KR102589217B1 - Hetero-cyclic compound and organic light emitting device using the same - Google Patents

Abstract

The present application provides a heterocyclic compound that can significantly improve the lifespan, efficiency, electrochemical stability, and thermal stability of an organic light-emitting device, and an organic light-emitting device in which the heterocyclic compound is contained in an organic compound layer.

Description

Heterocyclic compound and organic light-emitting device using the same {HETERO-CYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE USING THE SAME}

This application relates to heterocyclic compounds and organic light-emitting devices using the same.

Electroluminescent devices are a type of self-luminous display devices and have the advantages of a wide viewing angle, excellent contrast, and fast response speed.

Organic light-emitting devices have a structure in which an organic thin film is placed between two electrodes. When voltage is applied to an organic light emitting device with this structure, electrons and holes injected from two electrodes combine in the organic thin film to form a pair and then disappear, emitting light. The organic thin film may be composed of a single layer or multiple layers, depending on need.

The material of the organic thin film may have a light-emitting function as needed. For example, as an organic thin film material, a compound that can independently form a light-emitting layer may be used, or a compound that can act as a host or dopant of a host-dopant-based light-emitting layer may be used. In addition, as a material for the organic thin film, compounds that can perform roles such as hole injection, hole transport, electron blocking, hole blocking, electron transport, and electron injection may be used.

In order to improve the performance, lifespan, or efficiency of organic light-emitting devices, the development of organic thin film materials is continuously required.

US Patent No. 4,356,429

A compound that can satisfy the conditions required for materials usable in organic light-emitting devices, such as appropriate energy level, electrochemical stability, and thermal stability, and has a chemical structure that can play various roles required in organic light-emitting devices depending on the substituent. Research on organic light-emitting devices containing is needed.

An exemplary embodiment of the present application provides a heterocyclic compound represented by the following formula (1):

[Formula 1]

In Formula 1,

Ar1 is a substituted or unsubstituted C ₆ to C ₆₀ aryl group; Or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group,

One of R1 to R4 is represented by the following formula (3), and the other is a substituted or unsubstituted aryl group of C ₆ to C ₆₀ ; or is represented by the following formula 4, the remainder being hydrogen,

R5 to R8 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; -CN; Substituted or unsubstituted C ₁ to C ₆₀ alkyl group; Substituted or unsubstituted C ₂ to C ₆₀ alkenyl group; Substituted or unsubstituted C ₂ to C ₆₀ alkynyl group; Substituted or unsubstituted C ₁ to C ₆₀ alkoxy group; Substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group; Substituted or unsubstituted C ₂ to C ₆₀ heterocycloalkyl group; Substituted or unsubstituted C ₆ to C ₆₀ aryl group; Substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group; -SiRR'R";-P(=O)RR'; and substituted with a C ₁ to C ₂₀ alkyl group, a substituted or unsubstituted C ₆ to C ₆₀ aryl group, or a C ₂ to C ₆₀ heteroaryl group, or selected from the group consisting of unsubstituted amine groups,

[Formula 3]

In Formula 3 above,

L1 is a direct bond or a substituted or unsubstituted C ₆ to C ₆₀ arylene group,

R9 to R16 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; -CN; Substituted or unsubstituted C ₁ to C ₆₀ alkyl group; Substituted or unsubstituted C ₂ to C ₆₀ alkenyl group; Substituted or unsubstituted C ₂ to C ₆₀ alkynyl group; Substituted or unsubstituted C ₁ to C ₆₀ alkoxy group; Substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group; Substituted or unsubstituted C ₂ to C ₆₀ heterocycloalkyl group; Substituted or unsubstituted C ₆ to C ₆₀ aryl group; Substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group; -SiRR'R";-P(=O)RR'; and substituted with a C ₁ to C ₂₀ alkyl group, a substituted or unsubstituted C ₆ to C ₆₀ aryl group, or a C ₂ to C ₆₀ heteroaryl group, or Two or more groups selected from the group consisting of unsubstituted amine groups, or adjacent to each other, combine with each other to form a substituted or unsubstituted hydrocarbon condensed ring or heterocondensed ring,

[Formula 4]

In Formula 4 above,

Ar2 is each independently hydrogen; heavy hydrogen; halogen group; -CN; Substituted or unsubstituted C ₁ to C ₆₀ alkyl group; Substituted or unsubstituted C ₂ to C ₆₀ alkenyl group; Substituted or unsubstituted C ₂ to C ₆₀ alkynyl group; Substituted or unsubstituted C ₁ to C ₆₀ alkoxy group; Substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group; Substituted or unsubstituted C ₂ to C ₆₀ heterocycloalkyl group; Substituted or unsubstituted C ₆ to C ₆₀ aryl group; Substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group; -SiRR'R";-P(=O)RR'; and substituted with a C ₁ to C ₂₀ alkyl group, a substituted or unsubstituted C ₆ to C ₆₀ aryl group, or a C ₂ to C ₆₀ heteroaryl group, or selected from the group consisting of unsubstituted amine groups,

t is an integer from 0 to 4,

R, R' and R" are the same or different from each other, and are each independently hydrogen; deuterium; -CN; substituted or unsubstituted C ₁ to C ₆₀ alkyl group; substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group ; A substituted or unsubstituted C ₆ to C ₆₀ aryl group; or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group.

In addition, another embodiment of the present application is an organic light-emitting device comprising an anode, a cathode, and at least one organic material layer provided between the anode and the cathode, wherein at least one layer of the organic material layer is a heterocyclic compound represented by the formula (1) It provides an organic light emitting device comprising a.

In addition, another embodiment of the present application provides a composition for an organic material layer of an organic light-emitting device, which simultaneously includes a heterocyclic compound represented by Formula 1 and a compound represented by Formula 2 below.

[Formula 2]

In Formula 2,

L1' and L2' are the same or different from each other, and are each independently a direct bond or a substituted or unsubstituted C ₆ to C ₆₀ arylene group,

Ar1' is a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group containing at least one N,

Ar2' is represented by any of the following formulas 5 and 6,

[Formula 5]

[Formula 6]

Y1 to Y4 are the same or different from each other, and each independently represents a substituted or unsubstituted C ₆ to C ₆₀ aromatic hydrocarbon ring; Or a substituted or unsubstituted C ₂ to C ₆₀ aromatic heterocycle,

R1' to R7' are the same or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; -CN; Substituted or unsubstituted C ₁ to C ₆₀ alkyl group; Substituted or unsubstituted C ₂ to C ₆₀ alkenyl group; Substituted or unsubstituted C ₂ to C ₆₀ alkynyl group; Substituted or unsubstituted C ₁ to C ₆₀ alkoxy group; Substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group; Substituted or unsubstituted C ₂ to C ₆₀ heterocycloalkyl group; Substituted or unsubstituted C ₆ to C ₆₀ aryl group; Substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group; -SiRR'R";-P(=O)RR'; and substituted with a C ₁ to C ₂₀ alkyl group, a substituted or unsubstituted C ₆ to C ₆₀ aryl group, or a C ₂ to C ₆₀ heteroaryl group, or Two or more groups selected from the group consisting of unsubstituted amine groups, or adjacent to each other, combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,

R, R' and R" are the same or different from each other, and are each independently hydrogen; deuterium; -CN; substituted or unsubstituted C ₁ to C ₆₀ alkyl group; substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group ; A substituted or unsubstituted C ₆ to C ₆₀ aryl group; or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group.

The heterocyclic compound according to an exemplary embodiment of the present application can be used as an organic layer material of an organic light-emitting device. The heterocyclic compound can be used as a material such as a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a charge generation layer in an organic light emitting device. In particular, the heterocyclic compound represented by Formula 1 can be used as a material for the electron transport layer, hole transport layer, or light-emitting layer of an organic light-emitting device. In addition, when the heterocyclic compound represented by Formula 1 is used in an organic light-emitting device, the driving voltage of the device can be lowered, luminous efficiency can be improved, and the lifespan characteristics of the device can be improved due to the thermal stability of the compound.

In addition, the heterocyclic compound represented by Formula 1 and the compound represented by Formula 2 can be simultaneously used as a material for the light-emitting layer of an organic light-emitting device. In addition, when the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 are used simultaneously in an organic light emitting device, the driving voltage of the device is lowered, the luminous efficiency is improved, and the thermal stability of the compound increases the temperature of the device. Lifespan characteristics can be improved.

1 to 3 are diagrams schematically showing the stacked structure of an organic light-emitting device according to an exemplary embodiment of the present application.

The present application will be described in detail below.

The heterocyclic compound according to an exemplary embodiment of the present application is characterized by being represented by the above formula (1). More specifically, the heterocyclic compound represented by Formula 1 can be used as an organic layer material of an organic light-emitting device due to the structural characteristics of the core structure and substituents as described above.

According to an exemplary embodiment of the present application, R2 in Formula 1 is represented by Formula 3, and R4 is a substituted or unsubstituted aryl group of C ₆ to C ₆₀ ; Alternatively, it may be represented by Formula 4 above.

According to an exemplary embodiment of the present application, R4 of Formula 1 is represented by Formula 3, and R2 is the substituted or unsubstituted aryl group of C ₆ to C ₆₀ ; Alternatively, it may be represented by Formula 4 above.

According to an exemplary embodiment of the present application, R1 of Formula 1 is represented by Formula 3, and R4 is the substituted or unsubstituted aryl group of C ₆ to C ₆₀ ; Alternatively, it may be represented by Formula 4 above.

According to an exemplary embodiment of the present application, R4 of Formula 1 is represented by Formula 3, and R1 is the substituted or unsubstituted aryl group of C ₆ to C ₆₀ ; Alternatively, it may be represented by Formula 4 above.

According to an exemplary embodiment of the present application, Chemical Formula 3 may be represented by any of the following structural formulas.

In the above structural formula, X4 to

R17 to R23 are the same or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; -CN; Substituted or unsubstituted C ₁ to C ₆₀ alkyl group; Substituted or unsubstituted C ₂ to C ₆₀ alkenyl group; Substituted or unsubstituted C ₂ to C ₆₀ alkynyl group; Substituted or unsubstituted C ₁ to C ₆₀ alkoxy group; Substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group; Substituted or unsubstituted C ₂ to C ₆₀ heterocycloalkyl group; Substituted or unsubstituted C ₆ to C ₆₀ aryl group; Substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group; -SiRR'R";-P(=O)RR'; and substituted with a C ₁ to C ₂₀ alkyl group, a substituted or unsubstituted C ₆ to C ₆₀ aryl group, or a C ₂ to C ₆₀ heteroaryl group, or Two or more groups selected from the group consisting of unsubstituted amine groups, or adjacent to each other, combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,

R, R' and R" are the same or different from each other, and are each independently hydrogen; deuterium; -CN; substituted or unsubstituted C ₁ to C ₆₀ alkyl group; substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group ; a substituted or unsubstituted C ₆ to C ₆₀ aryl group; or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group,

m is an integer from 0 to 8, and n, o, p, q, r and s are each independently integers from 0 to 6.

In an exemplary embodiment of the present application, R5 to R8 in Formula 1 may each independently be hydrogen or deuterium.

In addition, the composition for the organic material layer of an organic light-emitting device according to an exemplary embodiment of the present application is characterized in that it simultaneously includes a heterocyclic compound represented by Formula 1 and a compound represented by Formula 2.

In Formulas 5 and 6, * indicates the position connected to L2' of Formula 2.

According to an exemplary embodiment of the present application, Chemical Formula 5 may be represented by any of the following structural formulas.

In the above structural formula, X1' to

R8' to R14' are the same or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; -CN; Substituted or unsubstituted C ₁ to C ₆₀ alkyl group; Substituted or unsubstituted C ₂ to C ₆₀ alkenyl group; Substituted or unsubstituted C ₂ to C ₆₀ alkynyl group; Substituted or unsubstituted C ₁ to C ₆₀ alkoxy group; Substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group; Substituted or unsubstituted C ₂ to C ₆₀ heterocycloalkyl group; Substituted or unsubstituted C ₆ to C ₆₀ aryl group; Substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group; -SiRR'R";-P(=O)RR'; and substituted with a C ₁ to C ₂₀ alkyl group, a substituted or unsubstituted C ₆ to C ₆₀ aryl group, or a C ₂ to C ₆₀ heteroaryl group, or Two or more groups selected from the group consisting of unsubstituted amine groups, or adjacent to each other, combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,

R, R' and R" are the same or different from each other, and are each independently hydrogen; deuterium; -CN; substituted or unsubstituted C ₁ to C ₆₀ alkyl group; substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group ; a substituted or unsubstituted C ₆ to C ₆₀ aryl group; or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group,

m' is an integer from 0 to 8, and n', o', p', q', r' and s' are each independently integers from 0 to 6.

According to an exemplary embodiment of the present application, Chemical Formula 6 may be represented by any of the following structural formulas.

In the above structural formula, X7' and X8' are the same or different from each other and are each independently NR, S, O or CR'R",

R15' to R18' are the same or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; -CN; Substituted or unsubstituted C ₁ to C ₆₀ alkyl group; Substituted or unsubstituted C ₂ to C ₆₀ alkenyl group; Substituted or unsubstituted C ₂ to C ₆₀ alkynyl group; Substituted or unsubstituted C ₁ to C ₆₀ alkoxy group; Substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group; Substituted or unsubstituted C ₂ to C ₆₀ heterocycloalkyl group; Substituted or unsubstituted C ₆ to C ₆₀ aryl group; Substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group; -SiRR'R";-P(=O)RR'; and substituted with a C ₁ to C ₂₀ alkyl group, a substituted or unsubstituted C ₆ to C ₆₀ aryl group, or a C ₂ to C ₆₀ heteroaryl group, or Two or more groups selected from the group consisting of unsubstituted amine groups, or adjacent to each other, combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,

R, R' and R" are the same or different from each other, and are each independently hydrogen; deuterium; -CN; substituted or unsubstituted C ₁ to C ₆₀ alkyl group; substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group ; a substituted or unsubstituted C ₆ to C ₆₀ aryl group; or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group,

t' is an integer from 0 to 7.

According to an exemplary embodiment of the present application, Formula 2 may be represented by any one of the following Formulas 7 to 12.

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

In Formulas 7 to 12, R1' to R6', R8', R9', R12', R13', R16', L1', Ar1', X1', X4', X5', m', n', q The definitions of ', r', and t' are the same as those in Chemical Formula 2 and the structural formula.

In an exemplary embodiment of the present application, R1' to R6' in Formula 2 may each independently be hydrogen or deuterium.

In an exemplary embodiment of the present application, R8' to R18' in the structural formula are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C ₆ to C ₆₀ aryl group; Or it may be a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group.

In an exemplary embodiment of the present application, R, R' and R" in Formula 2 are the same or different from each other, and are each independently hydrogen; a substituted or unsubstituted C ₁ to C ₆₀ alkyl group; or a substituted or unsubstituted It is an aryl group of C ₆ to C ₆₀ .

In the present application, the substituents of Formulas 1 and 2 are described in more detail as follows.

In this specification, “substituted or unsubstituted” means deuterium; halogen group; -CN; C ₁ to C ₆₀ alkyl group; C ₂ to C ₆₀ alkenyl group; C ₂ to C ₆₀ alkynyl group; C ₃ to C ₆₀ cycloalkyl group; C ₂ to C ₆₀ heterocycloalkyl group; C ₆ to C ₆₀ aryl group; C ₂ to C ₆₀ heteroaryl group; -SiRR'R"; -P(=O)RR'; C ₁ to C ₂₀ alkylamine group; C ₆ to C ₆₀ arylamine group; and substituted or unsubstituted with one or more substituents selected from the group consisting of C ₂ to C ₆₀ heteroarylamine groups, or substituted or unsubstituted with substituents in which two or more of the substituents are combined, or where two or more substituents selected from the above substituents are connected. It means substituted or unsubstituted with a substituent. 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. The additional substituents may be further substituted. R, R' and R" are the same or different from each other, and each independently represents hydrogen; deuterium; -CN; substituted or unsubstituted C ₁ to C ₆₀ alkyl group; substituted or unsubstituted C ₃ to C ₆₀ cyclo An alkyl group; a substituted or unsubstituted C ₆ to C ₆₀ aryl group; or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group.

According to an exemplary embodiment of the present application, the "substituted or unsubstituted" refers to deuterium, halogen group, -CN, SiRR'R", P(=O)RR', C ₁ to C ₂₀ straight or branched alkyl group. , C ₆ to C ₆₀ aryl group, and C ₂ to C ₆₀ heteroaryl group, which is substituted or unsubstituted with one or more substituents selected from the group consisting of,

R, R' and R" are the same or different from each other, and each independently represents hydrogen; deuterium; -CN; deuterium, halogen group, -CN, C ₁ to C ₂₀ alkyl group, C ₆ to C ₆₀ aryl group, and a C ₁ to C ₆₀ alkyl group substituted or unsubstituted with a C ₂ to C ₆₀ heteroaryl group; deuterium, halogen, -CN, C ₁ to C ₂₀ alkyl group, C ₆ to C ₆₀ aryl group, and C ₂ C ₃ to C ₆₀ cycloalkyl group substituted or unsubstituted with C ₆₀ heteroaryl group; deuterium, halogen, -CN, C ₁ to C ₂₀ alkyl group, C ₆ to C ₆₀ aryl group, and C ₂ to C C ₆ to C 60 aryl group substituted or unsubstituted with ₆₀ heteroaryl group; or deuterium, halogen, -CN, C _{1 to} C ₂₀ alkyl group, C ₆ to C ₆₀ aryl group, and C ₂ to C ₆₀ It is a C ₂ to C ₆₀ heteroaryl group that is substituted or unsubstituted with a heteroaryl group.

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.

In the present specification, the halogen may be fluorine, chlorine, bromine, or iodine.

In the present specification, the alkyl group includes a straight chain or branched chain having 1 to 60 carbon atoms, and may be further substituted by another substituent. The carbon number of the alkyl group may be 1 to 60, specifically 1 to 40, and more specifically 1 to 20. Specific examples include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1- Ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl- 2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert -Octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group , isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, etc., but is not limited thereto.

In the present specification, the alkenyl group includes a straight chain or branched chain having 2 to 60 carbon atoms, and may be further substituted by another substituent. The alkenyl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, and more specifically 2 to 20 carbon atoms. Specific examples include vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 3-methyl-1 -Butenyl group, 1,3-butadienyl group, allyl group, 1-phenylvinyl-1-yl group, 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2 -(naphthyl-1-yl)vinyl-1-yl group, 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, stilbenyl group, styrenyl group, etc., but is not limited to these.

In the present specification, the alkynyl group includes a straight chain or branched chain having 2 to 60 carbon atoms, and may be further substituted by another substituent. The carbon number of the alkynyl group may be 2 to 60, specifically 2 to 40, and more specifically, 2 to 20.

In the present specification, the cycloalkyl group includes a monocyclic or polycyclic ring having 3 to 60 carbon atoms, and may be further substituted by another substituent. Here, polycyclic refers to a group in which a cycloalkyl group is directly connected to or condensed with another ring group. Here, the other ring group may be a cycloalkyl group, but may also be another type of ring group, such as a heterocycloalkyl group, an aryl group, or a heteroaryl group. The carbon number of the cycloalkyl group may be 3 to 60, specifically 3 to 40, and more specifically 5 to 20. Specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2 , 3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, etc., but is not limited thereto.

In the present specification, the heterocycloalkyl group contains O, S, Se, N or Si as a hetero atom, contains a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by another substituent. Here, polycyclic refers to a group in which a heterocycloalkyl group is directly connected to or condensed with another ring group. Here, the other ring group may be a heterocycloalkyl group, but may also be another type of ring group, such as a cycloalkyl group, an aryl group, or a heteroaryl group. The carbon number of the heterocycloalkyl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 20.

In the present specification, the aryl group includes a monocyclic or polycyclic ring having 6 to 60 carbon atoms, and may be further substituted by another substituent. Here, polycyclic refers to a group in which an aryl group is directly connected to or condensed with another ring group. Here, the other ring group may be an aryl group, but may also be another type of ring group, such as a cycloalkyl group, heterocycloalkyl group, heteroaryl group, etc. The aryl group includes a spiro group. The aryl group may have 6 to 60 carbon atoms, specifically 6 to 40 carbon atoms, and more specifically 6 to 25 carbon atoms. Specific examples of the aryl group include phenyl group, biphenyl group, triphenyl group, naphthyl group, anthryl group, chrysenyl group, phenanthrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, phenalenyl group, and pyrethyl group. Nyl group, tetracenyl group, pentacenyl group, fluorenyl group, indenyl group, acenaphthylenyl group, benzofluorenyl group, spirobifluorenyl group, 2,3-dihydro-1H-indenyl group, and condensed rings thereof These may include, but are not limited to this.

In the present specification, the spiro group is a group containing a spiro structure and may have 15 to 60 carbon atoms. For example, the spiro group may include a structure in which a 2,3-dihydro-1H-indene group or a cyclohexane group is spiro bonded to a fluorenyl group. Specifically, the spiro group below may include any one of the groups of the structural formula below.

In the present specification, the heteroaryl group includes S, O, Se, N, or Si as a hetero atom, includes a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by another substituent. Here, the polycyclic refers to a group in which a heteroaryl group is directly connected to or condensed with another ring group. Here, the other ring group may be a heteroaryl group, but may also be another type of ring group, such as a cycloalkyl group, heterocycloalkyl group, or aryl group. The carbon number of the heteroaryl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 25. Specific examples of the heteroaryl group include pyridyl group, pyrrolyl group, pyrimidyl group, pyridazinyl group, furanyl group, thiophene group, imidazolyl group, pyrazolyl group, oxazolyl group, isoxazolyl group, and thiazolyl group. group, isothiazolyl group, triazolyl group, furazanyl group, oxadiazolyl group, thiadiazolyl group, dithiazolyl group, tetrazolyl group, pyranyl group, thiopyranyl group, diazinyl group, oxazinyl group , thiazinyl group, deoxynyl group, triazinyl group, tetrazinyl group, quinolyl group, isoquinolyl group, quinazolinyl group, isoquinazolinyl group, quinozolyryl group, naphthyridyl group, acridinyl group, phenanthridide Nyl group, imidazopyridinyl group, diazanaphthalenyl group, triazindene group, indolyl group, indolizinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiophene group, benzofuran group , dibenzothiophene group, dibenzofuran group, carbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, phenazinyl group, dibenzosilol group, spirobi (dibenzosilol), dihydrophenazinyl group, Phenoxazinyl group, phenanthridyl group, imidazopyridinyl group, thienyl group, indolo[2,3-a]carbazolyl group, indolo[2,3-b]carbazolyl group, indolinyl group, 10, 11-dihydro-dibenzo[b,f]azepine group, 9,10-dihydroacridinyl group, phenanthrazinyl group, phenothiathiazinyl group, phthalazinyl group, naphthylidinyl group, phenanthrolinyl group, Benzo[c][1,2,5]thiadiazolyl group, 5,10-dihydrodibenzo[b,e][1,4]azacylinyl, pyrazolo[1,5-c]quinazolinyl group , pyrido [1,2-b] indazolyl group, pyrido [1,2-a] imidazo [1,2-e] indolinyl group, 5,11-dihydroindeno [1,2-b ] Carbazolyl group, etc. may be mentioned, but it is not limited thereto.

In the present specification, the amine group is a monoalkylamine group; monoarylamine group; Monoheteroarylamine group; -NH ₂ ; dialkylamine group; Diarylamine group; Diheteroarylamine group; Alkylarylamine group; Alkylheteroarylamine group; and an arylheteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, dibiphenylamine group, anthracenylamine group, 9- Methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group, biphenylnaphthylamine group, phenylbiphenylamine group, biphenyl fluorescein Examples include a nylamine group, phenyltriphenylenylamine group, and biphenyltriphenylenylamine group, but are not limited to these.

In the present specification, an arylene group refers to an aryl group having two bonding positions, that is, a bivalent group. The description of the aryl group described above can be applied, except that each of these is a divalent group. In addition, a heteroarylene group means that a heteroaryl group has two bonding positions, that is, a bivalent group. The description of the heteroaryl group described above can be applied, except that each of these is a divalent group.

According to an exemplary embodiment of the present application, Formula 1 may be represented by any one of the following compounds, but is not limited thereto.

According to an exemplary embodiment of the present application, Formula 2 may be represented by any one of the following compounds, but is not limited thereto.

Additionally, by introducing various substituents into the structures of Formulas 1 and 2, compounds having the unique properties of the introduced substituents can be synthesized. For example, by introducing substituents mainly used in hole injection layer materials, hole transport materials, light emitting layer materials, electron transport layer materials, and charge generation layer materials used in the manufacture of organic light-emitting devices into the core structure, the conditions required for each organic material layer are met. You can synthesize the desired substance.

In addition, by introducing various substituents into the structures of Formulas 1 and 2, the energy band gap can be finely adjusted, while improving the properties at the interface between organic materials and diversifying the uses of the material. .

Meanwhile, the heterocyclic compound has a high glass transition temperature (Tg) and has excellent thermal stability. This increase in thermal stability is an important factor in providing driving stability to the device.

Heterocyclic compounds according to an exemplary embodiment of the present application can be produced through a multi-step chemical reaction. Some intermediate compounds are first prepared, and the compounds of Formula 1 or 2 can be prepared from the intermediate compounds. More specifically, the heterocyclic compound according to an exemplary embodiment of the present application can be prepared based on the production example described later.

In addition, another embodiment of the present application provides a composition for an organic material layer of an organic light-emitting device, characterized in that it simultaneously contains a heterocyclic compound represented by Formula 1 and a compound represented by Formula 2.

Specific details about the heterocyclic compound represented by Formula 1 and the compound represented by Formula 2 are the same as described above.

The weight ratio of the heterocyclic compound represented by Formula 1 to the compound represented by Formula 2 in the composition may be 1:10 to 10:1, 1:8 to 8:1, and 1:5 to 5. : 1, and 1 : 2 to 2 : 1, but is not limited thereto.

The composition can be used when forming an organic material of an organic light-emitting device, and can be particularly preferably used when forming a host for a light-emitting layer.

The composition is a simple mixture of two or more compounds, and powdered materials may be mixed before forming the organic material layer of the organic light-emitting device, or compounds in a liquid state at an appropriate temperature or higher may be mixed. The composition is in a solid state below the melting point of each material, and can be maintained in a liquid state by adjusting the temperature.

Another embodiment of the present application provides an organic light-emitting device containing the heterocyclic compound represented by Formula 1 above.

In addition, the organic light-emitting device according to an exemplary embodiment of the present application includes an anode, a cathode, and at least one organic material layer provided between the anode and the cathode, and at least one layer of the organic material layer is a heterocyclic compound represented by the formula (1) It is characterized in that it includes a compound and a compound represented by the above formula (2).

The organic light emitting device according to an exemplary embodiment of the present application is a conventional organic material layer, except that one or more organic layers are formed using the heterocyclic compound represented by the above-described formula 1 and the heterocyclic compound represented by formula 2. It can be manufactured using light emitting device manufacturing methods and materials.

The compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 may be formed into an organic 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.

Specifically, the organic light-emitting device according to an exemplary embodiment of the present application includes an anode, a cathode, and at least one organic material layer provided between the anode and the cathode, and at least one layer of the organic material layer is a heterocyclic compound represented by Formula 1 above. Contains compounds.

In addition, the organic light-emitting device according to an exemplary embodiment of the present application includes an anode, a cathode, and at least one organic material layer provided between the anode and the cathode, and at least one layer of the organic material layer is a heterocyclic compound represented by Formula 1 above. , and a heterocyclic compound represented by Formula 2 above.

1 to 3 illustrate the stacking order of electrodes and organic material layers of an organic light-emitting device according to an exemplary embodiment of the present application. However, it is not intended that the scope of the present application be limited by these drawings, and structures of organic light-emitting devices known in the art may also be applied to the present application.

According to Figure 1, an organic light emitting device is shown in which an anode 200, an organic material layer 300, and a cathode 400 are sequentially stacked on a substrate 100. However, it is not limited to this structure, and an organic light-emitting device may be implemented in which a cathode, an organic material layer, and an anode are sequentially stacked on a substrate, as shown in FIG. 2.

Figure 3 illustrates the case where the organic material layer is multi-layered. The organic light emitting device according to FIG. 3 includes a hole injection layer 301, a hole transport layer 302, a light emitting layer 303, a hole blocking layer 304, an electron transport layer 305, and an electron injection layer 306. However, the scope of the present application is not limited by this laminated structure, and if necessary, the remaining layers except the light-emitting layer may be omitted, and other necessary functional layers may be added.

The organic light-emitting device according to the present specification includes a heterocyclic compound represented by Formula 1 above in one or more layers of the organic material layer, or simultaneously contains a heterocyclic compound represented by Formula 1 and a heterocyclic compound represented by Formula 2. Except that it can be manufactured using materials and methods known in the art.

The heterocyclic compound represented by Formula 1 may independently constitute one or more layers among the organic material layers of the organic light-emitting device. However, if necessary, it can be mixed with other materials to form an organic layer.

The heterocyclic compound represented by Formula 1 can be used as a material for an electron transport layer, hole blocking layer, and light emitting layer in an organic light-emitting device. As an example, the heterocyclic compound represented by Formula 1 may be used as a material for the electron transport layer, hole transport layer, or light emitting layer of an organic light-emitting device.

In addition, the heterocyclic compound represented by Formula 1 can be used as a material for the light-emitting layer in an organic light-emitting device. As an example, the heterocyclic compound represented by Formula 1 can be used as a phosphorescent host material of the light-emitting layer in an organic light-emitting device.

In addition, the organic material layer containing the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 may further include other materials as needed.

The heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 can be used as a material for a charge generation layer in an organic light-emitting device.

The heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 may be used as materials for an electron transport layer, a hole blocking layer, and a light-emitting layer in an organic light-emitting device. As an example, the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 may be used as a material for an electron transport layer, a hole transport layer, or a light-emitting layer of an organic light-emitting device.

Additionally, the heterocyclic compound represented by Formula 1 and the compound represented by Formula 2 can be used as a material for an emitting layer in an organic light-emitting device. As an example, the heterocyclic compound represented by Formula 1 and the compound represented by Formula 2 can be used as a material for a phosphorescent host of a light-emitting layer in an organic light-emitting device.

The organic light-emitting device of the present invention includes a host and a light-emitting layer using a phosphorescent dopant, and the host is composed of a host compound (p-n type) that is a mixture of two or more compounds, and thus includes a host compound composed of a conventional single compound. It has the effect of having superior lifespan characteristics compared to organic light emitting devices.

In particular, in the case of the p-n type host of the present invention, there is an advantage in that the luminescence characteristics can be increased by adjusting the ratio of the host, which is achieved by combining a P host (heterocyclic compound represented by Formula 1) with good hole mobility and electron mobility. This is a result that can be achieved with an appropriate combination of a good n host (compound represented by Chemical Formula 2).

In the organic light-emitting device according to an exemplary embodiment of the present application, materials other than the heterocyclic compound of Formula 1 and the heterocyclic compound of Formula 2 are illustrated below, but these are for illustrative purposes only and do not cover the scope of the present application. It is not intended to be limiting, and may be replaced with materials known in the art.

As the anode material, materials with a relatively large work function can be used, and transparent conductive oxides, metals, or conductive polymers can be used. Specific examples of the anode material 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] (PEDT), polypyrrole, and polyaniline are included, but are not limited to these.

As the cathode material, materials with a relatively low work function can be used, and metals, metal oxides, or conductive polymers can be used. Specific examples of the cathode material 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.

As the hole injection material, known hole injection materials may be used, for example, phthalocyanine compounds such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429 or described in Advanced Material, 6, p.677 (1994). Starburst type amine derivatives such as tris(4-carbazoyl-9-ylphenyl)amine (TCTA), 4,4',4"-tri[phenyl(m-tolyl)amino]triphenylamine (m- MTDATA), 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB), polyaniline/dodecylbenzenesulfonic acid, a soluble conductive polymer, or poly( 3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate), Polyaniline/Camphor sulfonic acid or polyaniline/ Poly(4-styrenesulfonate) (Polyaniline/Poly(4-styrene-sulfonate)) can be used.

As hole transport materials, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, etc. may be used, and low molecular or high molecular materials may also be used.

Electron transport materials include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, and fluorenone. Derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, etc. may be used, and not only low molecular substances but also high molecular substances may be used.

For example, LiF is typically used as an electron injection material in the industry, but the present application is not limited thereto.

Red, green, or blue light-emitting materials may be used as the light-emitting material, and if necessary, two or more light-emitting materials may be mixed. At this time, two or more light emitting materials can be deposited and used from individual sources, or they can be premixed and deposited from a single source. Additionally, a fluorescent material can be used as a light-emitting material, but it can also be used as a phosphorescent material. As a light-emitting material, a material that emits light by combining holes and electrons injected from an anode and a cathode, respectively, may be used, but materials that participate in light emission together with a host material and a dopant material may also be used.

When using a mixture of hosts of a light emitting material, hosts of the same series may be mixed and used, or hosts of different series may be mixed and used. For example, any two or more types of materials, such as an n-type host material or a P-type host material, can be selected and used as a host material for the light-emitting layer.

The organic light emitting device according to an exemplary embodiment of the present application may be a front emitting type, a rear emitting type, or a double-sided emitting type depending on the material used.

The heterocyclic compound according to an exemplary embodiment of the present application may function in organic electronic devices, including organic solar cells, organic photoreceptors, organic transistors, etc., on a principle similar to that applied to organic light-emitting devices.

Below, the present specification is described in more detail through examples, but these are only for illustrating the present application and are not intended to limit the scope of the present application.

< Example >

< Manufacturing example 1> Preparation of Compound 1

1) Preparation of compound 1-1

One neck r.b.f. (2-chloro-4-fluorophenyl)boronic acid (55g, 315.4 mmol), 1-bromo-2-nitrobenzene (58g, 287mmol), Tetrakis(triphenylPhosphine)Palladium(0)(16.6g, 14.35mmol) , Pottasium carbonate (79g, 574mmol), and toluene/ethanol/water (800ml/160ml/160ml) mixture were refluxed at 110°C.

Extracted with MC and dried with MgSO ₄ . After column purification and packing HX:MC=4:1, the ratio was lowered to 4:1, and after removing the upper side, the ratio was lowered to HX:MC=3:1 to obtain compound 1-1 (72.3g, 93%).

2) Preparation of Compound 1-2

A mixture of 1-1 (70g, 278 mmol), PPh ₃ (218g, 834 mmol), and 1,2-DCB (700ml) was stirred at 160°C for 18h in one neck rbf. After removing the solvent of the reaction product, column purification and packing of HX:MC = 4:1 were lowered to 4:1, the upper side was removed, and the reaction product was obtained by lowering it to MC. After concentration, HX stirring and filtering were performed to obtain compound 1-2 (50g, 82%).

3) Preparation of Compound 1-3

One neck rbf 1-2 (37g, 168.4mmol), Iodobenzene (24.3 ml, 219mmol), CuI (32g, 168mmol), Trans-1,2-diaminocyclohexane (20g, 168mmol), K ₃ PO ₄ (71g, 336mmol) ), the 1,4-dioxane (400ml) mixture was refluxed at 120°C. After the reaction was completed, the reactant was filtered, washed with MC, and the filtrate was concentrated and filtered with silica gel to obtain compound 1-3 (48.8 g, 98%).

4) Preparation of compounds 1-4

One neck rbf 1-3 (6g, 20.2mmol), phenylboronic acid (3.2g, 26.26mmol), Pd ₂ (dba) ₃ (924mg, 11.01mmol), Sphos (0.821g, 2mmol), K ₃ PO ₄ ( A mixture of 8.5 g, 40.4 mmol) of Xylene/EtOH/H ₂ O (100ml/20ml/20ml) was refluxed at 180°C. Extracted with MC and dried with MgSO ₄ . Column purification was performed at HX:MC=2:1 to obtain compound 1-4 (4.68g, 68%).

5) Preparation of Compound 1

One neck rbf 1-4 (4.68g, 13.9mmol), 9-phenyl-9H,9'H-3,3'-bicarbazole (5.7g, 13.9mmol), Cs ₂ CO ₃ (22.6g, 69.5mmol) The DMA (60ml) mixture was refluxed at 160°C for 12h. After filtering, MC washing, and solvent removal in a hot state, compound 1 was obtained by column purification (HX:MC = 2:1) (7.3g, 73%).

< Manufacturing example 2> Preparation of compound 23

Preparation of Compound 1 except that 11,11-dimethyl-5,11-dihydroindeno[1,2-b]carbazole was used instead of 9-phenyl-9H,9'H-3,3'-bicarbazole in Preparation Example 1. By preparing in the same manner, the target compound 23 was obtained (6.8 g, 79%).

< Manufacturing example 3> Preparation of compound 27

The same method as the preparation of Compound 1 except that 11-phenyl-11,12-dihydroindolo[2,3-a]carbazole was used instead of 9-phenyl-9H,9'H-3,3'-bicarbazole in Preparation Example 1. The target compound 27 was obtained (6.8g, 72%).

< Manufacturing example 4> Preparation of compound 29

The same method as the preparation of Compound 1 except that 12H-benzo[4,5]thieno[2,3-a]carbazole was used instead of 9-phenyl-9H,9'H-3,3'-bicarbazole in Preparation Example 1. The target compound 29 was obtained (8.3g, 78%).

< Manufacturing example 5> Preparation of compound 31

Target compound 31 was prepared in the same manner as the preparation of compound 1, except that 5H-benzofuro[3,2-c]carbazole was used instead of 9-phenyl-9H,9'H-3,3'-bicarbazole in Preparation Example 1. was obtained (5.9g, 69%).

< Manufacturing example 6> Preparation of compound 7

1) Preparation of compound 1-1

One neck r.b.f. (2-chloro-4-fluorophenyl)boronic acid (55g, 315.4 mmol), 1-bromo-2-nitrobenzene (58g, 287mmol), Tetrakis(triphenylPhosphine)Palladium(0)(16.6g, 14.35mmol) , Pottasium carbonate (79g, 574mmol), and toluene/ethanol/water (800ml/160ml/160ml) mixture were refluxed at 110°C.

Extracted with MC and dried with MgSO ₄ . After column purification and packing HX:MC=4:1, the ratio was lowered to 4:1, and after removing the upper side, the ratio was lowered to HX:MC=3:1 to obtain compound 1-1 (72.3g, 93%).

2) Preparation of Compound 1-2

A mixture of 1-1 (70g, 278 mmol), PPh ₃ (218g, 834 mmol), and 1,2-DCB (700ml) was stirred at 160°C for 18h in one neck rbf. After removing the solvent of the reaction product, column purification and packing of HX:MC = 4:1 were lowered to 4:1, the upper side was removed, and the reaction product was obtained by lowering it to MC. After concentration, HX stirring and filtering were performed to obtain compound 1-2 (50g, 82%).

3) Preparation of Compound 1-3

One neck rbf 1-2 (37g, 168.4 mmol), Iodobenzene (24.3ml, 219mmol), CuI (32g, 168mmol), Trans-1,2-diaminocyclohexane (20g, 168mmol), K ₃ PO ₄ (71g, 336mmol) ), the 1,4-dioxane (400ml) mixture was refluxed at 120°C. After the reaction was completed, the reactant was filtered, washed with MC, and the filtrate was concentrated and filtered with silica gel to obtain compound 1-3 (48.8 g, 98%).

4) Preparation of compound 7-1

DMA of 1-3 (10g, 33.8 mmol), 9-phenyl-9H,9'H-3,3'-bicarbazole (15.2g, 37.1mmol), and Cs ₂ CO ₃ (55g, 169mmol) in one neck rbf. 100ml) The mixture was refluxed at 160°C for 12h. After filtering, MC washing, and removing the solvent in a hot state, compound 7-1 was obtained by column purification with HX:MC = 3:1 (18.3g, 79%).

5) Compound 7 of manufacturing

One neck rbf 7-1 (18g, 26.3 mmol), [1,1'-biphenyl]-3-ylboronic acid (6.7g, 34.19mmol), Pd ₂ (dba) ₃ (1.2g, 1.31mmol), Sphos (1g, 2.6mmol) and K ₃ PO ₄ (11g, 52mmol) in Xylene/EtOH/H2O (200ml/50ml/50ml) were refluxed at 180°C. Extracted with MC and dried with MgSO ₄ . Compound 7 was obtained through column purification at HX:MC = 2:1 (16.1g, 76%).

< Manufacturing example 7> Preparation of compound 9

The target compound 9 was prepared in the same manner as the preparation of compound 7, except that [1,1'-biphenyl]-4-ylboronic acid was used instead of [1,1'-biphenyl]-3-ylboronic acid in Preparation Example 6. obtained (7.4g, 72%).

< Manufacturing example 8> Preparation of compound 11

The target compound 11 was obtained in the same manner as the preparation of compound 7, except that dibenzo[b,d]thiophen-4-ylboronic acid was used instead of [1,1'-biphenyl]-3-ylboronic acid in Preparation Example 6. (6.9g, 83%).

< Manufacturing example 9> Preparation of Compound 12

The target compound 12 was obtained in the same manner as the preparation of compound 7, except that dibenzo[b,d]furan-4-ylboronic acid was used instead of [1,1'-biphenyl]-3-ylboronic acid in Preparation Example 6. (8.2g, 87%).

< Manufacturing example 10> Preparation of Compound 20

1) Preparation of compound 1-1

One neck r.b.f. (2-chloro-4-fluorophenyl)boronic acid (55g, 315.4mmol), 1-bromo-2-nitrobenzene (58g, 287mmol), Tetrakis(triphenylPhosphine)Palladium(0)(16.6g, 14.35mmol) , Pottasium carbonate (79g, 574mmol), and toluene/ethanol/water (800ml/160ml/160ml) mixture were refluxed at 110°C.

Extracted with MC and dried with MgSO ₄ . After column purification and packing HX:MC=4:1, the ratio was lowered to 4:1, and after removing the upper side, the ratio was lowered to HX:MC=3:1 to obtain compound 1-1 (72.3g, 93%).

2) Preparation of Compound 1-2

A mixture of 1-1 (70g, 278 mmol), PPh ₃ (218g, 834mmol), and 1,2-DCB (700ml) was stirred at 160°C for 18h in one neck rbf. After removing the solvent of the reaction product, column purification and packing of HX:MC = 4:1 were lowered to 4:1, the upper side was removed, and the reaction product was obtained by lowering it to MC. After concentration, HX stirring and filtering were performed to obtain compound 1-2 (50g, 82%).

3) Preparation of compound 20-1

One neck rbf contains 1-2 (12.3g, 56.1 mmol), 4-bromodibenzo[b,d]furan (15.2g, 61.7mmol), CuI (10.6g, 56mmol), Trans-1,2-diaminocyclohexane (6.6g) ,56mmol), K ₃ PO ₄ (23.6g, 112mmol), and 1,4-dioxane (130ml) were refluxed at 120°C.

After the reaction was completed, the reactant was filtered, washed with MC, and the filtrate was concentrated and filtered with silica gel to obtain compound 20-1 (15.2 g, 70%).

4) Preparation of compound 20-2

One neck rbf 20-1 (15.2g, 39.39 mmol), phenylboronic acid (6.2g, 51.2mmol), Pd ₂ (dba) ₃ (1.8g, 1.96mmol), Sphos (1.6g, 3.93mmol), K ₃ A mixture of PO ₄ (16.7g, 78.78mmol) in Xylene/EtOH/H2O (100ml/20ml/20ml) was refluxed at 180°C. It was extracted with MC and dried with MgSO ₄ . Column purification was performed at HX:MC=1:1 to obtain compound 20-2 (12.3g, 73%).

5) Preparation of Compound 20

DMA of 20-2 (12.3g, 28.7mmol), 9-phenyl-9H,9'H-3,3'-bicarbazole (14g, 34.4mmol), Cs ₂ CO ₃ (46.8g, 143mmol) in one neck rbf. (120ml) The mixture was refluxed at 160°C for 12h. After filtering, MC washing, and removing the solvent in a hot state, column purification was reduced to HX:MC = 2:1, and then acetone hot filtered to obtain compound 20 (18.9g, 80%).

< Manufacturing example 11 > Preparation of compound 21

The target compound 21 was obtained in the same manner as the preparation of compound 20, except that 4-bromodibenzo[b,d]thiophene was used instead of 4-bromodibenzo[b,d]furan in Preparation Example 10 (17.9 g, 76%). .

< Manufacturing example 12 > Preparation of compound 33

The target compound 33 was obtained in the same manner as the preparation of compound 1, except that (4-chloro-2-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 1 (9.8 g) , 88%).

< Manufacturing example 13> Preparation of compound 55

The target compound 55 was obtained in the same manner as the preparation of compound 23, except that (4-chloro-2-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 2 (7.7 g) , 76%).

< Manufacturing example 14> Preparation of Compound 59

The target compound 59 was obtained in the same manner as the preparation of compound 27, except that (4-chloro-2-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 3 (11.3 g) , 81%).

< Manufacturing example 15> Preparation of Compound 61

The target compound 61 was obtained in the same manner as the preparation of compound 29, except that (4-chloro-2-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 4 (12.1 g) , 84%).

< Manufacturing example 16> Preparation of Compound 63

The target compound 63 was obtained in the same manner as the preparation of compound 31, except that (4-chloro-2-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 5 (10.4 g) , 78%).

< Manufacturing example 17> Preparation of compound 39

The target compound 39 was obtained in the same manner as the preparation of compound 7, except that (4-chloro-2-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 6 (9.8 g) , 85%).

< Manufacturing example 18> Preparation of Compound 41

The target compound 41 was obtained in the same manner as the preparation of compound 9, except that (4-chloro-2-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 7 (12.7 g) , 83%).

< Manufacturing example 19> Preparation of compound 43

The target compound 43 was obtained in the same manner as the preparation of compound 11, except that (4-chloro-2-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 8 (12.3 g) , 80%).

< Manufacturing example 20> Preparation of Compound 44

The target compound 44 was obtained in the same manner as the preparation of compound 12, except that (4-chloro-2-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 9 (7.3 g) , 75%).

< Manufacturing example 21> Preparation of Compound 52

The target compound 52 was obtained in the same manner as the preparation of compound 20, except that (4-chloro-2-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 10 (8.7 g) , 79%).

< Manufacturing example 22> Preparation of compound 53

The target compound 53 was obtained in the same manner as the preparation of compound 21, except that (4-chloro-2-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 11 (10.1 g) , 81%).

< Manufacturing example 23> Preparation of Compound 65

The target compound 65 was obtained in the same manner as the preparation of Compound 1, except that (2-chloro-5-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 1 (15.3 g) , 86%).

< Manufacturing example 24> Preparation of Compound 87

The target compound 87 was obtained in the same manner as the preparation of compound 23, except that (2-chloro-5-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 2 (7.1, 79%).

< Manufacturing example 25> Preparation of Compound 95

The target compound 95 was obtained in the same manner as the preparation of compound 31, except that (2-chloro-5-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 5 (9.9, 82%).

< Manufacturing example 26> Preparation of Compound 75

The target compound 75 was obtained in the same manner as the preparation of compound 11, except that (2-chloro-5-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 8 (9.2, 72%).

< Manufacturing example 27> Preparation of Compound 76

The target compound 76 was obtained in the same manner as the preparation of compound 12, except that (2-chloro-5-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 9 (6.9, 71%).

< Manufacturing example 28> Preparation of Compound 84

The target compound 84 was obtained in the same manner as the preparation of compound 20, except that (2-chloro-5-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 10 (7.9, 77%).

< Manufacturing example 29> Preparation of Compound 85

The target compound 85 was obtained in the same manner as the preparation of compound 21, except that (2-chloro-5-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 11 (8.3, 79%).

< Manufacturing example 30> Preparation of Compound 97

The target compound 97 was obtained in the same manner as the preparation of Compound 1, except that (5-chloro-2-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 1 (11.3 g) , 81%).

< Manufacturing example 31> Preparation of Compound 123

The target compound 123 was obtained in the same manner as the preparation of compound 27, except that (5-chloro-2-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 3 (9.8 g) , 72%).

< Manufacturing example 32> Preparation of Compound 125

The target compound 125 was obtained in the same manner as the preparation of compound 29, except that (5-chloro-2-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 4 (10.3 g) , 84%).

< Manufacturing example 33> Preparation of Compound 107

The target compound 107 was obtained in the same manner as the preparation of compound 11, except that (5-chloro-2-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 8 (13.2 g) , 79%).

< Manufacturing example 34> Preparation of Compound 108

The target compound 108 was obtained in the same manner as the preparation of compound 12, except that (5-chloro-2-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 9 (11.3 g) , 83%).

< Manufacturing example 35> Preparation of Compound 116

The target compound 116 was obtained in the same manner as the preparation of compound 20, except that (5-chloro-2-fluorophenyl)boronic acid was used instead of (2-chloro-4-fluorophenyl)boronic acid in Preparation Example 10 (8.2 g) , 87%).

Compounds were prepared in the same manner as in the above preparation examples, and the synthesis confirmation results are shown in Tables 1 and 2 below.

[Table 1]

[Table 2]

Table 1 above shows the NMR values, and Table 2 shows the measured values of FD-mass spectrometry (FD-MS: Field desorption mass spectrometry).

< Experiment example 1>

1) Fabrication of organic light emitting device

A glass substrate coated with a thin film of ITO with a thickness of 1,500 Å was washed with distilled water ultrasonic waves. After washing with distilled water, it was ultrasonic washed with solvents such as acetone, methanol, and isopropyl alcohol, dried, and then treated with UV for 5 minutes using UV light in a UV cleaner. Afterwards, the substrate was transferred to a plasma cleaner (PT), then plasma treated in a vacuum to remove the ITO work function and residual film, and then transferred to a thermal evaporation equipment for organic deposition.

On the ITO transparent electrode (anode), a common hole injection layer 2-TNATA (4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine) and a hole transport layer NPB(N,N'-Di( 1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) was formed.

A light emitting layer was thermally vacuum deposited thereon as follows. The light emitting layer was deposited at 400 Å by doping 7% of Ir ₍ ppy) 3 on the host using the compound listed in Table 3 below and Ir(ppy) ₃ (tris(2-phenylpyridine)iridium) as the green phosphorescent dopant. Afterwards, 60Å of BCP was deposited as a hole blocking layer, and 200Å of Alq ₃ was deposited on top of it as an electron transport layer. Finally, lithium fluoride (LiF) was deposited to a thickness of 10Å on the electron transport layer to form an electron injection layer, and then an aluminum (Al) cathode was deposited to a thickness of 1200Å to form a cathode on the electron injection layer, thereby reducing the organic electric field. A light emitting device was manufactured.

Meanwhile, all organic compounds required for OLED device production were purified by vacuum sublimation under 10 ^-6 to 10 ^-8 torr for each material and used for OLED production.

2) Organic electric field Driving voltage and luminous efficiency of light emitting elements

The electroluminescence (EL) characteristics of the organic electroluminescent device manufactured as described above were measured using the M7000 from MacScience, and the standard luminance was measured to be 6,000 using the lifespan measurement equipment (M6000) manufactured by MacScience based on the measurement results. When cd/m ² , T90 was measured. The characteristics of the organic electroluminescent device of the present invention are shown in Table 3.

[Comparative Example 1]

[Comparative Example 2]

[Comparative Example 3]

[Comparative Example 4]

[Comparative Example 5]

[Comparative Example 6]

[Comparative Example 7]

[Table 3]

< Experiment example 2> Fabrication of organic light emitting devices

A glass substrate coated with a thin film of ITO with a thickness of 1,500 Å was washed with distilled water ultrasonic waves. After washing with distilled water, it was ultrasonic washed with solvents such as acetone, methanol, and isopropyl alcohol, dried, and treated with UV for 5 minutes using UV light in a UV cleaner. Afterwards, the substrate was transferred to a plasma cleaner (PT), then plasma treated in a vacuum to remove the ITO work function and residual film, and then transferred to a thermal evaporation equipment for organic deposition.

On the ITO transparent electrode (anode), a common hole injection layer 2-TNATA (4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine) and a hole transport layer NPB(N,N'-Di( 1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) was formed.

A light emitting layer was thermally vacuum deposited thereon as follows. As a host, the light-emitting layer was deposited with 400 Å of one compound shown in Chemical Formula 1 and one compound shown in Chemical Formula 2 from each individual source, as shown in Table 4 below, and the green phosphorescent dopant was deposited by doping 7% of Ir(ppy) ₃ . Afterwards, 60Å of BCP was deposited as a hole blocking layer, and 200Å of Alq ₃ was deposited on top of it as an electron transport layer. Finally, lithium fluoride (LiF) was deposited to a thickness of 10Å on the electron transport layer to form an electron injection layer, and then an aluminum (Al) cathode was deposited to a thickness of 1,200Å on the electron injection layer to form the cathode, thereby forming an organic An electroluminescent device was manufactured.

Meanwhile, all organic compounds required for OLED device production were purified by vacuum sublimation under 10 ^-6 to 10 ^-8 torr for each material and used for OLED production.

< Experiment example 3> Fabrication of organic light emitting devices

A glass substrate coated with a thin film of ITO with a thickness of 1,500 Å was washed with distilled water ultrasonic waves. After washing with distilled water, it was ultrasonic washed with solvents such as acetone, methanol, and isopropyl alcohol, dried, and treated with UV for 5 minutes using UV light in a UV cleaner. Afterwards, the substrate was transferred to a plasma cleaner (PT), then plasma treated in a vacuum to remove the ITO work function and residual film, and then transferred to a thermal evaporation equipment for organic deposition.

On the ITO transparent electrode (anode), a common hole injection layer 2-TNATA (4,4',4"-Tris[2-naphthyl(phenyl)amino]triphenylamine) and a hole transport layer NPB(N,N'-Di( 1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) was formed.

A light emitting layer was thermally vacuum deposited thereon as follows. The light-emitting layer was deposited at 400 Å from one source after premixing one compound shown in Chemical Formula 1 and one compound shown in Chemical Formula 2 as a host, as shown in Table 5 below, and the green phosphorescent dopant was deposited by doping 7% of Ir(ppy) ₃ did. Afterwards, 60Å of BCP was deposited as a hole blocking layer, and 200Å of Alq ₃ was deposited on top of it as an electron transport layer. Finally, lithium fluoride (LiF) was deposited to a thickness of 10Å on the electron transport layer to form an electron injection layer, and then an aluminum (Al) cathode was deposited to a thickness of 1,200Å on the electron injection layer to form the cathode, thereby forming an organic An electroluminescent device was manufactured.

Meanwhile, all organic compounds required for OLED device production were purified by vacuum sublimation under 10 ^-6 to 10 ^-8 torr for each material and used for OLED production.

The driving voltage and luminous efficiency of the organic electroluminescent devices according to Experimental Examples 2 and 3 are as follows.

The electroluminescence (EL) characteristics of the organic electroluminescent device manufactured as described above were measured using the M7000 from McScience, and the standard luminance was measured to be 6,000 using the lifespan measurement equipment (M6000) manufactured by McScience based on the measurement results. When cd/m ² , T90 was measured.

The characteristics of the organic electroluminescent device of the present invention are shown in Tables 4 and 5 below. For reference, Table 4 is an example of simultaneous deposition of the two host compounds of Experimental Example 2 from separate sources, and Table 5 is an example of the two light-emitting layer compounds of Experimental Example 3 deposited from a single source after premixing.

[Ref 1]

[Ref 2]

[Ref 3]

[Ref 4]

[Table 4]

[Table 5]

The organic light-emitting device of the present invention includes a host and a light-emitting layer using a phosphorescent dopant, and the host is composed of a host compound (p-n type) that is a mixture of two or more compounds, and thus includes a host compound composed of a conventional single compound. It has the effect of having superior lifespan characteristics compared to organic light emitting devices.

In particular, in the case of the p-n type host of the present invention, there is an advantage in that the luminescence characteristics can be increased by adjusting the ratio of the host. This is a result that can be achieved by an appropriate combination of a P host with good hole mobility and an n host with good electron mobility. am.

In addition, in the present invention, a light-emitting host composed of multiple types of compounds was deposited by premixing the compounds and forming a single deposition source. Therefore, the uniformity and characteristics of the thin film can be improved, the process process can be simplified, the cost can be reduced, and a device with improved efficiency and lifespan can be formed.

100: substrate
200: anode
300: Organic layer
301: hole injection layer
302: hole transport layer
303: light emitting layer
304: hole blocking layer
305: electron transport layer
306: electron injection layer
400: cathode

Claims (17)

Heterocyclic compound represented by the following formula (1):
[Formula 1]

In Formula 1,
Ar1 is a substituted or unsubstituted C ₆ to C ₆₀ aryl group; Or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group,
One of R1 to R4 is represented by the following formula (3), and the other is a substituted or unsubstituted aryl group of C ₆ to C ₆₀ ; or is represented by the following formula 4, the remainder being hydrogen,
R5 to R8 are the same as or different from each other, and are each independently hydrogen; or deuterium;
[Formula 3]

Formula 3 is represented by any of the following structural formulas,


In the above structural formula, X4, X6 to
R18, R20, R21 and R22 are the same or different from each other and are each independently hydrogen; or deuterium,
R17 is a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group,
m is an integer from 0 to 8, n, p, q and r are each independently an integer from 0 to 6,
[Formula 4]

In Formula 4 above,
X1 is O; or S;,
Ar2 is each independently hydrogen; or deuterium,
t is an integer from 0 to 4,
R, R' and R" are the same or different from each other, and each independently represents a substituted or unsubstituted C ₁ to C ₆₀ alkyl group; or a substituted or unsubstituted C ₆ to C ₆₀ aryl group. The method according to claim 1, wherein R2 in Formula 1 is represented by Formula 3, and R4 is a substituted or unsubstituted aryl group of C ₆ to C ₆₀ ; Or a heterocyclic compound characterized by being represented by the above formula (4). The method according to claim 1, wherein R4 in Formula 1 is represented by Formula 3, and R2 is a substituted or unsubstituted aryl group of C ₆ to C ₆₀ ; Or a heterocyclic compound characterized by being represented by the above formula (4). The method according to claim 1, wherein R1 in Formula 1 is represented by Formula 3, and R4 is a substituted or unsubstituted aryl group of C ₆ to C ₆₀ ; Or a heterocyclic compound characterized by being represented by the above formula (4). The method according to claim 1, wherein R4 in Formula 1 is represented by Formula 3, and R1 is a substituted or unsubstituted aryl group of C ₆ to C ₆₀ ; Or a heterocyclic compound characterized by being represented by the above formula (4). delete delete The heterocyclic compound according to claim 1, wherein Formula 1 is represented by any one of the following compounds:

An organic light-emitting device comprising an anode, a cathode, and at least one organic material layer provided between the anode and the cathode, wherein at least one layer of the organic material layer includes the heterocyclic compound according to any one of claims 1 to 5 and 8. The method of claim 9, wherein the organic material layer includes at least one layer of a hole blocking layer, an electron injection layer, and an electron transport layer, and at least one layer of the hole blocking layer, an electron injection layer, and an electron transport layer includes the heterocyclic compound. Characterized by an organic light-emitting device. The organic light-emitting device of claim 9, wherein the organic material layer includes a light-emitting layer, and the light-emitting layer includes the heterocyclic compound. The method of claim 9, wherein the organic material layer includes one or more layers among a hole injection layer, a hole transport layer, and a layer that simultaneously performs hole injection and hole transport, and one of the layers includes the heterocyclic compound. Organic light-emitting device. The organic light-emitting device of claim 9, wherein the organic material layer containing the heterocyclic compound further includes a compound represented by the following formula (2):
[Formula 2]

In Formula 2,
L1' and L2' are the same or different from each other, and are each independently a direct bond or a substituted or unsubstituted C ₆ to C ₆₀ arylene group,
Ar1' is a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group containing at least one N,
Ar2' is represented by any of the following formulas 5 and 6,
[Formula 5]

[Formula 6]

Y1 to Y4 are the same or different from each other, and are each independently a substituted or unsubstituted benzene ring; Substituted or unsubstituted dimethylfluorene ring; Substituted or unsubstituted carbazole ring; Substituted or unsubstituted dibenzofuran ring; Or a substituted or unsubstituted dibenzothiophene ring,
R1' to R6' are the same or different from each other, and are each independently hydrogen; or deuterium;
R7' is a substituted or unsubstituted aryl group having C ₆ to C ₆₀ ; Or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group. delete The organic light-emitting device according to claim 13, wherein Formula 2 is represented by any one of the following compounds:

A composition for the organic material layer of an organic light-emitting device, characterized in that it simultaneously contains a heterocyclic compound represented by the following formula (1) and a compound represented by the following formula (2):
[Formula 1]

[Formula 2]

In Formulas 1 and 2,
Ar1 is a substituted or unsubstituted C ₆ to C ₆₀ aryl group; Or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group,
One of R1 to R4 is represented by the following formula (3), and the other is a substituted or unsubstituted aryl group of C ₆ to C ₆₀ ; or is represented by the following formula 4, the remainder being hydrogen,
R5 to R8 are the same as or different from each other, and are each independently hydrogen; or deuterium;
[Formula 3]

Formula 3 is represented by any of the following structural formulas,


In the above structural formula, X4, X6 to
R18, R20, R21 and R22 are the same or different from each other and are each independently hydrogen; or deuterium,
R17 is a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group,
m is an integer from 0 to 8, n, p, q and r are each independently an integer from 0 to 6,
[Formula 4]

In Formula 4 above,
X1 is O; or S;,
Ar2 is each independently hydrogen; or deuterium,
t is an integer from 0 to 4,
R, R' and R" are the same or different from each other, and are each independently a substituted or unsubstituted C ₁ to C ₆₀ alkyl group; or a substituted or unsubstituted C ₆ to C ₆₀ aryl group;
L1' and L2' are the same or different from each other, and are each independently a direct bond or a substituted or unsubstituted C ₆ to C ₆₀ arylene group,
Ar1' is a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group containing at least one N,
Ar2' is represented by any of the following formulas 5 and 6,
[Formula 5]

[Formula 6]

Y1 to Y4 are the same or different from each other, and are each independently a substituted or unsubstituted benzene ring; Substituted or unsubstituted dimethylfluorene ring; Substituted or unsubstituted carbazole ring; Substituted or unsubstituted dibenzofuran ring; Or a substituted or unsubstituted dibenzothiophene ring,
R1' to R6' are the same or different from each other, and are each independently hydrogen; or deuterium;
R7' is a substituted or unsubstituted aryl group having C ₆ to C ₆₀ ; Or a substituted or unsubstituted C ₂ to C ₆₀ heteroaryl group. The composition for an organic material layer of an organic light-emitting device according to claim 16, wherein the weight ratio of the heterocyclic compound represented by Formula 1 to the compound represented by Formula 2 in the composition is 1:10 to 10:1.

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