KR20220081059A - 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 comprising the same

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

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

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic material layer is often formed 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, a hole injection layer, a hole transport layer, a light emitting layer, an electron suppression layer, an electron transport layer, an electron injection layer, etc. can get In the structure of the organic light emitting device, when a voltage is applied between the two electrodes, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons When it falls back to the ground state, it lights up. Such an organic light emitting device is known to have characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, and high contrast.

A material used as an organic layer in an organic light emitting device may be classified into a light emitting material and a charge transporting material, such as a hole injecting material, a hole transporting material, an electron suppressing material, an electron transporting material, an electron injecting material, and the like, according to functions. The light-emitting material includes blue, green, and red light-emitting materials depending on the light-emitting color, and yellow and orange light-emitting materials necessary for realizing better natural colors.

In addition, in order to increase color purity and increase luminous efficiency through energy transfer, a host/dopant system may be used as a light emitting material. The principle is that when a small amount of a dopant having a smaller energy band gap and superior luminous efficiency than the host constituting the emission layer is mixed in a small amount in the emission layer, excitons generated from the host are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength band of the dopant, light having a desired wavelength can be obtained according to the type of dopant used.

In order to sufficiently exhibit the excellent characteristics of the above-described organic light emitting device, materials constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron suppressing material, an electron transport material, an electron injection material, etc. are stable and efficient materials. The development of new materials continues to be demanded as it is supported by

International Patent Publication No. 2017-126443

In the present specification, a heterocyclic compound and an organic light emitting device including the same are described.

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

[Formula 1]

In Formula 1,

X is O or S;

Ar1 is a substituted or unsubstituted phenyl group, a substituted or unsubstituted 2-naphthyl group, an unsubstituted 1-naphthyl group,

Ar2 and Ar3 are the same as or different from each other, and each independently represent a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Ra and Rb are the same as or different from each other, and each independently represents hydrogen, deuterium, a halogen group, a nitrile group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or an unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted silyl group,

a is an integer from 0 to 5;

b is an integer from 0 to 8;

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

When b is plural, Rb is the same as or different from each other.

In addition, according to an exemplary embodiment of the present invention, the first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one organic material layer of the organic material layer provides an organic light-emitting device including the above-described heterocyclic compound.

The compound of the present invention may be used as a material for an organic layer of an organic light emitting device. When an organic light emitting device is manufactured by including the compound of the present invention, an organic light emitting device having high efficiency, low voltage and long lifespan characteristics can be obtained. An organic light emitting device can be manufactured.

1 and 2 show an example of an organic light emitting device according to the present invention.

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

The present specification provides a heterocyclic compound of Formula 1 below. When the heterocyclic compound of Formula 1 is used in the organic material layer of the organic light emitting device, the efficiency and lifespan characteristics of the organic light emitting device are improved. In particular, the conventional compound having a high sublimation temperature has a low compound stability, and when applied to a device, the efficiency and lifespan of the device are deteriorated. It has a sublimation temperature and thus has high stability, so that when applied to a device, a device having excellent efficiency and long life can be obtained.

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

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

Examples of substituents in the present 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 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, a position where the substituent is substitutable, is not limited, and when two or more are substituted , two or more substituents may be the same as 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; a substituted or unsubstituted alkyl group; a substituted or unsubstituted amine group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; And it means that it is substituted with one or two or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group, is substituted with a substituent to which two or more of the above-exemplified substituents are connected, or does not have any substituents. For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected.

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

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

In the present specification, the silyl group may be represented by the formula of -SiY1Y2Y3, wherein Y1, Y2 and Y3 are each hydrogen; a substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group. The silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like, but is not limited thereto. does not

In the present specification, the boron group may be represented by the formula of -BY4Y5, wherein Y4 and Y5 are each hydrogen; a substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group. Specifically, the boron group includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, and a phenylboron group.

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

In the present specification, the amine group is -NH ₂ ; an alkylamine group; N-alkylarylamine group; arylamine group; N-aryl heteroarylamine group; It may be selected from the group consisting of an N-alkylheteroarylamine group and a heteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group; dimethylamine group; ethylamine group; diethylamine group; phenylamine group; naphthylamine group; biphenylamine group; anthracenylamine group; 9-methylanthracenylamine group; diphenylamine group; N-phenylnaphthylamine 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 and the like, but is not limited thereto.

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

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

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

In the present specification, the alkyl group in the alkylamine group, N-arylalkylamine group, alkylthioxy group, alkylsulfoxy group, and N-alkylheteroarylamine group is the same as the above-described alkyl group. Specifically, the alkyl thiooxy group includes a methyl thiooxy group; ethyl thiooxy group; tert-butyl thiooxy group; hexyl thiooxy group; octylthiooxy group and the like, and examples of the alkylsulfoxy group include mesyl; ethyl sulfoxy group; propyl sulfoxy group; Butyl sulfoxy group and the like, 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 an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, there are a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like, 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 an exemplary embodiment, the carbon number of the aryl group is 6 to 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may include, but is not limited to, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a triphenyl group, a chrysenyl group, a fluorenyl group, and the like.

In the present specification, the heteroaryl group is a cyclic group including at least one of N, O, P, S, Si and Se as a heteroatom, and the number of carbon atoms is not particularly limited, but it is preferably from 2 to 60 carbon atoms. According to an exemplary embodiment, the heterocyclic group has 2 to 30 carbon atoms. Examples of the heterocyclic group include a pyridine group, a pyrrole group, a pyrimidine group, a pyridazinyl group, a furan group, a thiophene group, an imidazole group, a pyrazole group, a dibenzofuran group, a dibenzothiophene group, a carbazole group, and the like. However, the present invention is not limited thereto.

According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of Chemical Formulas 1-1 to 1-3 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3, Ra, Rb, X, Ar2, Ar3, a and b are as defined in Formula 1,

Rc and Rd are the same as or different from each other, and each independently represents hydrogen, deuterium, a halogen group, a nitrile group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or an unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted silyl group,

c is an integer from 0 to 5;

d is an integer from 0 to 7,

When c is plural, Rc is the same as or different from each other,

When d is plural, Rd is the same as or different from each other

According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of Chemical Formulas 1-4 to 1-9 below.

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

In Formulas 1-4 to 1-9, Ra, Rb, Ar2, Ar3, a and b are as defined in Formula 1,

Rc and Rd are the same as or different from each other, and each independently represents hydrogen, deuterium, a halogen group, a nitrile group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or an unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted silyl group,

c is an integer from 0 to 5;

d is an integer from 0 to 7,

When c is plural, Rc is the same as or different from each other,

When d is plural, Rd is the same as or different from each other.

According to an exemplary embodiment of the present specification, X is O.

According to an exemplary embodiment of the present specification, X ₁ is S.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a heteroaryl group having 3 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as or different from each other, and each independently a substituted or unsubstituted C6-C20 aryl group or a substituted or unsubstituted C3-C20 heteroaryl group .

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as or different from each other, and each independently a substituted or unsubstituted C6 to C15 aryl group or a substituted or unsubstituted C3 to C15 heteroaryl group .

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as or different from each other, and each independently represents an aryl group having 6 to 30 carbon atoms or a heteroaryl group having 3 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as or different from each other, and each independently represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as or different from each other, and each independently represents an aryl group having 6 to 15 carbon atoms or a heteroaryl group having 3 to 15 carbon atoms.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, substituted or unsubstituted anthracene group, substituted or unsubstituted phenanthrene group, substituted or unsubstituted triphenylene group, substituted or unsubstituted fluorene group, substituted or unsubstituted pyrene group, or substituted or It is an unsubstituted fluoranthene group.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as or different from each other, and each independently a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, an anthracene group, a phenanthrene group, a triphenylene group, a dimethylfluorene group, a diphenylfluorene group, a pyrene group, or a fluoranthene group.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as or different from each other, and each independently represents a phenyl group or a naphthyl group.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as each other and are a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a heteroaryl group having 3 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as each other and represent a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as each other and are a substituted or unsubstituted aryl group having 6 to 15 carbon atoms or a substituted or unsubstituted heteroaryl group having 3 to 15 carbon atoms.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as each other and are an aryl group having 6 to 30 carbon atoms or a heteroaryl group having 3 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as each other and are an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as each other and are an aryl group having 6 to 15 carbon atoms or a heteroaryl group having 3 to 15 carbon atoms.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as each other and a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted a substituted anthracene group, a substituted or unsubstituted phenanthrene group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorene group, a substituted or unsubstituted pyrene group, or a substituted or unsubstituted fluoranthene group .

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as each other and a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, an anthracene group, a phenanthrene group, a triphenylene group, a dimethylfluorene group, a diphenylfluorene group, pi It is a ren group, or a fluoranthene group.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are the same as each other and are a phenyl group or a naphthyl group.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are different from each other and are a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a heteroaryl group having 3 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are different from each other and represent a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are different from each other and represent a substituted or unsubstituted aryl group having 6 to 15 carbon atoms or a substituted or unsubstituted heteroaryl group having 3 to 15 carbon atoms.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are different from each other and are an aryl group having 6 to 30 carbon atoms or a heteroaryl group having 3 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are different from each other and are an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are different from each other and are an aryl group having 6 to 15 carbon atoms or a heteroaryl group having 3 to 15 carbon atoms.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are different from each other and represent a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or An unsubstituted anthracene group, a substituted or unsubstituted phenanthrene group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorene group, a substituted or unsubstituted pyrene group, or a substituted or unsubstituted fluoranthene group to be.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are different from each other and are a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, an anthracene group, a phenanthrene group, a triphenylene group, a dimethylfluorene group, a diphenylfluorene group, It is a pyrene group or a fluoranthene group.

According to an exemplary embodiment of the present specification, Ar2 and Ar3 are different from each other and are a phenyl group or a naphthyl group.

According to an exemplary embodiment of the present specification, Ra and Rb are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a nitrile group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or an unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted silyl group.

According to an exemplary embodiment of the present specification, Ra and Rb are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a nitrile group, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, a cycloalkyl group, or It is a silyl group.

According to an exemplary embodiment of the present specification, Ra and Rb are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a nitrile group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, carbon number a silyl group substituted with a heteroaryl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an alkyl group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, Ra and Rb are hydrogen.

According to an exemplary embodiment of the present specification, Rc and Rd are the same as or different from each other, and each independently hydrogen, deuterium, halogen group, nitrile group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or an unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted silyl group.

According to an exemplary embodiment of the present specification, Rc and Rd are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a nitrile group, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, a cycloalkyl group, or It is a silyl group.

According to an exemplary embodiment of the present specification, Rc and Rd are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a nitrile group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, a carbon number a silyl group substituted with a heteroaryl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or an alkyl group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, Rc and Rd are hydrogen.

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

Substituents of the heterocyclic 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.

The conjugation length of the compound and the energy bandgap are closely related. Specifically, the longer the conjugation length of the compound, the smaller the energy bandgap.

In the present invention, compounds having various energy band gaps can be synthesized by introducing various substituents into the core structure as described above. In addition, in the present invention, the HOMO and LUMO energy levels of the compound can be controlled by introducing various substituents into the core structure of the structure as described above.

In addition, by introducing various substituents into the core structure of the structure as described above, a compound having the intrinsic properties of the introduced substituent can be synthesized. For example, by introducing a substituent mainly used for a hole injection layer material, a hole transport material, a light emitting layer material, and an electron transport layer material used in manufacturing an organic light emitting device into the core structure, a material satisfying the conditions required for each organic material layer can be synthesized. can

In addition, the organic light emitting device according to the present invention includes a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the heterocyclic compound described above.

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

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 coating method refers to spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but 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 injects and transports holes, 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 thereto and may include a smaller number of organic material layers or a larger number of organic material layers.

In the organic light emitting device of the present invention, the organic material layer may include at least one of an electron transport layer, an electron injection layer, and a layer that simultaneously injects and transports electrons, and at least one of the layers is a heterocyclic ring of Formula 1 compounds may be included.

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 may include the heterocyclic compound of Formula 1 above.

In the organic light emitting device of the present invention, the organic material layer may include at least one of a hole injection layer, a hole transport layer, and a layer that simultaneously injects and transports holes, and at least one of the layers is a heterocyclic ring of Formula 1 compounds may be included.

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 heterocyclic compound of Formula 1 above.

In another exemplary embodiment, the organic material layer includes an emission layer, and the emission layer includes the heterocyclic compound of Formula 1 above. As an example, the heterocyclic compound of Formula 1 may be included as a host of the emission layer.

In the exemplary embodiment of the present specification, the organic light emitting device is a green organic light emitting device in which the light emitting layer includes the heterocyclic compound of Formula 1 as a host.

According to an exemplary embodiment of the present specification, the organic light emitting device is a red organic light emitting device in which the light emitting layer includes the heterocyclic compound of Formula 1 as a host.

In another exemplary embodiment, the organic light emitting device is a blue organic light emitting device in which the light emitting layer includes the heterocyclic compound of Formula 1 as a host.

As another example, the organic material layer including the heterocyclic compound of Formula 1 may include the heterocyclic compound of Formula 1 as a host, and an organic compound such as a boron-based compound or an amine-based compound as a dopant.

In the organic light emitting device of the present invention, the light emitting layer includes a host and a dopant in a mass ratio of 99:1 to 50:50, respectively.

In the organic light emitting device of the present invention, the light emitting layer includes a host and a dopant in a mass ratio of 99:1 to 80:20, respectively.

In the organic light emitting device of the present invention, the light emitting layer includes a host and a dopant in a mass ratio of 99:1 to 90:10, respectively. In an exemplary embodiment of the present specification, the first electrode is an anode, and the second electrode is negative pole

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 blocking layer / electron transport layer / cathode

(15) anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode

(16) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode

(17) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode

(18) anode / hole injection layer / hole transport layer / electron blocking 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 FIG. 1 , but is not limited thereto.

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

1 illustrates a 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 such a structure, the heterocyclic compound of Formula 1 may be included in the organic layer 3 .

2, the anode 2, the hole injection layer 5, the hole transport layer 6, the light emitting layer 7, the electron transport layer 8, the electron injection layer 9 and the cathode 4 are sequentially on the substrate 1 The structure of the organic light-emitting device stacked with In such a structure, the heterocyclic compound of Formula 1 may be included in the emission layer 7 .

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 to form a metal or a conductive metal oxide or an alloy thereof on a substrate. from the group consisting of a hole injection layer, a hole transport layer, a layer that transports and injects holes at the same time, a light emitting layer, an electron transport layer, an electron injection layer, and a layer that simultaneously performs electron transport and electron injection. After forming an organic material layer including one or more selected layers, it may be manufactured by depositing a material that can be used as a cathode thereon. 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.

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

The anode is an electrode for injecting holes, and 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 anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO, Indium Tin Oxide), and indium zinc oxide (IZO, Indium Zinc Oxide); ZnO: Al or SnO ₂ : Combination of metals and oxides such as Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

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

The hole injection layer is a layer that facilitates injection of holes from the anode to the light emitting layer. As the hole injection material, holes can be well injected from the anode at a low voltage, and the highest occupied (HOMO) of the hole injection material is The molecular orbital) is preferably between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto. The hole injection layer may have a thickness of 1 to 150 nm. When the thickness of the hole injection layer is 1 nm or more, there is an advantage in that the hole injection characteristics can be prevented from being deteriorated, and when it is 150 nm or less, the thickness of the hole injection layer is too thick and the driving voltage is increased to improve hole movement There are advantages to avoiding this.

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

An additional hole buffer layer may be provided between the hole injection layer and the hole transport layer, and may include hole injection or transport materials known in the art.

An electron blocking layer may be provided between the hole transport layer and the light emitting layer. The electron-blocking layer may be the aforementioned spiro compound 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 ray region by receiving and combining 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 compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene, rubrene, and the like, but is not limited thereto.

Examples of the host material for the light emitting layer include a condensed aromatic ring derivative or a heterocyclic compound containing compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

When the emission layer emits red light, the emission dopant is PIQIr(acac)(bis(1-phenylisoquinoline)acetylacetonateiridium), PQIr(acac)(bis(1-phenylquinoline)acetylacetonate iridium), PQIr(tris(1-phenylquinoline)iridium) ), a phosphorescent material such as octaethylporphyrin platinum (PtOEP), or a fluorescent material such as Alq ₃ (tris(8-hydroxyquinolino)aluminum) may be used, but is not limited thereto. When the emission 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) may be used as the emission dopant. However, the present invention is not limited thereto. When the light-emitting layer emits blue light, the light-emitting dopant includes a phosphorescent material such as (4,6-F2ppy) ₂ Irpic, spiro-DPVBi, spiro-6P, distylbenzene (DSB), distrylarylene (DSA), A fluorescent material such as a PFO-based polymer or a PPV-based polymer may be used, but is not limited thereto.

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

The electron transport layer may serve to facilitate the transport of electrons. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high electron mobility is suitable. Specific examples include Al complex of 8-hydroxyquinoline; complexes containing Alq ₃ ; organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. 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 that the electron transport properties can be prevented from being deteriorated, and if it is 50 nm or less, the thickness of the electron transport layer is too thick to prevent the driving voltage from being raised to improve the movement of electrons. There are advantages that can be

The electron injection layer may serve to facilitate electron injection. The electron injection material has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, prevents the movement of excitons generated in the light emitting layer to the hole injection layer, and , a compound having excellent thin film forming ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc., derivatives thereof, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-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-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.

The hole blocking layer is a layer that blocks the 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 complex, and the like, but is not limited thereto.

The organic light emitting device according to the present invention may be a top emission type, a back emission type, or a double side emission type depending on the material used.

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

A method of preparing the heterocyclic compound of Formula 1 and manufacturing an organic light emitting device using the same will be described in detail in Examples below. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

In the following reaction scheme, various types of intermediates can be synthesized according to a suitable selection of known starting materials by those skilled in the art for the type and number of substituents. As the reaction type and reaction conditions, those known in the art may be used.

All of the heterocyclic compounds of Formula 1 described in the present specification can be prepared by appropriately combining the preparation formulas described in the Examples of the present specification and the intermediates based on common technical knowledge.

<Synthesis example>

One. Synthesis of compound 1

Synthesis Example 1-1. Synthesis of compound 1-a

(4-bromo-2-fluoro-6-methoxyphenyl) boronic acid (100 g, 402 mmol) and 5-chloro-2-iodophenol (102 g, 402 mmol) were dissolved in 2000 ml of THF, and then Pd (PPh ₃ ) ₄ (9.3g, 8.0mmol) and 400ml of 2M Na ₂ CO ₃ aqueous solution were added and stirred under reflux for 24 hours. After cooling the reaction solution, the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure and purified using column chromatography to obtain compound 1-a (94 g, yield 71%).

Synthesis Example 1-2. Synthesis of compound 1-b

After dissolving compound 1-a (94g, 284mmol) in DMF (1500ml), K ₂ CO ₃ (118g, 850mmol) was added, and the mixture was stirred under reflux for 2 hours. After cooling the reaction solution, it is poured into 4.5L of distilled water to form a solid. After filtering the solid, it is dissolved in chloroform, extracted several times with water, and the organic layer is dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure and purified by column chromatography to obtain compound 1-b (52 g, yield 59%).

Synthesis Example 1-3. Synthesis of compound 1-c

Compound 1-b (52 g, 167 mmol) and phenylboronic acid (41 g, 334 mmol) were dissolved in 1,4-dioxane (900 ml), and then bis (tri-tert-butylphosphine) palladium (0) (0.17 g) , 0.33 mmol) and 200 ml of 2M K ₂ CO ₃ aqueous solution were added and stirred under reflux for 24 hours. After cooling the reaction solution, the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. Purification was performed using column chromatography to obtain compound 1-c (42 g, yield 72%).

Synthesis Example 1-4. Synthesis of compound 1-d

Dissolve compound 1-c (42 g, 120 mmol) in 300 ml of methylene chloride under a nitrogen atmosphere. After lowering the temperature to 0°C, a BBr ₃ solution (1M in DCM, 300ml) is slowly added dropwise. The reaction solution was gradually heated to room temperature and stirred for 24 hours. After slowly adding 1000 ml of ice water dropwise, the mixture is stirred at room temperature for 30 minutes. After filtering the resulting solid, it is dissolved in chloroform, extracted several times with water, and the organic layer is dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure and recrystallized from EA/Hex to obtain compound 1-d (29 g, yield 72%).

Synthesis Example 1-5. Synthesis of compound 1-e

After dissolving compound 1-d (29g, 86mmol) in acetonitrile (500ml), K ₂ CO ₃ (36g, 258mmol) and nonafluorobutane-1-sulfonylfluoride (39g, 129mmol) dissolved in 100ml distilled water were added put it in After stirring at room temperature for 3 hours, acetonitrile is distilled off under reduced pressure, dissolved in chloroform, and extracted several times with water. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure to remove the organic solvent, and purified using column chromatography to obtain compound 1-e (41 g, yield 77%).

Synthesis Example 1-6. Synthesis of compound 1-f

Compound 1-e (41 g, 66 mmol), bis (pinacolato) diboron (20 g, 80 mmol), and KOAc (13 g, 133 mmol) were put in a flask together with 200 ml of dioxane and dispersed. After adding Pd(dba)2 (0.76g, 1.3mmol) and PCy3 (0.74g, 2.7mmol), the mixture was stirred under reflux for 24 hours. After completion of the reaction, dioxane is removed by distillation under reduced pressure. After dissolving in chloroform and extracting three times with distilled water, the organic layer was distilled under reduced pressure to remove chloroform. Compound 1-f was obtained by purification using column chromatography. (22 g, yield 74%)

Synthesis Example 1-7. Synthesis of compound 1

Compound 1-f (22 g, 49 mmol) and 9-bromo-10-phenylanthracene (16.4 g, 49 mmol) were dissolved in 1,4-dioxane (250 ml), and then bis (tri-tert-butylphosphine) Palladium (0) (0.05 g, 0.1 mmol) and 50 ml of 2M K ₂ CO ₃ aqueous solution were added and stirred under reflux for 24 hours. After cooling the reaction solution, the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. Recrystallization from EA gave compound 1 (16 g, yield 57%). [M+H ⁺ ]= 573.2

2. Synthesis of compound 2

Synthesis Example 2-1. Synthesis of compound 2-a

After dissolving 9-bromoanthracene (50 g, 194 mmol) and [1,1'-biphenyl]-3-ylboronic acid (39 g, 194 mmol) in THF (1000 ml), Pd (PPh ₃ ) ₄ (4.5 g, 3.9 mmol) and 200 ml of 2M K ₂ CO ₃ aqueous solution were added and stirred under reflux for 24 hours. After cooling the reaction solution, the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. Recrystallization from ethyl acetate gave compound 2-a (43 g, yield 67%).

Synthesis Example 2-2. Synthesis of compound 2-b

Compound 2-a (43 g, 130 mmol) was dissolved in 550 ml of DMF, and then N-bromosuccinimide (23.2 g, 130 mmol) dissolved in 100 ml of DMF was slowly added dropwise. After stirring at room temperature for 2 hours, 1500 ml of water was added dropwise. When a solid is formed, it is dissolved in chloroform after filtering and extracted several times with distilled water. Recrystallization from ethyl acetate gave compound 2-b. (37 g, yield 69%)

Synthesis Example 2-3. Synthesis of compound 2

After dissolving compound 1-f (20 g, 45 mmol) and compound 2-b (18.3 g, 45 mmol) in 1,4-dioxane (220 ml), bis (tri-tert-butylphosphine) palladium (0) ( 0.045 g, 0.09 mmol) and 50 ml of 2M K ₂ CO ₃ aqueous solution were added and stirred under reflux for 24 hours. After cooling the reaction solution, the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. Recrystallization from EA gave compound 2 (15 g, yield 61%). [M+H ⁺ ]= 649.3

3. Synthesis of compound 3

Synthesis Example 3-1. Synthesis of compound 3-a

In Synthesis Example 2-1, except that (3-(naphthalen-1-yl)phenyl)boronic acid was used instead of [1,1'-biphenyl]-3-ylboronic acid, it was synthesized and purified in the same manner as Compound 3- got a.

Synthesis Example 3-2. Synthesis of compound 3-b

Compound 3-b was obtained by synthesis and purification in the same manner as in Synthesis Example 2-2, except that compound 3-a was used instead of compound 2-a.

Synthesis Example 3-3. Synthesis of compound 3

Compound 3 was obtained by synthesis and purification in the same manner as in Synthesis Example 2-3, except that compound 3-b was used instead of compound 2-b. [M+H ⁺ ]= 699.3

4. Synthesis of compound 4

Synthesis Example 4-1. Synthesis of compound 4

Compound 4 was obtained by the same synthesis and purification as in Synthesis Example 2-3, except that 9-bromo-10-(naphthalen-2-yl)anthracene was used instead of compound 2-b. [M+H ⁺ ]= 623.2

5. Synthesis of compound 5

Synthesis Example 5-1. Synthesis of compound 5-a

Compound 5-a was synthesized and purified in the same manner as in Synthesis Example 2-1, except that (6-phenylnaphthalen-2-yl)boronic acid was used instead of [1,1'-biphenyl]-3-ylboronic acid. got it

Synthesis Example 5-2. Synthesis of compound 5-b

Compound 5-b was obtained by synthesis and purification in the same manner as in Synthesis Example 2-2, except that compound 5-a was used instead of compound 2-a.

Synthesis Example 5-3. Synthesis of compound 5

Compound 5 was obtained by synthesis and purification in the same manner as in Synthesis Example 2-3, except that compound 5-b was used instead of compound 2-b. [M+H ⁺ ]= 699.3

6. Synthesis of compound 6

Synthesis Example 6-1. Synthesis of compound 6

Compound 6 was obtained by the same synthesis and purification in Synthesis Example 2-3, except that 9-bromo-10-(naphthalen-1-yl)anthracene was used instead of compound 2-b. [M+H ⁺ ]= 623.2

7. Synthesis of compound 7

Synthesis Example 7-1. Synthesis of compound 7-a

After dissolving compound 1-b (100 g, 321 mmol) and phenylboronic acid (39 g, 321 mmol) in THF (1500 ml), Pd(PPh ₃ ) ₄ (7.4 g, 6.4 mmol) and 2M K ₂ CO ₃ aqueous solution 300 ml and stirred under reflux for 24 hours. After cooling the reaction solution, the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. Recrystallization from ethyl acetate gave compound 7-a (75 g, yield 76%).

Synthesis Example 7-2. Synthesis of compound 7-b

Compound 7-a (75 g, 243 mmol) and naphthalen-1-ylboronic acid (42 g, 243 mmol) were dissolved in 1,4-dioxane (1200 ml), and then bis (tri-tert-butylphosphine) palladium (0) (0.25 g, 0.49 mmol) and 300 ml of 2M K ₂ CO ₃ aqueous solution were added and stirred under reflux for 24 hours. After cooling the reaction solution, the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. Recrystallization from EA gave compound 7-b (67 g, yield 69%).

Synthesis Example 7-3. Synthesis of compound 7-c

Dissolve compound 7-b (67g, 167mmol) in 400ml of methylene chloride under a nitrogen atmosphere. After lowering the temperature to 0°C, a BBr ₃ solution (1M in DCM, 420ml) is slowly added dropwise. The reaction solution was gradually heated to room temperature and stirred for 24 hours. After slowly adding 1500 ml of ice water dropwise, the mixture was stirred at room temperature for 30 minutes. After filtering the resulting solid, it is dissolved in chloroform, extracted several times with water, and the organic layer is dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure and recrystallized from EA/Hex to obtain compound 7-c (48 g, yield 74%).

Synthesis Example 7-4. Synthesis of compound 7-d

After dissolving compound 7-c (48g, 124mmol) in acetonitrile (500ml), K ₂ CO ₃ (51.5g, 373mmol) and nonafluorobutane-1-sulfonylfluoride (56.3g, 186mmol) dissolved in distilled water 100ml ) is put in After stirring at room temperature for 3 hours, acetonitrile is distilled off under reduced pressure, dissolved in chloroform, and extracted several times with water. The organic layer was dried over anhydrous magnesium sulfate, distilled under reduced pressure to remove the organic solvent, and purified using column chromatography to obtain compound 7-d (57 g, yield 69%).

Synthesis Example 7-5. Synthesis of compound 7-e

Compound 7-d (57g, 85mmol), bis(pinacolato)diboron (26g, 102mmol), and KOAc (17g, 125mmol) were put in a flask together with 300ml of dioxane and dispersed. After adding Pd(dba)2 (0.98g, 1.7mmol) and PCy3 (0.95g, 3.4mmol), the mixture was stirred under reflux for 24 hours. After completion of the reaction, dioxane is removed by distillation under reduced pressure. After dissolving in chloroform and extracting with distilled water three times, the organic layer was distilled under reduced pressure to remove chloroform. Compound 7-e was obtained by purification using column chromatography. (31 g, yield 73%)

Synthesis Example 7-6. Synthesis of compound 7

Compound 7-e (31 g, 62 mmol) and 9-bromo-10-phenylanthracene (20.8 g, 62 mmol) were dissolved in 1,4-dioxane (300 ml), followed by bis (tri-tert-butylphosphine) Palladium (0) (0.06 g, 0.13 mmol) and 2M K ₂ CO ₃ aqueous solution 60 ml were added and stirred under reflux for 24 hours. After cooling the reaction solution, the organic layer was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. Recrystallization from EA gave compound 7 (24 g, yield 62%). [M+H ⁺ ]= 623.2

8. Synthesis of compound 8

Synthesis Example 8-1. Synthesis of compound 8-a

Compound 8-a was synthesized in the same manner as in Synthesis Example 7-2, except that dibenzo[b,d]furan-1-ylboronic acid was used instead of naphthalen-1-ylboronic acid.

Synthesis Example 8-2. Synthesis of compound 8-b

Compound 8-b was synthesized in the same manner as in Synthesis Example 7-3, except that compound 8-a was used instead of compound 7-b.

Synthesis Example 8-3. Synthesis of compound 8-c

Compound 8-c was synthesized in the same manner as in Synthesis Example 7-4, except that compound 8-b was used instead of compound 7-c.

Synthesis Example 8-4. Synthesis of compound 8-d

Compound 8-d was synthesized in the same manner as in Synthesis Example 7-5, except that compound 8-c was used instead of compound 7-d.

Synthesis Example 8-5. Synthesis of compound 8

In Synthesis Example 7-6, in the same manner except for using compound 8-d instead of compound 7-e and 9-bromo-10-(naphthalen-2-yl)anthracene instead of 9-bromo-10-phenylanthracene By synthesis and purification, compound 8 was synthesized. [M+H ⁺ ]= 713.2

9. Synthesis of compound 9

Synthesis Example 9-1. Synthesis of compound 9-a

Compound 9-a was synthesized in the same manner as in Synthesis Example 7-1, except that naphthalen-1-ylboronic acid was used instead of phenylboronic acid.

Synthesis Example 9-2. Synthesis of compound 9-b

Compound 9-b was synthesized in the same manner as in Synthesis Example 7-2, except that naphthalen-2-ylboronic acid was used instead of naphthalen-1-ylboronic acid.

Synthesis Example 9-3. Synthesis of compound 9-c

Compound 9-c was synthesized in the same manner as in Synthesis Example 7-3, except that compound 9-b was used instead of compound 7-b.

Synthesis Example 9-4. Synthesis of compound 9-d

Compound 9-d was synthesized in the same manner as in Synthesis Example 7-4, except that compound 9-c was used instead of compound 7-c.

Synthesis Example 9-5. Synthesis of compound 9-e

Compound 9-e was synthesized in the same manner as in Synthesis Example 7-5, except that compound 9-d was used instead of compound 7-d.

Synthesis Example 9-6. Synthesis of compound 9

Compound 9 was synthesized in the same manner as in Synthesis Example 7-6, except that compound 9-e was used instead of compound 7-e. [M+H ⁺ ]=723.3

10. Synthesis of compound 10

Synthesis Example 10-1. Synthesis of compound 10

Compound 1 (50g) and AlCl ₃ (10g) were added to C ₆ D ₆ (1000 ml) and stirred for 2 hours. After completion of the reaction, D ₂ O (75ml) was added and stirred for 30 minutes, and then trimethylamine (6ml) was added dropwise. The reaction solution was transferred to a separatory funnel, and extracted with water and toluene. The extract was dried over MgSO ₄ , and recrystallized from ethyl acetate to obtain compound 10. (38 g, yield 74%) [M+H ⁺ ]= 601.4

11. Synthesis of compound 11

Synthesis Example 11-1. Synthesis of compound 11-a

Compound 11-a was obtained by synthesis and purification in the same manner as in Synthesis Example 10-1, except that 9-(naphthalen-2-yl)anthracene was used instead of Compound 1.

Synthesis Example 11-2. Synthesis of compound 11-b

Compound 11-b was obtained by the same synthesis and purification, except that compound 11-a was used instead of compound 2-a in Synthesis Example 2-2.

Synthesis Example 11-3. Synthesis of compound 11

Compound 11 was obtained by the same synthesis and purification, except that compound 11-b was used instead of compound 2-b in Synthesis Example 2-3. [M+H ⁺ ]=638.3

12. Synthesis of compound 12

Synthesis Example 12-1. Synthesis of compound 12-a

Compound 12-a was obtained by the same synthesis and purification, except that (phenyl-d5)boronic acid was used instead of phenylboronic acid in Synthesis Example 1-3.

Synthesis Example 12-2. Synthesis of compound 12-b

Compound 12-b was obtained by synthesis and purification in the same manner except for using Compound 12-a instead of Compound 1-c in Synthesis Example 1-4.

Synthesis Example 12-3. Synthesis of compound 12-c

Compound 12-c was obtained by the same synthesis and purification in Synthesis Example 1-5, except that 12-b was used instead of compound 1-d.

Synthesis Example 12-4. Synthesis of compound 12-d

In Synthesis Example 1-6, compound 12-d was obtained by the same synthesis and purification, except that compound 12-c was used instead of compound 1-e.

Synthesis Example 12-5. Synthesis of compound 12-e

Compound 12-e was obtained by synthesis and purification in the same manner as in Synthesis Example 10-1, except that 9-(naphthalen-1-yl)anthracene was used instead of Compound 1.

Synthesis Example 12-6. Synthesis of compound 12-f

Compound 12-f was obtained by synthesis and purification in the same manner except for using Compound 12-e instead of Compound 2-a in Synthesis Example 2-2.

Synthesis Example 12-7. Synthesis of compound 12

Compound 12 was obtained by synthesis and purification in the same manner as in Synthesis Example 2-3, except that compound 12-f was used instead of compound 2-b and compound 12-d was used instead of compound 1-f. [M+H ⁺ ]=648.4

<Example>

<Comparative example>

Example 1

A glass substrate coated with indium tin oxide (ITO) to a thickness of 150 nm was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing the ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, and after drying, it was transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using nitrogen plasma, the substrate was transported to a vacuum evaporator. On the thus prepared ITO transparent electrode, the following HAT-CN compound was thermally vacuum deposited to a thickness of 5 nm to form a hole injection layer. Then, HTL1 was thermally vacuum deposited to a thickness of 100 nm, and then HTL2 was thermally vacuum deposited to a thickness of 10 nm to form a hole transport layer. Then, compound 1 as a host and BD-A (weight ratio 95:5) as a dopant were simultaneously vacuum-deposited to form a light emitting layer with a thickness of 20 nm. Then, ETL was vacuum-deposited to a thickness of 20 nm to form an electron transport layer. Then, LiF was vacuum-deposited to a thickness of 0.5 nm to form an electron injection layer. Then, aluminum was deposited to a thickness of 100 nm to form a cathode, thereby manufacturing an organic light emitting diode.

The structures of the compounds used in the Examples are as follows.

Examples 2 to 12 and Comparative Examples 1 to 5

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the compounds shown in Table 1 were used instead of Compound 1 as the host of the light emitting layer. At this time, among the following structures, the heterocyclic compound of Formula 1 of the present invention was prepared through the same process as in Synthesis Examples 1 to 12, respectively.

In the organic light emitting devices prepared in Examples 1 to 12 and Comparative Examples 1 to 5, the driving voltage and luminous efficiency were measured at a current density of 10 mA/cm ² , and initial luminance at a current density of 20 mA/cm ² The time (LT) to be 95% of the contrast was measured, and the results are shown in Table 1 below.

compound
(light emitting layer host) 10 mA/cm ² measured value LT (T95%) Vop Cd/A Example 1 compound 1 3.53 6.98 183 Example 2 compound 2 3.62 7.05 154 Example 3 compound 3 3.65 7.03 149 Example 4 compound 4 3.49 7.07 166 Example 5 compound 5 3.45 7.05 143 Example 6 compound 6 3.60 7.11 145 Example 7 compound 7 3.56 7.02 150 Example 8 compound 8 3.47 6.95 153 Example 9 compound 9 3.67 7.00 159 Example 10 compound 10 3.53 6.99 352 Example 11 compound 11 3.49 7.06 253 Example 12 compound 12 3.60 7.12 273 Comparative Example 1 BH-A 3.75 6.42 98 Comparative Example 2 BH-B 3.84 6.52 86 Comparative Example 3 BH-C 3.92 6.35 102 Comparative Example 4 BH-D 4.02 6.54 92 Comparative Example 5 BH-E 3.75 6.44 112

All of Examples 1 to 12 using the heterocyclic compound of Formula 1 of the present invention exhibited characteristics of low voltage and high efficiency, and showed superior lifespan compared to Comparative Examples 1 to 5. In particular, Examples 10 to 12 showed that the lifetime was further improved by deuterium substitution.

Comparative Examples 1 and 2 in which Ar2 or Ar3 is hydrogen had a high driving voltage and were not advantageous in terms of efficiency and lifespan. In Comparative Examples 3 and 4, in which the substitution position of dibenzofuran connected to anthracene is different from Chemical Formula 1, particularly, the driving voltage was high, the efficiency was low, and the lifespan was low. In addition, even in the case of Comparative Example 5 in which the substituent of Ar1 is a substituted 1-naphthalene group, the efficiency was very low and the lifespan was not good.

1: Substrate
2: first electrode
3: organic layer
4: second electrode
5: hole injection layer
6: hole transport layer
7: light emitting layer
8: electron transport layer
9: electron injection layer

Claims (10)

Heterocyclic compound of formula (1):
[Formula 1]

In Formula 1,
X is O or S;
Ar1 is a substituted or unsubstituted phenyl group, a substituted or unsubstituted 2-naphthyl group, an unsubstituted 1-naphthyl group,
Ar2 and Ar3 are the same as or different from each other, and each independently represent a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
Ra and Rb are the same as or different from each other, and each independently represents hydrogen, deuterium, a halogen group, a nitrile group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or an unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted silyl group,
a is an integer from 0 to 5;
b is an integer from 0 to 8;
When a is plural, Ra is the same as or different from each other,
When b is plural, Rb is the same as or different from each other. The heterocyclic compound according to claim 1, wherein Chemical Formula 1 is represented by any one of Chemical Formulas 1-1 to 1-3:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3, Ra, Rb, X, Ar2, Ar3, a and b are as defined in Formula 1,
Rc and Rd are the same as or different from each other, and each independently represents hydrogen, deuterium, a halogen group, a nitrile group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or an unsubstituted alkoxy group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted silyl group,
c is an integer from 0 to 5;
d is an integer from 0 to 7,
When c is plural, Rc is the same as or different from each other,
When d is plural, Rd is the same as or different from each other. The heterocyclic compound of claim 2, wherein Rc and Rd are hydrogen. The heterocyclic compound according to claim 1, wherein Ar2 and Ar3 are the same as or different from each other, and each independently a phenyl group or a naphthyl group. The heterocyclic compound according to claim 1, wherein the heterocyclic compound of Formula 1 is any one selected from the following compounds:

a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one organic material layer of the organic material layer contains the heterocyclic compound according to any one of claims 1 to 5. light emitting element. 7. The method of claim 6,
The organic material layer includes a hole injection layer or a hole transport layer, and the hole injection layer or the hole transport layer is an organic light emitting device including the heterocyclic compound. 7. The method of claim 6,
The organic material layer includes an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes the heterocyclic compound. 7. The method of claim 6,
The organic material layer includes an emission layer, and the emission layer includes the heterocyclic compound. 7. The method of claim 6,
The organic material layer includes an emission layer, and the emission layer includes the heterocyclic compound as a host of the emission layer.

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