CN110036013B

CN110036013B - Heterocyclic compound and organic light-emitting device using the same

Info

Publication number: CN110036013B
Application number: CN201780074623.5A
Authority: CN
Inventors: 罗炫柱; 许柔珍; 郑元场; 崔珍硕; 崔大赫; 李柱东
Original assignee: LT Materials Co Ltd
Current assignee: LT Materials Co Ltd
Priority date: 2016-11-30
Filing date: 2017-11-30
Publication date: 2022-04-12
Anticipated expiration: 2037-11-30
Also published as: CN110036013A; WO2018101764A1

Abstract

The present application relates to a heterocyclic compound represented by chemical formula 1, and an organic light emitting device including the same. In chemical formula 1, the definition of each substituent is the same as that defined in the embodiment. The use of the heterocyclic compound represented by chemical formula 1 in an organic light emitting device reduces the driving voltage of the device, enhances light efficiency, and can enhance the life span characteristics of the device through thermal stability of the compound. [ chemical formula 1]

Description

Heterocyclic compound and organic light-emitting device using the same

The present application claims the priority and benefit of Korean patent application No. 10-2016-.

Technical Field

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

Background

An electroluminescent device is an automatic light emitting display device and has advantages of having a wide viewing angle and a fast response speed and having excellent contrast.

The organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to the organic light emitting device having such a structure, electrons and holes injected from the two electrodes are combined and paired in the organic thin film, and light is emitted when the electrons and the holes are annihilated. If necessary, a single-layer or multi-layer organic thin film may be formed.

If necessary, the material for the organic thin film may have a light emitting function. For example, a compound capable of forming the light emitting layer itself may be used alone as a material of the organic thin film, or a compound capable of serving as a host or a dopant of the host-dopant-based light emitting layer may also be used. Further, as the material of the organic thin film, a compound capable of functioning as hole injection, hole transfer, electron blocking, hole blocking, electron transfer, electron injection, and the like can also be used.

The development of organic thin film materials is continuously demanding improvements in the performance, lifetime, or efficiency of organic light emitting devices.

Disclosure of Invention

Technical problem

The present application relates to a novel heterocyclic compound and an organic light emitting device using the same.

Technical scheme

One embodiment of the present application provides a heterocyclic compound represented by the following chemical formula 1:

[ chemical formula 1]

In the chemical formula 1, the first and second,

at least one of R1 to R5 is represented by- (L1) p- (Z1) q, and the remainder are hydrogen, substituted or unsubstituted C₆To C₆₀Aryl, or C₂To C₆₀(ii) a heteroaryl group, wherein,

l1 is a direct bond; substituted or unsubstituted C₆To C₆₀An arylene group; or C₂To C₆₀A heteroarylene group, a heteroaryl group,

z1 is selected from the group consisting of: a halo group; -CN; substituted or unsubstituted C₁To C₆₀An alkyl group; substituted or unsubstituted C₆To C₆₀An aryl group; substituted or unsubstituted C₂To C₆₀A heteroaryl group; -SiRR' R "; -P (═ O) RR'; and unsubstituted or substituted by C₁To C₂₀Alkyl radical, C₆To C₆₀Aryl or C₂To C₆₀An amino group substituted with a heteroaryl group,

p is an integer of 0 to 4,

q is an integer of 1 to 4,

r6 to R13 are the same or different from each other and are each independently selected from the group consisting of: hydrogen; deuterium; a halo group; -CN; substituted or unsubstituted C₁To C₆₀An alkyl group; substituted or unsubstituted C₂To C₆₀An alkenyl group; substituted or unsubstituted C₂To C₆₀An alkynyl group; by substitutionOr unsubstituted C₁To C₆₀An alkoxy group; substituted or unsubstituted C₃To C₆₀A cycloalkyl group; substituted or unsubstituted C₂To C₆₀A heterocycloalkyl group; substituted or unsubstituted C₆To C₆₀An aryl group; substituted or unsubstituted C₂To C₆₀A heteroaryl group; -SiRR' R "; -P (═ O) RR'; and unsubstituted or substituted by C₁To C₂₀Alkyl radical, C₆To C₆₀Aryl or C₂To C₆₀Heteroaryl-substituted amine groups, or two or more groups adjacent to each other, bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,

m and n are each independently an integer of 0 to 5, and

r, R 'and R' are the same or different from each other and are each independently hydrogen; deuterium; -CN; substituted or unsubstituted C₁To C₆₀An alkyl group; substituted or unsubstituted C₃To C₆₀A cycloalkyl group; substituted or unsubstituted C₆To C₆₀An aryl group; or substituted or unsubstituted C₂To C₆₀A heteroaryl group.

Another embodiment of the present application provides an organic light emitting device including an anode, a cathode, and organic material layers disposed between the anode and the cathode, wherein one or more of the organic material layers includes a heterocyclic compound represented by chemical formula 1.

Effect of the invention

The heterocyclic compound according to one embodiment of the present invention can be used as an organic material layer material of an organic light-emitting device. The heterocyclic compound is useful as a material for a hole injection layer, a hole transfer layer, a light emitting layer, an electron transfer layer, an electron injection layer, a charge generation layer, or the like in an organic light emitting device. In particular, the heterocyclic compound represented by chemical formula 1 may be used as a material of an electron transfer layer or a charge generation layer in an organic light emitting device. In addition, the use of the heterocyclic compound represented by chemical formula 1 in the organic light emitting device reduces the driving voltage of the device, enhances light efficiency, and can enhance the life span characteristics of the device through thermal stability of the compound.

Drawings

Fig. 1 to 4 are drawings, each of which schematically illustrates a stacked-layer structure of an organic light emitting device according to an embodiment of the present invention.

< description of symbols >

100: substrate

200: anode

300: organic material layer

301: hole injection layer

302: hole transport layer

303: luminescent layer

304: hole blocking layer

305: electron transport layer

306: electron injection layer

400: cathode electrode

Detailed Description

Hereinafter, the present application will be described in detail.

A heterocyclic compound according to one embodiment of the present application is represented by chemical formula 1. More specifically, the heterocyclic compound represented by chemical formula 1, which has such a core structure and structural characteristics of substituents, can be used as a material for an organic material layer of an organic light emitting device.

In one embodiment of the present application, when p of chemical formula 1 is 2 or more, two or more L1 may be the same as or different from each other. Further, when q of chemical formula 1 is 2 or more, two or more Z1 may be the same as or different from each other.

In one embodiment of the present application, at least one of R1 to R5 of chemical formula 1 is represented by- (L1) p- (Z1) q, and the others may be hydrogen.

In one embodiment of the present application, R3 in R1 to R5 of chemical formula 1 is represented by- (L1) p- (Z1) q, and the rest may be hydrogen.

In one embodiment of the present application, R4 in R1 to R5 of chemical formula 1 is represented by- (L1) p- (Z1) q, and the rest may be hydrogen.

Specifically, when a compound in which the position of R3 or R4 in R1 to R5 of chemical formula 1 is substituted with a substituent of- (L1) p- (Z1) q is subsequently used as a material of an electron transfer layer of an organic light-emitting device, the intermolecular interaction is smooth to facilitate the intermolecular electron transfer.

The compound in which the position of R1 or R5 of chemical formula 1 is substituted with a substituent of- (L1) p- (Z1) q has a larger molecular size than the compound in which the position of R3 or R4 in R1 to R5 of chemical formula 1 is substituted with a substituent of- (L1) p- (Z1) q, and thus, the amount of electron migration is reduced due to reduced molecular interaction.

In one embodiment of the present application, L1 of formula 1 may be a direct bond; substituted or unsubstituted C₆To C₆₀An arylene group; or C₂To C₆₀A heteroarylene group.

In another embodiment, L1 of formula 1 may be a direct bond; substituted or unsubstituted C₆To C₄₀An arylene group; or C₂To C₄₀A heteroarylene group.

In another embodiment, L1 of formula 1 may be a direct bond; c₆To C₄₀An arylene group; or C₂To C₄₀A heteroarylene group.

In another embodiment, L1 of formula 1 may be a direct bond; a phenylene group; a biphenylene group; an anthracenylene group; a naphthylene group; a divalent imidazo [1,2-a ] pyridinyl group; a divalent pyridyl group; a divalent pyrimidinyl group; a divalent triazine group; a divalent quinazolinyl group; or a divalent benzimidazolyl group.

In one embodiment of the present application, Z1 of formula 1 can be selected from the group consisting of: substituted or unsubstituted C₁To C₆₀An alkyl group; substituted or unsubstituted C₆To C₆₀An aryl group; substituted or unsubstituted C₂To C₆₀A heteroaryl group; p (═ O) RR'; -CN; and unsubstituted or substituted by C₆To C₆₀Aryl or C₂To C₆₀Heteroaryl substituted amino.

In another embodiment, Z1 of formula 1 can be selected from the group consisting of: substituted or notSubstituted C₁To C₄₀An alkyl group; substituted or unsubstituted C₆To C₄₀An aryl group; substituted or unsubstituted C₂To C₄₀A heteroaryl group; p (═ O) RR'; -CN; and unsubstituted or substituted by C₆To C₄₀Aryl or C₂To C₄₀Heteroaryl substituted amino.

In another embodiment, Z1 of formula 1 can be selected from the group consisting of: c₁To C₄₀An alkyl group; unsubstituted or via P (═ O) RR', C₆To C₄₀Aryl and C₂To C₄₀C substituted by one or more substituents selected from the group consisting of heteroaryl₆To C₄₀An aryl group; unsubstituted or via C₁To C₄₀Alkyl radical, C₆To C₄₀Aryl and C₂To C₄₀C substituted by one or more substituents selected from the group consisting of heteroaryl₂To C₄₀A heteroaryl group; -P (═ O) RR'; and-CN.

In another embodiment, Z1 of formula 1 can be selected from the group consisting of: c₁To C₄₀An alkyl group; unsubstituted or via P (═ O) RR', C₆To C₄₀Aryl and C₂To C₄₀C substituted by one or more and three or less substituents selected from the group consisting of heteroaryl₆To C₄₀An aryl group; unsubstituted or via C₁To C₄₀Alkyl radical, C₆To C₄₀Aryl and C₂To C₄₀C substituted by one or more and three or less substituents selected from the group consisting of heteroaryl₂To C₄₀A heteroaryl group; -P (═ O) RR'; and-CN.

In another embodiment, Z1 of formula 1 can be selected from the group consisting of: phenyl unsubstituted or substituted by one or more substituents selected from the group consisting of P (═ O) RR', phenyl and carbazolyl; naphthyl unsubstituted or substituted with P (═ O) RR'; anthracenyl unsubstituted or substituted by one or more substituents selected from the group consisting of P (═ O) RR' and naphthyl; a biphenyl group; triphenylene biylidene; and phenanthryl.

In another embodiment, Z1 of formula 1 can be selected from the group consisting of: an ethyl group; p (═ O) RR'; and-CN.

In another embodiment, Z1 of formula 1 can be unsubstituted or via C₁To C₄₀Alkyl radical, C₆To C₄₀Aryl and C₂To C₄₀C substituted by one or more substituents selected from the group consisting of heteroaryl₂To C₄₀Heteroaryl, and heteroaryl may include N, O as a heteroatom and at least one or more of S.

In another embodiment, Z1 of formula 1 can be selected from the group consisting of: pyridyl unsubstituted or substituted with one or more substituents selected from the group consisting of phenyl, naphthyl and pyridyl; pyrimidinyl unsubstituted or substituted with one or more substituents selected from the group consisting of phenyl, biphenyl, naphthyl and pyridyl; triazinyl which is unsubstituted or substituted with one or more substituents selected from the group consisting of phenyl, biphenyl, naphthyl and pyridyl; a quinazolinyl group that is unsubstituted or substituted with one or more substituents selected from the group consisting of phenyl, biphenyl, and naphthyl; a quinolyl group; a carbazolyl group; an unsubstituted or phenyl-substituted phenanthrolinyl group; unsubstituted or phenyl-substituted imidazo [1,2-a ] pyridinyl; unsubstituted or ethyl-substituted benzimidazolyl; unsubstituted or phenyl-substituted benzothiazolyl; pyrido [1,2-b ] indazolyl; an unsubstituted or phenyl-substituted oxadiazolyl group; unsubstituted or phenyl-substituted pyrazolo [1,5-c ] quinazolinyl; and 1, 5-naphthyridinyl.

In one embodiment of the present application, R1, R2, R4, R5, and R6 to R13 of chemical formula 1 may each independently be hydrogen or deuterium.

In one embodiment of the present application, R1, R2, R3, R5, and R6 to R13 of chemical formula 1 may each independently be hydrogen or deuterium.

In one embodiment of the present application, R, R' and R "of chemical formula 1 are the same or different from each other and may each independently be hydrogen; substituted or unsubstitutedC of (A)₁To C₆₀An alkyl group; or substituted or unsubstituted C₆To C₆₀And (4) an aryl group.

In another embodiment, R, R' and R "of formula 1 are the same or different from each other and can each independently be a substituted or unsubstituted C₁To C₄₀An alkyl group; or substituted or unsubstituted C₆To C₄₀And (4) an aryl group.

In another embodiment, R, R 'and R' of formula 1 are the same or different from each other and can each independently be C₆To C₄₀And (4) an aryl group.

In another embodiment, R, R' and R "of formula 1 are the same or different from each other and can each independently be a phenyl group.

In the present specification, the term "substituted or unsubstituted" means substituted by one or more substituents selected from the group consisting of: deuterium; a halo group; -CN; c₁To C₆₀An alkyl group; c₂To C₆₀An alkenyl group; c₂To C₆₀An alkynyl group; c₃To C₆₀A cycloalkyl group; c₂To C₆₀A heterocycloalkyl group; c₆To C₆₀An aryl group; c₂To C₆₀A heteroaryl group; -SiRR' R "; -P (═ O) RR'; c₁To C₂₀An alkylamino group; c₆To C₆₀An arylamine group; and C₂To C₆₀The heteroarylamino group is unsubstituted, substituted with a substituent bonding two or more of the above substituents, substituted with a substituent linking two or more substituents selected from the above substituents, or unsubstituted. For example, "a substituent linking two or more substituents" may include biphenyl. In other words, biphenyl can be an aryl group, or can be interpreted as a substituent linking two phenyl groups. The additional substituents may be further substituted. R, R 'and R' are the same or different from each other and are each independently hydrogen; deuterium; -CN; substituted or unsubstituted C₁To C₆₀An alkyl group; substituted or unsubstituted C₃To C₆₀A cycloalkyl group; substituted or unsubstituted C₆To C₆₀An aryl group; or substituted or unsubstituted C₂To C₆₀A heteroaryl group.

According to one embodiment of the present application, "substituted or unsubstituted" means via deuterium, halo, -CN, SiRR 'R ", P (═ O) RR', C₁To C₂₀Straight-chain or branched chain alkyl, C₆To C₆₀Aryl and C₂To C₆₀Substituted or unsubstituted with one or more substituents selected from the group consisting of heteroaryl, and

r, R 'and R' are the same or different from each other and are each independently hydrogen; deuterium; -CN; unsubstituted or substituted by deuterium, halo, -CN, C₁To C₂₀Alkyl radical, C₆To C₆₀Aryl and C₂To C₆₀Heteroaryl substituted C₁To C₆₀An alkyl group; unsubstituted or substituted by deuterium, halogen, -CN, C₁To C₂₀Alkyl radical, C₆To C₆₀Aryl and C₂To C₆₀Heteroaryl substituted C₃To C₆₀A cycloalkyl group; unsubstituted or substituted by deuterium, halogen, -CN, C₁To C₂₀Alkyl radical, C₆To C₆₀Aryl and C₂To C₆₀Heteroaryl substituted C₆To C₆₀An aryl group; or unsubstituted or substituted by deuterium, halogen, -CN, C₁To C₂₀Alkyl radical, C₆To C₆₀Aryl and C₂To C₆₀Heteroaryl substituted C₂To C₆₀A heteroaryl group.

The term "substituted" means that a hydrogen atom bonded to a carbon atom of a compound is changed to another substituent, and the substitution position is not limited as long as it is a position at which the hydrogen atom is substituted, that is, a position at which the substituent may be substituted, and when two or more substituents are substituted, the two or more substituents may be the same as 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 a branched chain having 1 to 60 carbon atoms, and may be further substituted with other substituents. The number of carbon atoms of the alkyl group can be 1 to 60, specifically 1 to 40, and more specifically 1 to 20. Specific examples thereof may include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, primary butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like.

In the present specification, the alkenyl group includes a straight chain or a branched chain having 2 to 60 carbon atoms, and may be further substituted with other substituents. The number of carbon atoms of the alkenyl group may be 2 to 60, specifically 2 to 40, and more specifically 2 to 20. Specific examples thereof may include, but are not limited to, vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-diphenylvinyl-1-yl, 2-phenyl-2- (naphthalen-1-yl) vinyl-1-yl, 2-bis (diphenyl-1-yl) vinyl-1-yl, stilbene, styryl, and the like.

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

In the present specification, the cycloalkyl group includes monocyclic or polycyclic rings having 3 to 60 carbon atoms, and may be further substituted with other substituents. In this context, polycyclic means a group in which the cycloalkyl group is directly connected to or fused to other cyclic groups. Herein, the other cyclic groups may be cycloalkyl groups, but may also be different types of cyclic groups, such as heterocycloalkyl, aryl, and heteroaryl. The cycloalkyl group can have a carbon number of 3 to 60, specifically 3 to 40, and more specifically 5 to 20. Specific examples thereof may include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like.

In the present specification, the heterocycloalkyl group includes O, S, Se, N or Si as a heteroatom, includes a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted with other substituents. In this context, polycyclic means a group in which the heterocycloalkyl group is directly connected to or fused to other cyclic groups. Herein, the other cyclic group may be a heterocycloalkyl group, but may also be different types of cyclic groups, such as cycloalkyl, aryl, and heteroaryl. The heterocycloalkyl group can have a number of carbon atoms of 2 to 60, specifically 2 to 40, and more specifically 3 to 20.

In the present specification, the aryl group includes monocyclic or polycyclic rings having 6 to 60 carbon atoms, and may be further substituted with other substituents. In this context, polycyclic means a group in which the aryl group is directly connected to or fused to other cyclic groups. Herein, the other cyclic groups may be aryl groups, but may also be different types of cyclic groups, such as cycloalkyl, heterocycloalkyl, and heteroaryl. Aryl includes spiro groups. The number of carbon atoms of the aryl group can be 6 to 60, specifically 6 to 40, and more specifically 6 to 25. Specific examples of the aryl group may include, but are not limited to, phenyl, biphenyl, terphenyl, naphthyl, anthryl, chrysenyl, phenanthryl, perylenyl, fluorene anthryl, terphenylene, propenylnaphthyl, pyrenyl, condensed tetraphenyl, condensed pentaphenyl, fluorene group, indenyl, acenaphthenyl, benzofluorene group, spirodiclofluorene group, 2, 3-dihydro-1H-indenyl, condensed rings thereof, and the like.

In the present specification, a spiro group is a group including a spiro structure, and may have 15 to 60 carbon atoms. For example, the spiro group may include a structure in which 2, 3-dihydro-1H-indenyl or cyclohexane is spiro-bonded to fluorene group. Specifically, the following spiro group may include any of the groups having the following structural formulae.

In the present specification, heteroaryl includes O, S, Se, N or Si as a heteroatom, includes monocyclic or polycyclic rings having 2 to 60 carbon atoms, and may be further substituted with other substituents. In this context, polycyclic means a group in which the heteroaryl is directly connected to or fused to other cyclic groups. Herein, the other cyclic groups may be heteroaryl groups, but may also be different types of cyclic groups, such as cycloalkyl, heterocycloalkyl, and aryl. The carbon number of the heteroaryl group can be 2 to 60, specifically 2 to 40 and more specifically 3 to 25. Specific examples of heteroaryl groups may include, but are not limited to, pyridyl, pyrrolyl, pyrimidinyl (pyrimidyl group), pyridazinyl (pyridazinyl group), furanyl (furanyl group), thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, furanyl, oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, diazinyl (diazinyl group), oxazinyl, thiazinyl, dioxynyl (dioxanyl), triazinyl, tetrazinyl, quinolyl, isoquinolyl, quinazolinyl, isoquinazolinyl, quinolizinyl (quinazolinolinyl), naphthyridinyl (naphthyridinyl group), acridinyl, oxazolyl, imidazopyridinyl (imidazopyridinyl), naphthyridinyl, triazainyl (triazainyl), indolyl, benzothiazolyl, isothiazolyl, triazolyl, thiadiazolyl, triazinyl, tetrazolyl, isoquinolinyl, quinazolinyl, quinoxalinyl (quinoxalinyl, indolinyl, benzothiazolyl, indolyl, benzothiazolyl, benzoxazinyl, indolyl, and benzothiazolyl, Benzofuranyl, dibenzothienyl, dibenzofuranyl, carbazolyl, benzocarbazolyl, dibenzocarbazolyl, phenazinyl, dibenzosilacyclopentadiene (dibenzosilazole group), spiro bis (dibenzosilacyclopentadiene) group, dihydrophenazinyl group, phenoxazinyl, phenanthridinyl (phenothroidinyl group), thienyl, imidazo [1,2-a ] pyridine, indolo [2,3-a ] carbazolyl, indolo [2,3-b ] carbazolyl, indolinyl, 10, 11-dihydro-dibenzo [ b, f ] azepine, 9, 10-dihydroacridinyl, phenanthreneanthrylinyl (phenothiazinyl), thiopheninyl (phenothiazinyl), phthalazinyl, naphthyridinyl (naphthyridinyl) quinolinyl, benzo [ c ] [1,2,5] thiadiazolyl ] [1,5, 10-dihydrophenazinyl ], 4] azasililinyl (5, 10-dihydrobenzol [ b, e ] [1,4] azasilinyl), pyrazolo [1,5-c ] quinazolinyl, pyrido [1,2-b ] indazolyl, pyrido [1,2-a ] imidazo [1,2-e ] indolinyl, 5,11-dihydroindeno [1,2-b ] carbazolyl (5,11-dihydroindeno [1,2-b ] carbazolyl group), and the like.

In the present specification, the amine group may be selected from the group consisting of: a monoalkylamino group; a monoarylamino group; a mono-heteroaryl amino group; -NH₂(ii) a A dialkylamino group; a diarylamino group; a diheteroarylamine group; an alkylaryl amino group; an alkylheteroarylamino group; and arylheteroarylamino groups, and although the number of carbon atoms is not particularly limited thereto, it is preferably 1 to 30. Specific examples of the amine group may include, but are not limited to, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, an anilino group, a naphthylamino group, a biphenylamino group, an anthracylamino group, a 9-methyl-anthracylamino group, a diphenylamino group, a phenylnaphthylamino group, a diphenylamino group, a phenylmethylanilino group, a triphenylamino group, a biphenylnaphthylamino group, a phenylbiphenylamino group, a biphenylfluorenylamino group, a phenyltriphenylamino group, a biphenyltriphenyltriphenylamino group, and the like.

In the present specification, arylene means an aryl group having two bonding sites, that is, a divalent group. The description provided above for aryl groups applies here in addition to each being a divalent group. Furthermore, heteroarylene means a heteroaryl group having two bonding sites, i.e., a divalent group. The description provided above for heteroaryl groups applies here in addition to each being a divalent group.

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

In addition, by introducing various substituents to the structure of chemical formula 1, a compound having unique characteristics of the introduced substituents can be synthesized. For example, by introducing a substituent (which is generally used as a hole injection layer material, a hole transport layer material, a light emitting layer material, an electron transport layer material, and a charge generation layer material for manufacturing an organic light emitting device) into the core structure, a material satisfying the conditions required for each organic material layer can be synthesized.

In addition, by introducing various substituents to the structure of chemical formula 1, the energy band gap may be finely controlled and, at the same time, the characteristics at the interface between organic materials are enhanced and the material applications may become diversified.

At the same time, the heterocyclic compounds have excellent thermal stability at higher glass transition temperatures (Tg). Such an increase in thermal stability becomes an important factor in providing driving stability to the device.

Heterocyclic compounds according to one embodiment of the present application may be prepared by a multi-step chemical reaction. Some intermediate compounds are first prepared, and the compound of chemical formula 1 may be prepared from the intermediate compounds. More specifically, the heterocyclic compound according to one embodiment of the present application may be prepared based on the preparation examples to be described below.

Another embodiment of the present application provides an organic light emitting device including a heterocyclic compound represented by chemical formula 1.

In addition to forming one or more organic material layers using the heterocyclic compound described above, an organic light-emitting device according to one embodiment of the present application may be manufactured using a general organic light-emitting device manufacturing method and materials.

In manufacturing an organic light-emitting device, the heterocyclic compound may be formed into an organic material layer by a solution coating method as well as a vacuum deposition method. Herein, the solution coating method means, but is not limited to, spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, and the like.

Specifically, an organic light emitting device according to one embodiment of the present application includes an anode, a cathode, and one or more organic material layers disposed between the anode and the cathode, wherein one or more layers of the organic material layers include a heterocyclic compound represented by chemical formula 1.

Fig. 1 to 3 illustrate a lamination order of an electrode and an organic material layer of an organic light emitting device according to one embodiment of the present application. However, the scope of the present application is not limited to these drawings, and the structure of an organic light emitting device known in the art may also be used in the present application.

Fig. 1 illustrates an organic light emitting device in which an anode 200, an organic material layer 300, and a cathode 400 are sequentially laminated on a substrate 100. However, the structure is not limited to such a structure, and as illustrated in fig. 2, an organic light emitting device in which a cathode, an organic material layer, and an anode are successively laminated on a substrate can also be obtained.

Fig. 3 illustrates a case where the organic material layer is a multilayer. 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 to such a stacked structure, and if necessary, other layers than the light emitting layer may not be included, and other necessary functional layers may be further included.

Further, an organic light emitting device according to one embodiment of the present application includes an anode, a cathode, and two or more stacked layers disposed between the anode and the cathode, wherein the two or more stacked layers each independently include a light emitting layer, and a charge generation layer is included between the two or more stacked layers, and the charge generation layer includes a heterocyclic compound represented by chemical formula 1.

In addition, an organic light emitting device according to an embodiment of the present application includes an anode, a first stack layer disposed on the anode, and includes a first light emitting layer, a charge generation layer disposed on the first stack layer, a second stack layer disposed on the charge generation layer, and includes a second light emitting layer and a cathode disposed on the second stack layer. Herein, the charge generation layer may include a heterocyclic compound represented by chemical formula 1. Furthermore, the first and second stacks may each independently further comprise one or more types of hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, and the like, as described above.

The charge generation layer may be an N-type charge generation layer, and the charge generation layer may further include a dopant known in the art in addition to the heterocyclic compound represented by chemical formula 1.

An organic light emitting device having a 2-stack tandem type structure as an organic light emitting device according to one embodiment of the present application is schematically illustrated in fig. 4.

Herein, the first electron blocking layer, the first hole blocking layer, the second hole blocking layer, and the like described in fig. 4 may not be included in some cases.

The organic light emitting device according to the present specification may be manufactured using methods and materials known in the art, except that one or more of the organic material layers include the heterocyclic compound represented by chemical formula 1.

The heterocyclic compound represented by chemical formula 1 may form one or more layers of the organic material layer of the organic light emitting device alone. However, if necessary, the heterocyclic compound represented by chemical formula 1 may be mixed with other materials to form an organic material layer.

The heterocyclic compound represented by chemical formula 1 may be used as a material of a charge generation layer in an organic light emitting device.

The heterocyclic compound represented by chemical formula 1 may be used as a material for an electron transfer layer, a hole blocking layer, a light emitting layer, or the like in an organic light emitting device. As one example, the heterocyclic compound represented by chemical formula 1 may be used as a material of an electron transfer layer, a hole transfer layer, or a light emitting layer in an organic light emitting device.

In addition, the heterocyclic compound represented by chemical formula 1 may be used as a material of a light emitting layer in an organic light emitting device. As one example, the heterocyclic compound represented by chemical formula 1 may be used as a phosphorescent host material of an emission layer in an organic light emitting device.

In the organic light emitting device according to one embodiment of the present application, materials other than the heterocyclic compound of chemical formula 1 are described below, however, these materials are only for the purpose of illustration and are not intended to limit the scope of the present application, and may be substituted with materials known in the art.

A material having a relatively large work function may be used as the anode material, and a transparent conductive oxide, a metal, a conductive polymer, or the like may be used. The anode material hasSpecific examples include (but are not limited to): metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals with oxides, e.g. ZnO Al or SnO₂Sb; conducting polymers, such as poly (3-methyl compounds), poly [3,4- (ethylene-1, 2-dioxy) thiophenes](PEDOT), polypyrrole, and polyaniline.

A material having a relatively small work function may be used as the cathode material, and a metal, a metal oxide, a conductive polymer, or the like may be used. Specific examples of cathode materials include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; materials of multilayer structure, e.g. LiF/Al or LiO₂Al and the like, but not limited thereto.

Known hole injection materials can be used as the hole injection material, and for example, phthalocyanine compounds such as copper phthalocyanine disclosed in U.S. Pat. No. 4,356,429; or starburst amine derivatives such as tris (4-hydrazinoformyl-9-ylphenyl) amine (TCTA), 4',4 ″ -tris [ phenyl (m-tolyl) amino ] triphenylamine (m-MTDATA) or 1,3, 5-tris [4- (3-methylphenylphenylamino) phenyl ] benzene (m-MTDAPB) described in the literature [ Advanced materials, 6, page 677 (p.677) (1994) ]; a conductive polymer having solubility, polyaniline/dodecylbenzenesulfonic acid (polyaniline/dodecenylbenzensulfonic acid), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (poly (3, 4-ethylenedioxythiophene)/poly (4-phenylenesulfonate)), polyaniline/camphorsulfonic acid (polyaniline/camphorsulfonic acid) or polyaniline/poly (4-styrene-sulfonate)); and the like.

Pyrazoline derivatives, aromatic amine derivatives, stilbene derivatives, triphenyldiamine derivatives, and the like may be used as the hole transporting material, and low-molecular or high-molecular materials may also be used.

Metal complexes of oxadiazole derivatives, anthraquinone dimethane (anthraquinone) and its derivatives, benzoquinone and its derivatives, naphthoquinone (naphthoquinone) and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinone dimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, 8-hydroxyquinoline and its derivatives, and the like can be used, and high molecular materials and low molecular materials can also be used as electron transfer materials.

As an example of the electron injecting material, LiF is generally used in the art, however, the present application is not limited thereto.

A material emitting red, green, or blue light may be used, and two or more light emitting materials may be mixed and used as a light emitting material as necessary. In addition, a fluorescent material may also be used as the light-emitting material, however, a phosphorescent material may also be used. A material that emits light by bonding electrons and holes injected from the anode and the cathode, respectively, may be used alone as the light emitting material, however, a material having a host material and a dopant material (participating in light emission at the same time) may also be used.

An organic light emitting device according to one embodiment of the present application may be a top emission type, a bottom emission type, or a double-sided emission type, depending on the material used.

The heterocyclic compound according to one embodiment of the present application may also be used in organic electronic devices including organic solar cells, organic photoconductors, organic transistors, and the like, which are used in organic light-emitting devices on a similar principle.

Modes for the invention

Hereinafter, the present specification will be described in more detail with reference to examples, however, these are for illustrative purposes only, and the scope of the present application is not limited thereto.

< example >

< preparation example 1> preparation of Compound 2

1) Preparation of Compound 2-1

After aniline (aniline) (19.8ml, 213mmol) and sodium acetate trihydrate (26.4g, 318mol) were added to the compound 1,4-dibromo-2-nitrobenzene (1,4-dibromo-2-nitrobenzene) (30g, 106mmol), the resulting material was stirred at 80 ℃ for 30 minutes and then refluxed at 160 ℃ for 72 hours. After completion of the reaction, the resultant was cooled to room temperature and extracted with distilled water and EA. With anhydrous MgSO₄After drying the organic layer, the solvent was removed using a rotary evaporator, and the resulting material was purified using column chromatography using dichloromethane and hexane as developing agents to obtain the target compound 2-1(31g, 99%).

2) Preparation of Compound 2-2

After compound 2-1(31g, 105mmol) was dissolved in THF (210ml), sodium dithionite (93g, 525mmol) dissolved in 370ml of distilled water was added thereto, and the resultant was stirred at room temperature for 12 hours. After completion of the reaction, the resultant was extracted with distilled water and EA. With anhydrous MgSO₄After drying the organic layer, the solvent was removed using a rotary evaporator, and the target compound 2-2(28g, 100%) was obtained without further purification.

3) Preparation of Compounds 2-3

After dissolving compound 2-2(28g, 106mmol) in nitrobenzene (nitrobenzene), the resulting material was refluxed at 180 ℃ for 6 hours. After completion of the reaction, the resultant was vacuum distilled to remove nitrobenzene (nitrobenzene), and then extracted with distilled water and EA. With anhydrous MgSO₄After drying the organic layer, the solvent was removed using a rotary evaporator, and the resulting material was purified using column chromatography with dichloromethane and hexane as developing agents to obtain the target compound 2-3(15g, 40%).

4) Preparation of Compounds 2-4

After dissolving the compound 2-3(15g, 43.0mmol) in 1,4-dioxane (1,4-dioxane), bis (pinacolato) diboron (21g, 86.0mmol), Pd (dppf) Cl was added thereto₂(1.6g, 2.15mmol) and potassium acetate (12.7g, 129mmol) and the resulting material was taken at 110 deg.CStirred for 2 hours. After completion of the reaction, the resultant was extracted with distilled water and EA. With anhydrous MgSO₄After drying the organic layer, the solvent was removed using a rotary evaporator and the target compound 2-4(9.5g, 56%) was obtained without further purification.

5) Preparation of Compounds 2-5

After dissolving compound 2-4(9.5g, 23.0mmol) in toluene (tolumen), EtOH and H₂After O, 2-bromoaniline (2-bromoaniline) (4.9g, 28.8mmol), Pd (PPh) were added thereto₃)₄(1.4g, 1.2mmol) and K₂CO₃(10.0g, 72.0mmol), and the resulting material was stirred at 110 ℃ for 6 hours. After completion of the reaction, the resultant was cooled to room temperature and extracted with distilled water and EA. With anhydrous MgSO₄After drying the organic layer, the solvent was removed using a rotary evaporator, and the resulting material was purified using column chromatography with dichloromethane and hexane as developing agents to obtain the target compound 2-5(7.1g, 82%).

6) Preparation of Compounds 2-6

After dissolving the compound 2-5(7.1g, 19.6mmol) in THF, 4-bromobenzoyl chloride (4-bromobenzoyl chloride) (3.8ml, 29.4mmol) and TEA (8.1ml, 58.8mmol) were added thereto at 0 deg.C, and the resulting material was stirred at room temperature for 2 hours. After completion of the reaction, EA and distilled water were added to the reactor for solidification, and the resulting solid was collected to obtain the target compound 2-6(11g, 100%).

7) Preparation of Compounds 2 to 7

After dissolving Compound 2-6(11g, 20.2mmol) in nitrobenzene (nitrobenzene), POCl was added thereto₃(1.9ml, 20.2mmol) and the resulting material was stirred at 150 ℃ for 18 h. After completion of the reaction, the resultant was vacuum distilled to remove nitrobenzene (nitrobenzene), followed by cooling to room temperature and extraction with distilled water and EA. With anhydrous MgSO₄After drying the organic layer, the solvent was removed using a rotary evaporator, and the resulting material was purified using column chromatography with dichloromethane and hexane as developing agents to obtain the target compound 2-7(7.4g, 69%).

8) Preparation of Compounds 2 to 8

After compounds 2-7(7.4g, 14.1mmol) were dissolved in 1,4-dioxane (1,4-dioxane), bis (pinacolato) diboron, Pd (dppf) Cl and₂and potassium acetate (potassium acetate), and the resultant was stirred at 110 ℃ for 2 hours. After completion of the reaction, the resultant was extracted with distilled water and EA. With anhydrous MgSO₄After drying the organic layer, the solvent was removed using a rotary evaporator, and the target compound 2-8(8.0g, 100%) was obtained without further purification.

9) Preparation of Compound 2

To compounds 2 to 8(8.0g, 14.1mmol) were added 9-bromo-10-phenylanthracene (9-bromoo-10-phenylanthracene) (5.6g, 16.9mmol), Pd (PPh)₃)₄(0.8g，0.71mmol)、K₂CO₃(5.8g, 42.3mmol) and toluene (tolumen)/EtOH/H₂After O, the resulting material was stirred at 110 ℃ for 2 hours. After completion of the reaction, the resultant was cooled to room temperature and extracted with distilled water and EA. With anhydrous MgSO₄After drying the organic layer, the solvent was removed using a rotary evaporator, and the resulting material was purified using column chromatography using dichloromethane and hexane as developing agents to obtain the target compound 2(8.4g, 86%).

< preparation example 2> preparation of Compound 5

After dissolving the compound 2-7(7.1g, 13.5mmol) in THF, 2.5M n-BuLi (7.0ml, 17.6mmol) was slowly added dropwise thereto at-78 deg.C, and the resultant was stirred for 30 minutes. Chlorobiphenyltrimetaphosphate (3.3ml, 17.6mmol) was added thereto, and the resultant was stirred for 1 hour. After the reaction was completed, methanol was added thereto, and the resultant was stirred for 1 hour, and then extracted with distilled water and EA. With anhydrous MgSO₄The organic layer was dried and then the solvent was removed using a rotary evaporator. The concentrated liquid was dissolved by adding dichloromethane (150ml)And hydrogen peroxide (7.0ml) was added thereto, and the resultant was stirred at room temperature for 3 hours. After completion of the reaction, the resultant was extracted with distilled water and EA. With anhydrous MgSO₄The organic layer was dried and then the solvent was removed using a rotary evaporator. The resulting material was dissolved by addition of toluene and heating, and then recrystallized to obtain the objective compound 5(7.1g, 81%).

< preparation example 3> preparation of Compound 10

To compounds 2 to 8(8.0g, 14.1mmol) were added 9-bromo-10-phenylanthracene (9-bromoo-10-phenylanthracene) (5.6g, 16.9mmol), Pd (PPh)₃)₄(0.8g，0.71mmol)、K₂CO₃(5.8g, 42.3mmol) and toluene (tolumen)/EtOH/H₂After O, the resulting material was stirred at 110 ℃ for 2 hours. After completion of the reaction, the resultant was cooled to room temperature and extracted with distilled water and EA. With anhydrous MgSO₄After drying the organic layer, the solvent was removed using a rotary evaporator, and the resulting material was purified using column chromatography using dichloromethane and hexane as developing agents to obtain the target compound 10(8.4g, 86%).

< preparation example 4> preparation of Compound 11

Target compound 11 was obtained in the same manner as in preparation example 1 except that 2-bromo-4,6-diphenyl-1,3,5-triazine (2-bromo-4,6-diphenyl-1,3, 5-triazene) was used instead of 9-bromo-10-phenylanthracene (9-bromo-10-phenylanthracene).

< preparation example 5> preparation of Compound 15

The objective compound 15 was obtained in the same manner as in the preparation of compound 2 in example 1, except that 2-bromo-4,6-di (naphthalen-2-yl) -1,3,5-triazine (2-bromo-4,6-di (naphthalen-2-yl) -1,3,5-triazine) was used instead of 9-bromo-10-phenylanthracene (9-bromo-10-phenylanthracene).

< preparation example 6> preparation of Compound 25

The objective compound 25 was obtained in the same manner as in the preparation of compound 2 in example 1, except that 4- ([1,1'-biphenyl ] -4-yl) -2-bromo-6-phenylpyrimidine (4- ([1,1' -biphenyl ] -4-yl) -2-bromo-6-phenylpyrimidine) was used instead of 9-bromo-10-phenylanthracene (9-bromo-10-phenylanthracene).

< preparation example 7> preparation of Compound 55

Target compound 55 was obtained in the same manner as in preparation example 1 except that 4- ([1,1'-biphenyl ] -4-yl) -2-bromoquinazoline (4- ([1,1' -biphenyl ] -4-yl) -2-bromoquinazoline) was used instead of 9-bromo-10-phenylanthracene (9-bromoo-10-phenylanthracene).

< preparation example 8> preparation of Compound 70

The objective compound 70 was obtained in the same manner as in preparation example 1 except that 5-bromo-2,4,6-triphenylpyrimidine (5-bromo-2,4,6-triphenylpyrimidine) was used instead of 9-bromo-10-phenylanthracene (9-bromo-10-phenylanthracene).

< preparation example 9> preparation of Compound 89

The target compound 89 was obtained in the same manner as in the preparation of compound 2 in example 1, except that 2-bromo-1,10-phenanthroline (2-bromo-1,10-phenanthroline) was used instead of 9-bromo-10-phenylanthracene (9-bromo-10-phenylanthracene).

< preparation example 10> preparation of Compound 94

Target compound 94 was obtained in the same manner as in preparation example 1 except that 6-bromo-2-phenylimidazo [1,2-a ] pyridine was used in place of 9-bromo-10-phenylanthracene (9-bromo-10-phenylanthracene).

< preparation example 11> preparation of Compound 101

The objective compound 101 was obtained in the same manner as in the preparation of compound 2 in example 1, except that 1- (4-bromophenyl) -2-ethyl-1H-benzo [ d ] imidazole (1- (4-bromophenyl) -2-ethyl-1H-benzol [ d ] imidazole) was used instead of 9-bromo-10-phenylanthracene (9-bromoo-10-phenylanthracene).

< preparative example 12> preparation of Compound 104

The objective compound 104 was obtained in the same manner as in preparation example 1 except that 2- (4-bromophenyl) benzo [ d ] thiazole (2- (4-bromophenyl) benzo [ d ] thiazole) was used instead of 9-bromo-10-phenylanthracene (9-bromoo-10-phenylanthracene).

< preparation example 13> preparation of Compound 126

The objective compound 126 was obtained in the same manner as in preparation example 1 except that 3-bromoquinoline (3-bromoquinoline) was used instead of 9-bromo-10-phenylanthracene (9-bromoo-10-phenylanthracene).

< preparative example 14> preparation of Compound 131

The objective compound 131 was obtained in the same manner as in the preparation of compound 2 in example 1, except that 6-bromo-2,2 '-binaphtylene (6-bromo-2,2' -binaphtylene) was used instead of 9-bromo-10-phenylanthracene (9-bromo-10-phenylanthracene).

< preparation example 15> preparation of Compound 133

The objective compound 133 was obtained in the same manner as in the preparation of compound 2 in example 1, except that 4-bromobenzonitrile (4-bromobenzonitrile) was used instead of 9-bromo-10-phenylanthracene (9-bromo-10-phenylanthracene).

< preparation example 16> preparation of Compound 136

Target compound 136 was obtained in the same manner as in preparation example 1 except that 2-bromopyridine (2-bromopyridinium) was used instead of 9-bromo-10-phenylanthracene (9-bromo-10-phenylanthracene).

< preparation example 17> preparation of Compound 152

The objective compound 152 was obtained in the same manner as in the preparation of compound 2 in example 1, except that 3- (4-bromophenyl) -2-phenylimidazo [1,2-a ] pyridine (3- (4-bromophenyl) -2-phenylimididazo [1,2-a ] pyridine) was used instead of 9-bromo-10-phenylanthracene (9-bromoo-10-phenylanthracene).

< preparation example 18> preparation of Compound 153

The target compound 153 was obtained in the same manner as in preparation example 1 except that 8-bromoquinoline (8-bromoquinoline) was used instead of 9-bromo-10-phenylanthracene (9-bromoo-10-phenylanthracene).

< preparation example 19> preparation of Compound 154

1) Preparation of Compound 154-1

After dissolving the compound 2-5(30g, 83.0mmol) in THF, 3-bromobenzoyl chloride (3-bromobenzoyl chloride) (16.5ml, 1.5eq) and TEA (34.5ml, 3.0eq.) were added thereto at 0 ℃, and the resulting material was stirred at room temperature for 2 hours. After completion of the reaction, EA and distilled water were added to the reactor for solidification, and the resulting solid was collected to obtain the target compound 154-1(44g, 97%).

2) Preparation of Compound 154-2

After dissolving the compounds 2-6(44g, 80.8mmol) in nitrobenzene (nitrobenzene), POCl was added thereto₃(7.5ml, 1.0eq.) and the resulting material was stirred at 150 ℃ for 18 hours. After completion of the reaction, the resultant was vacuum distilled to remove nitrobenzene (nitrobenzene), followed by cooling to room temperature and extraction with distilled water and EA. With anhydrous MgSO₄After drying the organic layer, the solvent was removed using a rotary evaporator,and the resulting substance was purified using column chromatography using dichloromethane and hexane as developing agents to obtain the objective compound 154-2(30g, 71%).

3) Preparation of Compound 154-3

After dissolving the compounds 2-7(30g, 57.0mmol) in 1,4-dioxane, bis (pinacolato) diboron, Pd (dppf) Cl and the like were added thereto₂And potassium acetate (potassium acetate), and the resultant was stirred at 110 ℃ for 2 hours. After completion of the reaction, the resultant was extracted with distilled water and EA. With anhydrous MgSO₄After drying the organic layer, the solvent was removed using a rotary evaporator, and the target compound 154-3(29 g, 89%) was obtained without further purification.

4) Preparation of Compound 154

After reaction of (4-bromophenyl) diphenylphosphine oxide ((4-bromophenyl) diphenylphosphine oxide) (5.5g, 15.3mmol), Pd (PPh)₃)₄(0.8g，0.71mmol)、K₂CO₃(5.8g, 42.3mmol) and toluene (tolumen)/EtOH/H₂After O was added to compound 154-1(8.0g, 14.1mmol), the resulting material was stirred at 110 ℃ for 2 hours. After completion of the reaction, the resultant was cooled to room temperature and extracted with distilled water and EA. With anhydrous MgSO₄After drying the organic layer, the solvent was removed using a rotary evaporator, and the resulting product was purified using column chromatography with dichloromethane and hexane as developing agents to obtain the target compound 154(8.5g, 83%).

< preparation example 20> preparation of Compound 155

The objective compound 155 was obtained in the same manner as in the preparation of the compound 154 in example 19, except that 2-bromo-4,6-diphenyl-1,3,5-triazine (2-bromo-4,6-diphenyl-1,3,5-triazine) was used instead of (4-bromophenyl) diphenylphosphine oxide ((4-bromo-diphenyl) diphenylphosphine oxide).

< preparation example 21> preparation of Compound 156

Target compound 156 was obtained in the same manner as in the preparation of the compound 154 in example 19, except that 9,9'- (5-bromo-1,3-phenylene) bis (9H-carbazole) (9,9' - (5-bromo-1,3-phenylene) bis (9H-carbazole)) was used instead of (4-bromophenyl) diphenylphosphine oxide ((4-bromophenyl) diphenylphosphine oxide).

< preparation example 22> preparation of Compound 158

Target compound 158 was obtained in the same manner as in preparation example 19 except that 4-chloro-2,6-diphenylpyrimidine (4-chloro-2, 6-diphenylpyrinidine) was used instead of (4-bromophenyl) diphenylphosphine oxide ((4-bromophenyl) diphenylphosphine oxide).

< preparation example 23> preparation of Compound 161

The objective compound 161 was obtained in the same manner as in the preparation of compound 154 in example 19, except that 4- ([1,1'-biphenyl ] -4-yl) -6- (4-chlorophenyl) -2-phenylpyrimidine (4- ([1,1' -biphenyl ] -4-yl) -6- (4-chlorophenylyl) -2-phenylpyrimidine) was used in place of (4-bromophenyl) diphenylphosphine oxide ((4-bromophenyl) diphenylphosphinoxide).

< preparation example 24> preparation of Compound 164

The target compound 164 was obtained in the same manner as in the preparation of the compound 154 in example 19, except that 2- (4-bromophenyl) -9-phenyl-1,10-phenanthroline (2- (4-bromophenyl) -9-phenyl-1,10-phenanthroline) was used instead of (4-bromophenyl) diphenylphosphine oxide ((4-bromophenyl) diphenylphosphine oxide).

< preparation example 25> preparation of Compound 165

Target compound 165 was obtained in the same manner as in preparation example 19 except that 1- (4-bromophenyl) -2-ethyl-1H-benzo [ d ] imidazole (1- (4-bromophenyl) -2-ethyl-1H-benzo [ d ] imidazole) was used instead of (4-bromophenyl) diphenylphosphine oxide ((4-bromophenyl) diphenylphosphine oxide).

The compounds were prepared in the same manner as in the preparation examples, and the synthetic identification results are shown in table 1 and table 2.

[ Table 1]

[ Table 2]

< Experimental examples >

< Experimental example 1>

1) Fabrication of organic light emitting devices

Ultrasonically cleaning a glass substrate with distilled water, ITO as a thin film

(angstrom) is coated onto the glass substrate. After the cleaning with distilled water was completed, the substrate was ultrasonically cleaned with a solvent (such as acetone, methanol, and isopropyl alcohol), followed by drying, and subjected to UVO treatment in a UV cleaner using UV for 5 minutes. Thereafter, the substrate is transferred to a plasma cleaner (PT) and plasma treated under vacuum in order to remove the ITO work function and the remaining thin film, and the substrate is transferred to a thermal deposition apparatus for organic deposition.

On the ITO transparent electrode (anode), an organic material is formed in a two-layer WOLED (white organic light emitting device) structure. For the first stack, TAPC was deposited by thermal vacuum to

First, a hole transport layer is formed. After the hole transport layer is formed, a light emitting layer is thermally vacuum deposited thereon as follows. Deposition by doping FIrpic as blue phosphorescent dopant 8% to TCz1 (host)

The light emitting layer of (1). The electron transfer layer is formed using TmPyPB

And then by mixing Cs₂CO₃Doping 20% to the compound described in Table 3 below, the charge generation layer was shaped

For the second stack, by thermal vacuum deposition

Thickness MoO₃And the hole injection layer is formed first. By mixing MoO₃Doped 20% to TAPC and shaped to

To form a hole transport layer (universal layer), and then depositing TAPC to

By mixing Ir (ppy)₃(Green phosphorescent dopant) doping 8% to TCz1 (host), deposition

Is formed using TmPyPB

The electron transport layer of (1). Finally, by deposition

Lithium fluoride (LiF) in a thickness such that an electron injection layer is formed on the electron transfer layer, and then by deposition

The aluminum (Al) cathode was formed to a thickness such that the cathode was formed on the electron injection layer, thereby fabricating an organic light emitting device.

At the same time, at 10^-6torr to 10^-8All organic compounds required for the fabrication of OLED devices were purified by vacuum sublimation of each material used for OLED fabrication under torr.

2) Driving voltage and light emitting efficiency of organic light emitting device

For the organic light emitting device manufactured as above, the electroluminescence light Emission (EL) characteristics were measured using M7000 manufactured by mccience corporation, and from the measurement results, when the standard luminosity was 3500cd/M²(candela/M), T was measured using a life test system (M6000) manufactured by McScience₉₅. Measuring the driving voltage, luminous efficiency, external quantum efficiency of the white organic light emitting device manufactured according to the present inventionThe results for the ratios and color Coordinates (CIE) are shown in table 3.

[ Table 3]

As shown in the results of table 3, the organic light emitting device using the charge generation layer material of the 2-stacked white organic light emitting device of the present invention has a lower driving voltage and improved light emitting efficiency than comparative example 1. Specifically, compound 5, compound 10, compound 11, compound 17, compound 25, compound 26, compound 43, compound 52, compound 124, and compound 147 were identified as being significantly superior in terms of drive, efficiency, and lifetime.

The reason for such results is presumably that the compound of the present invention used as the N-type charge generation layer (formed of the framework of the present invention having appropriate length, strength and planar characteristics and an appropriate hybrid compound capable of binding to a metal) is doped with an alkali metal or an alkaline earth metal to form a spaced state within the N-type charge generation layer, and electrons generated from the P-type charge generation layer are easily injected into the electron transfer layer by the spaced state generated within the N-type charge generation layer. Accordingly, the P-type charge generation layer smoothly performs electron injection and electron transfer to the N-type charge generation layer, and thus, it is considered that the driving voltage of the organic light emitting device is reduced and the efficiency and the lifetime are improved.

< Experimental example 2>

1) Fabrication of organic light emitting devices

A transparent electrode ITO film obtained from Glass for OLED (manufactured by Samsung-Corning Advanced Glass) was continuously ultrasonically cleaned for 5 minutes each using trichloroethylene, acetone, ethanol, and distilled water, placed in isopropyl alcohol and stored, and then used.

Then, the ITO substrate was set in a substrate holder of a vacuum deposition apparatus, and subsequently 4,4',4 ″ -tris (N, N- (2-naphthyl) -anilino) triphenylamine (4,4',4 ″ -tris (N, N- (2-naphthyl) -phenylaminoo) triphenylamine: 2-TNATA) was introduced into a vacuum chamber in the vacuum deposition apparatus.

Subsequently, the chamber is evacuated until the vacuum level inside the chamber reaches 10^-6torr (torr), and then applying a current to the vacuum chamber to vaporize the 2-TNATA to deposit a film having

And a hole injection layer with a thickness is arranged on the ITO substrate.

The following N, N '-bis (. alpha. -naphthyl) -N, N' -diphenyl-4,4'-diamine (N, N' -bis (. alpha. -naphthyl) -N, N '-diphenyl-4,4' -diamine: NPB) was introduced into different chambers in the vacuum deposition apparatus, and a current was applied to the chamber for evaporation to deposit a film having a hole injection layer on the hole injection layer

A hole transport layer of thickness.

After the hole injection layer and the hole transfer layer are formed as described above, a blue light emitting material having the following structure is deposited thereon as a light emitting layer. In particular, vacuum deposition in one vacuum chamber of a vacuum deposition apparatus

H1 (blue light emitting host material) in thickness, and 5% D1 (blue light emitting dopant material) relative to the host material was vacuum deposited thereon.

Subsequently, depositing

The compound of the following structural formula E1 as an electron transfer layer in thickness.

Deposition of

A thickness of lithium fluoride (LiF) as an electron injection layer, and formed

Al cathode of thickness, thereby fabricating an OLED device.

An OLED device was manufactured in the same manner as in experimental example 2, except that the compound of table 4 below was used instead of compound E1 as an electron transfer layer.

For the organic light emitting device manufactured as above, the electroluminescence light Emission (EL) characteristics were measured using M7000 manufactured by McScience, Inc., and from the measurement results, when the standard luminosity was 700cd/M²In time, T was measured using a life test system (M6000) manufactured by McScience corporation₉₅. The results of measuring the driving voltage, the light emitting efficiency, the external quantum efficiency, and the color Coordinate (CIE) of the white organic light emitting device manufactured according to the present invention are shown in table 4.

[ Table 4]

As shown in the results of table 4, the organic light emitting device using the electron transport layer material of the blue organic light emitting device of the present invention has a lower driving voltage and significantly improved light emitting efficiency and lifetime compared to comparative example 3. Specifically, compound 5, compound 10, compound 11, compound 17, compound 25, compound 26, compound 43, compound 52, compound 124, and compound 147 were identified as being significantly superior in terms of drive, efficiency, and lifetime.

The reason for such results is presumably that, when the compound of the present invention having appropriate length, strength and planar characteristics is used as an electron transfer layer, a compound in an excited state is generated by receiving electrons under specific conditions, and in particular, when the excited state is formed in a hetero skeleton site of the compound, excitation energy is transferred to a stable state before the excited hetero skeleton site undergoes various reactions, and a relatively stable compound is capable of efficiently transferring electrons without decomposing or destroying the compound. For reference, it is believed that those compounds having a stable state when excited are aryl or acene-based compounds or polycyclic hetero compounds. Therefore, it is considered that the compound of the present invention enhances electron transfer characteristics or improves stability so as to be excellent in driving, efficiency and lifetime.

Claims

1. A heterocyclic compound represented by the following chemical formula 1:

[ chemical formula 1]

Wherein, in chemical formula 1,

r3 or R4 in R1 to R5 is represented by- (L1) p- (Z1) q, and the rest are hydrogen;

l1 is a direct bond; a phenylene group; a biphenylene group; an anthracenylene group; a naphthylene group; a divalent imidazo [1,2-a ] pyridinyl group; a divalent pyridyl group; a divalent pyrimidinyl group; a divalent triazine group; a divalent quinazolinyl group; or a divalent benzimidazolyl group;

z1 is selected from the group consisting of: phenyl unsubstituted or substituted by one or more substituents selected from the group consisting of P (═ O) RR', phenyl and carbazolyl; naphthyl unsubstituted or substituted with P (═ O) RR'; anthracenyl unsubstituted or substituted by one or more substituents selected from the group consisting of P (═ O) RR' and naphthyl; a biphenyl group; triphenylene biylidene; phenanthryl; an ethyl group; p (═ O) RR'; -CN; pyridyl unsubstituted or substituted with one or more substituents selected from the group consisting of phenyl, naphthyl and pyridyl; pyrimidinyl unsubstituted or substituted with one or more substituents selected from the group consisting of phenyl, biphenyl, naphthyl and pyridyl; triazinyl which is unsubstituted or substituted with one or more substituents selected from the group consisting of phenyl, biphenyl, naphthyl and pyridyl; a quinazolinyl group that is unsubstituted or substituted with one or more substituents selected from the group consisting of phenyl, biphenyl, and naphthyl; a quinolyl group; a carbazolyl group; an unsubstituted or phenyl-substituted phenanthrolinyl group; unsubstituted or phenyl-substituted imidazo [1,2-a ] pyridinyl; unsubstituted or ethyl-substituted benzimidazolyl; unsubstituted or phenyl-substituted benzothiazolyl; pyrido [1,2-b ] indazolyl; an unsubstituted or phenyl-substituted oxadiazolyl group; unsubstituted or phenyl-substituted pyrazolo [1,5-c ] quinazolinyl; and 1, 5-naphthyridinyl;

p is an integer of 0 to 2;

q is an integer of 1 to 4;

r6 to R13 are the same or different from each other and are each independently selected from the group consisting of: hydrogen; and deuterium;

m and n are each independently an integer of 0 to 5; and

r and R' are phenyl.

2. The heterocyclic compound according to claim 1, wherein R3 in R1 to R5 of chemical formula 1 is represented by- (L1) p- (Z1) q, and the remainder are hydrogen, and

l1, Z1, p and q have the same definitions as in claim 1.

3. The heterocyclic compound according to claim 1, wherein R4 in R1 to R5 of chemical formula 1 is represented by- (L1) p- (Z1) q, and the remainder are hydrogen, and

l1, Z1, p and q have the same definitions as in claim 1.

4. The heterocyclic compound according to claim 1, wherein chemical formula 1 is represented by any one of the following compounds:

5. an organic light emitting device comprising:

an anode;

a cathode; and

one or more layers of organic material disposed between the anode and the cathode,

wherein one or more of the layers of organic material comprise the heterocyclic compound of any one of claims 1 to 4.

6. The organic light-emitting device according to claim 5, wherein the organic material layer comprises a light-emitting layer, and the light-emitting layer comprises the heterocyclic compound.

7. The organic light-emitting device according to claim 5, wherein the organic material layer comprises a charge generation layer, and the charge generation layer comprises the heterocyclic compound.

8. The organic light emitting device of claim 5, comprising:

the anode;

a first stack layer disposed on the anode and including a first light emitting layer;

a charge generation layer disposed on the first stack;

a second stack layer disposed on the charge generation layer and including a second light emitting layer; and

the cathode is arranged on the second lamination layer.