-2-yl)-9H-carbazole. Compound 14 (MS[M+H] ⁺ = 831.3) was prepared using the preparation method.

Experimental Example 1

A glass substrate coated with a thin film of ITO (indium tin oxide) with a thickness of 1,000 Å was placed in distilled water with a detergent dissolved in it and washed ultrasonically. At this time, a detergent manufactured by Fischer Co. was used, and distilled water filtered secondarily using a filter manufactured by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing with distilled water, it was ultrasonic washed with solvents of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Additionally, the substrate was cleaned for 5 minutes using oxygen plasma and then transported to a vacuum evaporator.

On the ITO transparent electrode prepared in this way, the following compound HI-A was thermally vacuum deposited to a thickness of 600 Å to form a hole injection layer. On the hole injection layer, hexanitrile hexaazatriphenylene (HAT, 50Å) of the following formula and HT-A (600Å) of the following compound were sequentially vacuum deposited to form a hole transport layer.

Subsequently, the following compounds BH and BD were vacuum deposited at a weight ratio of 25:1 to a film thickness of 200 Å on the hole transport layer to form a light emitting layer.

On the emitting layer, Compound 1 prepared in Synthesis Example 1 and the following compound [LiQ] (Lithiumquinolate) were vacuum deposited at a 1:1 weight ratio to form an electron injection and transport layer with a thickness of 360 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 10 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.

In the above process, the deposition rate of organic matter was maintained at 0.4 ~ 0.9 Å/sec, the deposition rate of lithium fluoride of the cathode was maintained at 0.3 Å/sec, and aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was 1 × 10. An organic light emitting device was manufactured by maintaining ^-7 to 5 × 10 ^-8 torr.

Experimental Examples 2 to 14

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

Comparative Experimental Examples 1 to 6

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1, except that the compound in Table 1 below was used instead of Compound 1 in Experimental Example 1. The compounds ET-1 to ET-6 used in Table 1 below are as follows.

For the organic light-emitting devices manufactured in the above experimental examples and comparative experimental examples, the driving voltage, luminous efficiency, and color coordinates were measured at a current density of 10 mA/cm ² , and the luminance was 90% of the initial luminance at a current density of 20 mA/cm ^2. The time to become (T ₉₀ ) was measured. The results are shown in Table 1 below.

compound
(Electron injection and transport layer) Voltage
(V@10mA/cm ² ) efficiency
(cd/A@10mA/cm ² ) Color coordinates
(x,y) _T90
(hr@20mA/cm ² ) Experimental Example 1 Compound 1 3.15 4.25 (0.136, 0.112) 180 Experimental Example 2 Compound 2 3.20 4.38 (0.136, 0.111) 177 Experimental Example 3 Compound 3 3.19 4.44 (0.136, 0.112) 198 Experimental Example 4 Compound 4 3.25 4.19 (0.136, 0.111) 169 Experimental Example 5 Compound 5 3.09 4.21 (0.136, 0.111) 172 Experimental Example 6 Compound 6 3.22 4.39 (0.136, 0.111) 159 Experimental Example 7 Compound 7 3.15 4.25 (0.136, 0.112) 220 Experimental Example 8 Compound 8 3.19 4.46 (0.136, 0.111) 240 Experimental Example 9 Compound 9 3.17 4.27 (0.136, 0.112) 171 Experimental Example 10 Compound 10 3.26 4.26 (0.136, 0.111) 165 Experimental Example 11 Compound 11 3.05 4.78 (0.136, 0.111) 158 Experimental Example 12 Compound 12 3.29 4.66 (0.136, 0.111) 160 Experimental Example 13 Compound 13 3.23 4.28 (0.136, 0.111) 189 Experimental Example 14 Compound 14 3.26 4.5 (0.136, 0.111) 177 Comparative Experiment Example 1 ET-1 4.93 3.01 (0.136, 0.111) 91 Comparative Experiment Example 2 ET-2 4.88 3.05 (0.136, 0.111) 95 Comparative Experiment Example 3 ET-3 4.75 3.08 (0.136, 0.112) 99 Comparative Experiment Example 4 ET-4 5.13 3.19 (0.136, 0.111) 54 Comparative Experiment Example 5 ET-5 5.55 2.78 (0.136, 0.112) 45 Comparative Experiment Example 6 ET-6 5.25 2.85 (0.136, 0.111) 59

As shown in Table 1, it was confirmed that the organic light-emitting device using the compound represented by Formula 1 of the present invention exhibited excellent characteristics in terms of voltage, efficiency, and/or lifespan (T ₉₀ ).

Comparing Experimental Examples 1 to 14 of Table 1 and Comparative Experimental Examples 1 and 2, the organic light-emitting device containing the compound of Formula 1 of the present invention has a heterocycle containing an N-containing 6-membered ring with electron transport properties. Because it is substituted with two or more elements, its electron transport ability can be adjusted in various ways. Therefore, it was confirmed that the organic light-emitting device showed significantly better properties in terms of efficiency and lifespan than an organic light-emitting device using a compound with one N-containing ring substituted.

Comparing Experimental Examples 1 to 14 of Table 1 and Comparative Experimental Examples 3 and 4, the organic light-emitting device containing the compound of Formula 1 of the present invention has a heterocycle containing an N-containing 6-membered ring with electron transport properties. Since it is adjacent to the ortho position of phenyl, structural distortion occurs, which is advantageous for electron transport. Therefore, the heterocycle containing an N-containing 6-membered ring has a higher voltage than the organic light emitting device using meta and para phenyl. It was confirmed that it showed significantly excellent characteristics in terms of efficiency and lifespan.

In Comparative Experiment Examples 5 and 6, A is heteroaryl containing an unsubstituted N-containing 6-membered ring. Experimental Examples 1 to 14 of the present invention are different in that A and B are heteroaryl groups containing an N-containing 6-membered ring substituted with an aryl group.

It can be seen that Experimental Examples 1 to 14 using the compounds of the present invention showed lower voltage, higher efficiency, and longer lifespan characteristics than Comparative Experimental Examples 5 and 6.

1: substrate
2: anode
3: Organic layer
4: cathode
5: Hole injection layer
6: Hole transport layer
7: Light-emitting layer
8: Electron injection and transport layer

Claims (10)

Compound of formula 1:
[Formula 1]

In Formula 1,
A is a heteroaryl group containing a 6-membered ring containing N substituted with a substituted or unsubstituted aryl group,
B is a heteroaryl group containing a 6-membered ring containing N substituted with a substituted or unsubstituted aryl group,
L is a direct bond, or a substituted or unsubstituted arylene group,
One of Q1 and Q2 is an aryl group having 6 to 30 carbon atoms, and the other is hydrogen or an aryl group having 6 to 30 carbon atoms,
When one of Q1 and Q2 is hydrogen, the remainder is one or more substituents selected from deuterium, nitro group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, and substituted or unsubstituted heteroaryl group. It is an aryl group having 6 to 30 carbon atoms that is substituted or unsubstituted,
When both Q1 and Q2 are aryl groups having 6 to 30 carbon atoms, the aryl group having 6 to 30 carbon atoms is deuterium, nitrile group, nitro group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, and substituted Or, it is substituted or unsubstituted with one or more substituents selected from unsubstituted heteroaryl groups. The compound according to claim 1, wherein the formula 1 is the formula 1-1 or 1-2 below:
[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2, A, B, L, Q1, and Q2 are as defined in Formula 1. The compound according to claim 1, wherein Formula 1 is Formula 1-3 below:
[Formula 1-3]

In Formula 1-3, A, B, and L are as defined in Formula 1,
R1 and R2 are the same or different from each other, and are each independently hydrogen, deuterium, nitrile group, nitro group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted heteroaryl group. Or, it combines with an adjacent group to form a substituted or unsubstituted ring,
a and b are integers from 1 to 5,
When a is 2 or more, R1 is the same or different,
When b is 2 or more, R2 is the same or different. The compound according to claim 1, wherein the formula 1 is the formula 1-4 below:
[Formula 1-4]

In Formula 1-4, L, Q1, and Q2 are as defined in Formula 1,
One of X1 to X3 is N, and the others are N or CR, respectively,
R is deuterium, nitrile group, nitro group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted heteroaryl group,
One of X4 to X8 is N, and the others are N or CR1, respectively,
R1 is deuterium, nitrile group, nitro group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted heteroaryl group, or is substituted or unsubstituted by combining with adjacent substituents. forms a ring The method of claim 1, wherein A is pyridine, pyrimidine, triazine, quinoline, quinazoline, or quinoxaline,
The pyridine, pyrimidine, triazine, quinoline, quinazoline, or quinoxaline is each independently substituted or unsubstituted aryl group having 6 to 20 carbon atoms. The method according to claim 1, wherein B is pyridine, pyrimidine, or triazine, and the pyridine, pyrimidine, or triazine is each independently substituted or unsubstituted aryl group having 6 to 20 carbon atoms. The method of claim 3, wherein R1 and R2 are the same as or different from each other, and are each independently hydrogen, deuterium, a nitrile group, a nitro group, a halogen group, an alkyl group with 1 to 10 carbon atoms, an aryl group with 6 to 30 carbon atoms, or a carbon number. A compound having 3 to 30 heteroaryl groups. The method according to claim 1, wherein Formula 1 is any one of the following compounds:












first electrode; a second electrode provided opposite the first electrode; And an organic light-emitting device comprising at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the compound according to any one of claims 1 to 8. . The organic light-emitting device of claim 9, wherein the organic material layer includes one or more of an electron transport layer, an electron injection layer, and an electron injection and transport layer, and one or more of the layers includes the compound.