TWI856950B - Heterocyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

The present specification relates to a heterocyclic compound represented by chemical formula 1, and an organic light emitting device comprising the same.

[Chemical Formula 1]

In Chemical Formula 1, the definition of each substituents is the same as in detail description.

Description

Heterocyclic compounds and organic light-emitting devices containing the same

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

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

An organic light-emitting device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to an 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. A single layer or multiple layers of organic thin films can be formed as needed.

If necessary, the material of the organic thin film may have a light-emitting function. For example, a compound that can form a light-emitting layer itself can be used alone as a material for the organic thin film, or a compound that can play the role of a host or dopant of a host-dopant-based light-emitting layer can be used as a material for the organic thin film. In addition, compounds that can play the role of hole injection, hole transfer, electron blocking, hole blocking, electron transfer, electron injection and the like can also be used as materials for the organic thin film.

The development of organic thin film materials continues to require the improvement of the performance, life or efficiency of organic light-emitting devices.

[Existing technical documents]

[Patent Documents]

U.S. Patent No. 4,356,429

The present invention relates to providing novel heterocyclic compounds and organic light-emitting devices comprising the same.

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

In Formula 1, R2 to R5 are the same as or different from each other and are independently selected from the group consisting of hydrogen, deuterium, halogen, -CN, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -S iRR'R", -P(=O)RR' and an amine group, the amine group is unsubstituted or substituted by: a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group; or two or more adjacent groups are bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring, Ra is hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, Ar ₁ is represented by -(L1)p-(Z1)q, Ar ₂ is represented by -(L2)r-(Z2)s, L1 and L2 are the same or different and are each independently a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, Z1 and Z2 are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, halogen, -CN, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl group, -SiRR'R", -P(=O)RR' and an amine group, wherein the amine group is unsubstituted or substituted with a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, R, R' and R" are the same as or different from each other and are each independently hydrogen, deuterium, -CN, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, p and r are integers from 1 to 4, q and s are integers from 1 to 3, and n is an integer from 0 to 4.

Another embodiment of the present application provides an organic light-emitting device, the organic light-emitting device comprising: a first electrode; a second electrode disposed opposite to the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein one or more layers of the organic material layer include a heterocyclic compound according to one embodiment of the present invention.

The compounds described in this specification can be used as organic material layer materials of organic light-emitting devices. The compounds can function as hole injection materials, hole transfer materials, light-emitting materials, electron transfer materials, electron injection materials, and the like in organic light-emitting devices. Specifically, the compounds can be used as electron transfer layer materials, hole blocking layer materials, or charge generation layer materials of organic light-emitting devices.

Specifically, when the compound represented by Chemical Formula 1 is used in an organic material layer, the driving voltage is reduced and the light efficiency is enhanced in the device, and the device life characteristics can be enhanced by the thermal stability of the compound.

100: Substrate

200: Yang pole

300: Organic material layer

301: Hole injection layer

302: Hole transfer layer

303: Luminous layer

304: Hole blocking layer

305:Electron transfer layer

306: Electron injection layer

400: cathode

Figures 1 to 4 are diagrams each schematically illustrating a laminated structure of an organic light-emitting device according to an embodiment of the present application.

Hereinafter, this application will be described in detail.

The term "substitution" 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 where a hydrogen atom is substituted, that is, a position where a substituent can be substituted, and when two or more substituents are substituted, the two or more substituents may be the same or different from each other.

In this specification, halogen can 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 by other substituents. The number of carbon atoms in the alkyl group may be 1 to 60, specifically 1 to 40, and more specifically 1 to 20. Specific examples thereof may include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but are not limited thereto.

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

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 by other substituents. The number of carbon atoms of the alkynyl group may be 2 to 60, specifically 2 to 40, and more specifically 2 to 20.

In the present invention, the alkoxy group may be a straight chain, a branched chain or a ring. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20. Specific examples thereof may include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexoxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, n-octoxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and similar groups, but are not limited thereto.

In the present specification, cycloalkyl includes monocyclic or polycyclic rings having 3 to 60 carbon atoms, and may be further substituted with other substituents. In this article, polycyclic means a group in which the cycloalkyl is directly connected to other cyclic groups or fused to other cyclic groups. In this article, other cyclic groups may be cycloalkyl groups, but may also be different types of cyclic groups, such as heterocycloalkyl, aryl and heteroaryl. The number of carbonyl groups of the cycloalkyl group may be 3 to 60, specifically 3 to 40, and more specifically 5 to 20. Specific examples thereof may include 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 similar groups, but are not limited thereto.

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

基、菲基、苝基、茀蒽基、聯伸三苯基、丙烯合萘基、芘基、稠四苯基、稠五苯基、茀基、茚基、苊基、苯并茀、螺聯茀基、2,3-二氫-1H-茚基、其稠環以及類似基團，但不限於此。 In the present specification, aryl includes monocyclic or polycyclic rings having 6 to 60 carbon atoms, and may be further substituted by other substituents. In this article, polycyclic means a group in which aryl is directly connected to other cyclic groups or fused with other cyclic groups. In this article, other cyclic groups may be aryl groups, but may also be different types of cyclic groups, such as cycloalkyl, heterocycloalkyl and heteroaryl. Aryl includes spirocyclic groups. The number of carbon atoms of aryl may be 6 to 60, specifically 6 to 40 and more specifically 6 to 25. Specific examples of aryl may include phenyl, biphenyl, terphenyl, naphthyl, anthracenyl,

The invention also includes, but is not limited to, 1,2-dihydro-1H-indenyl, 2,3-dihydro-1H-indenyl, 2,4 ...

In the present specification _, a silyl group is a substituent including Si, having a Si atom directly connected as a group, and is represented by _{-SiR104R105R106} . _R104 to _R106 are _the same or different from each other, and may each independently be a substituent formed of at least one of the following: hydrogen, deuterium, halogen, alkyl, alkenyl, alkoxy, cycloalkyl, aryl, and heterocyclic groups. Specific examples of the silyl group may include trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, and the like, but are not limited thereto.

In the present invention, the fluorene group may be substituted, and adjacent substituents may bond to each other to form a ring.

、

、

、

、

、

以及類似基團。然而，所述結構不限於此。 When the fluorene group is substituted, it may contain

,

,

,

,

,

And similar groups. However, the structure is not limited thereto.

In the present specification, heteroaryl includes O, S, Se, N or Si as heteroatoms, including monocyclic or polycyclic rings with 2 to 60 carbon atoms, and may be further substituted by other substituents. In this article, polycyclic means a group in which the heteroaryl is directly connected to other cyclic groups or fused to other cyclic groups. In this article, other cyclic groups can be heteroaryl, but can also be different types of cyclic groups, such as cycloalkyl, heterocycloalkyl and aryl. The number of carbon atoms of the heteroaryl can be 2 to 60, specifically 2 to 40 and more specifically 3 to 25. Specific examples of the heteroaryl group may include pyridyl, pyrrolyl, pyrimidinyl, pyridazine, furanyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, furazolyl, oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, diazinyl, oxazinyl, thiazinyl, dioxynyl, triazinyl, tetrazinyl, quinolyl group, isoquinolyl, quinazolinyl group, isoquinazolinyl, quinozolinyl group, naphthyridinyl, acridinyl, phenanthidinyl, imidazopyridinyl, diazanaphthalenyl group, triazaindene group, group), indolyl, indolizinyl group, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzothiophenyl, benzofuranyl, dibenzothiophenyl, dibenzofuranyl, carbazolyl, benzocarbazolyl, dibenzocarbazolyl, phenazinyl, dibenzosilole group, spirobi(dibenzosilole) group, dihydrophenazinyl group, phenoxazinyl, phenanthridyl group), imidazopyridyl, thienyl, indolo[2,3-a]carbazolyl, indolo[2,3-b]carbazolyl, dihydroindolyl, 10,11-dihydro-dibenzo[b,f]aziryl, 9,10-dihydroaziridine, phenanthrazinyl group, phenothiathiazinyl group, phthalazinyl, naphthyldinyl group, phenanthrydinyl, benzo[c][1,2,5]thiadiazolyl group), 5,10-dihydrobenzo[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, and similar groups, but not limited thereto.

In the present specification, the amine group may be selected from the group consisting of monoalkylamine, monoarylamine, monoheteroarylamine, _-NH2 , dialkylamine, diarylamine, diheteroarylamine, alkylarylamine, alkylheteroarylamine and arylheteroarylamine, and although the number of carbon atoms is not particularly limited, it is preferably 1 to 30. Specific examples of the amino group may include methylamino, dimethylamino, ethylamino, diethylamino, aniline, naphthylamino, benzidine, dibenzidine, anthracenyl, 9-methyl-anthridine, diphenylamine, phenylnaphthylamine, dimethylamino, phenyltoluidine, triphenylamine, diphenylnaphthylamine, phenylbenzidine, diphenylfluorenylamine, phenyltriphenylamine, diphenyltriphenylamine and the like, but are not limited thereto.

In this specification, an aryl group means an aryl group having two bonding sites, i.e., a divalent group. Except for each being a divalent group, the description of the aryl group provided above can be applied here. In addition, a heteroaryl group means a heteroaryl group having two bonding sites, i.e., a divalent group. Except for each being a divalent group, the description of the heteroaryl group provided above can be applied here.

In this specification, specific examples of phosphine oxide groups may include diphenylphosphine oxide, dinaphthylphosphine oxide, and similar groups, but are not limited thereto.

In this specification, "adjacent" groups may mean a substituent that replaces an atom directly bonded to the atom replaced by the corresponding substituent, a substituent that is closest in space to the corresponding substituent, or another substituent that replaces the atom replaced by the corresponding substituent. For example, two substituents that replace adjacent positions in a benzene ring and two substituents that replace the same carbon in an aliphatic ring can be interpreted as "adjacent" groups to each other.

In this specification, the term "substituted" means that the hydrogen atom bonded to the carbon atom of the compound is changed into another substituent, and the position of substitution is not limited, as long as the position is the position where the hydrogen atom is substituted, that is, the position where the substituent can be substituted, and when two or more substituents are substituted, the two or more substituents can be the same or different from each other.

In the present specification, "substituted or unsubstituted" means substituted by one or more substituents selected from the group consisting of: C1 to C60 straight or branched chain alkyl, C2 to C60 straight or branched chain alkenyl, C2 to C60 straight or branched chain alkynyl, C3 to C60 monocyclic or polycyclic cycloalkyl, C2 to C60 monocyclic or polycyclic heterocyclic alkyl, C6 to C60 monocyclic or polycyclic heterocyclic alkyl, Cyclic or polycyclic aromatic group, C2 to C60 monocyclic or polycyclic heteroaromatic group, -SiRR'R", -P(=O)RR', C1 to C20 alkylamine, C6 to C60 monocyclic or polycyclic aromatic amine and C2 to C60 monocyclic or polycyclic heteroaromatic amine, or unsubstituted, or substituted by a substituent connected by two or more substituents selected from the substituents shown above, or unsubstituted.

An embodiment of the present application provides a compound represented by Chemical Formula 1.

Chemical formula 1 has a structure in which a quinoline group is fused to an indole group, and when having an indole group, Chemical formula 1 has an sp3 unshared electron pair in the structure instead of an sp2 unshared electron pair. Therefore, compared with benzothiophene or benzofuran having an sp2 non-covalent bond, the hole transfer property is particularly excellent. This affects the formation of excitons in the light-emitting layer when it is later used as an organic material layer of an organic light-emitting device, thereby causing an increase in device efficiency and life.

In one embodiment of the present application, R ₂ to R ₅ are the same as or different from each other and may be each independently selected from the group consisting of hydrogen, deuterium, halogen, -CN, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, SiRR'R", -P(=O)RR' and amine, wherein the amine is unsubstituted or substituted with substituted or unsubstituted alkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, or two or more groups adjacent to each other may be bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring.

In another embodiment, _R2 to _R5 of Chemical Formula 1 are the same as or different from each other, and may be independently selected from the group consisting of hydrogen, a substituted or unsubstituted C1 to C60 aryl group, and a substituted or unsubstituted C2 to C60 heteroaryl group, or two or more adjacent groups may be bonded to each other to form a substituted or unsubstituted aromatic hydrocarbon ring.

In another embodiment, _R2 to _R5 of Chemical Formula 1 are the same as or different from each other and may each independently be hydrogen, or two or more adjacent groups may be bonded to each other to form a substituted or unsubstituted C6 to C60 aromatic hydrocarbon ring.

In another embodiment, _R2 to _R5 of Chemical Formula 1 are the same as or different from each other and may each independently be hydrogen, or two or more adjacent groups may be bonded to each other to form a C6 to C40 aromatic hydrocarbon ring.

In another embodiment, _R2 to _R5 in Chemical Formula 1 are the same as or different from each other and may each independently be hydrogen, or two or more adjacent groups may be bonded to each other to form a benzene ring.

In one embodiment of the present application, R ₂ and R ₃ among R ₂ to R ₅ in Chemical Formula 1 are bonded to each other to form a benzene ring, and the remainder may be hydrogen.

In one embodiment of the present application, R ₃ and R ₄ among R ₂ to R ₅ in Chemical Formula 1 are bonded to each other to form a benzene ring, and the rest may be hydrogen.

In one embodiment of the present application, R ₄ and R ₅ among R ₂ to R ₅ in Chemical Formula 1 are bonded to each other to form a benzene ring, and the rest may be hydrogen.

In one embodiment of the present application, Ra of Chemical Formula 1 may be hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

In another embodiment, Ra of Chemical Formula 1 may be hydrogen, a substituted or unsubstituted C6 to C60 aryl group, or a substituted or unsubstituted C2 to C60 heteroaryl group.

In another embodiment, Ra of Chemical Formula 1 may be hydrogen, C6 to C40 aryl, or C2 to C40 heteroaryl.

In another embodiment, Ra of Chemical Formula 1 may be hydrogen.

In one embodiment of the present application, Ar ₁ may be represented by -(L1)p-(Z1)q, and Ar ₂ may be represented by -(L2)r-(Z2)s.

Since Ar ₁ and Ar ₂ in Chemical Formula 1 of the present application are substituted with various substituents, the thermal stability is better than when they are substituted with a single group, and compared with when they are substituted with a single group, substituents with an indole structure that control the hole transfer characteristics can be introduced in a more diverse manner, and the structural characteristics can be controlled better.

In one embodiment of the present application, L1 and L2 are the same or different from each other, and can be independently a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

In another embodiment, L1 and L2 are the same or different from each other, and can each independently be a substituted or unsubstituted C6 to C60 aryl group, or a substituted or unsubstituted C2 to C60 heteroaryl group.

In another embodiment, L1 and L2 are the same or different from each other, and can each independently be a C6 to C40 aryl group, or a C2 to C40 heteroaryl group.

In another embodiment, L1 and L2 are the same or different from each other, and can each independently be a C6 to C40 aryl group, or a C2 to C40 heteroaryl group.

In another embodiment, L1 and L2 are the same or different from each other, and can be independently a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a triphenyl group, a fluorenthranyl group, a pyrene group, a divalent pyridyl group, a divalent pyrimidyl group, or a divalent triazine group.

In one embodiment of the present application, L1 may be a substituted or unsubstituted C6 to C60 aryl group, or a substituted or unsubstituted C2 to C60 heteroaryl group.

In another embodiment, L1 may be a substituted or unsubstituted C6 to C40 aryl group, or a substituted or unsubstituted C2 to C40 heteroaryl group.

In another embodiment, L1 may be a C6 to C40 aryl group, or a C2 to C40 heteroaryl group.

In another embodiment, L1 can be a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a divalent pyridyl group, a divalent pyrimidyl group, or a divalent triazine group.

In one embodiment of the present application, L2 may be a substituted or unsubstituted C6 to C60 aryl group, or a substituted or unsubstituted C2 to C60 heteroaryl group.

In another embodiment, L2 may be a substituted or unsubstituted C6 to C40 aryl group, or a substituted or unsubstituted C2 to C40 heteroaryl group.

In another embodiment, L2 may be a C6 to C40 aryl group, or a C2 to C40 heteroaryl group.

In another embodiment, L2 can be a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a triphenyl group, a fluorenanthryl group, a pyrene group, a divalent pyridyl group, a divalent pyrimidyl group, or a divalent triazine group.

In one embodiment of the present application, Z1 and Z2 are the same or different from each other, and can be independently selected from the group consisting of: hydrogen; deuterium; halogen; -CN; substituted or unsubstituted alkyl; substituted or unsubstituted alkenyl; substituted or unsubstituted alkynyl; substituted or unsubstituted alkoxy; substituted or unsubstituted cycloalkyl; substituted or unsubstituted heterocycloalkyl; substituted or unsubstituted aryl; substituted or unsubstituted heteroaryl; -SiRR'R"; -P(=O)RR'; and amino, which is unsubstituted or substituted with: substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl.

In another embodiment, Z1 and Z2 are the same or different from each other, and can each independently be hydrogen, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or P(=O)RR'.

In another embodiment, Z1 and Z2 are the same or different from each other and can be independently hydrogen, a substituted or unsubstituted C6 to C60 aryl group, a substituted or unsubstituted C2 to C60 heteroaryl group or P(=O)RR'.

In another embodiment, Z1 and Z2 are the same or different from each other, and can each independently be hydrogen, a substituted or unsubstituted C6 to C40 aryl group, a substituted or unsubstituted C2 to C40 heteroaryl group, or P(=O)RR'.

In another embodiment, Z1 and Z2 are the same or different from each other and may be independently hydrogen; C6 to C40 aryl, which is unsubstituted or substituted by one or more substituents selected from the group consisting of: C6 to C40 aryl, C2 to C40 heteroaryl, C1 to C40 alkyl and -CN; C2 to C40 heteroaryl, which is unsubstituted or substituted by C6 to C40 aryl; or P(=O)RR', and the substituent may be unsubstituted or substituted again by C1 to C40 alkyl or C6 to C40 aryl.

In another embodiment, Z1 and Z2 are the same or different from each other and can be independently hydrogen; P(=O)RR'; phenyl, which is unsubstituted or substituted by one or more substituents selected from the group consisting of: 9,9'-dimethylfluorenyl, -CN, triphenylene, phenanthrenyl, phenyl, dibenzofuranyl and dibenzothienyl; phenyl, which is unsubstituted or substituted by carbazolyl, which is unsubstituted or substituted by phenyl; biphenyl; triphenylene; fluorenyl, which is unsubstituted or substituted by methyl; phenanthrenyl; spirofluorenyl; pyridyl; carbazolyl; dibenzofuranyl; dibenzothienyl; or phenanthroline, which is unsubstituted or substituted by phenyl.

In one embodiment of the present application, Z1 may be hydrogen; P(=O)RR'; phenyl, which is unsubstituted or substituted by one or more substituents selected from the group consisting of: carbazolyl, which is unsubstituted or substituted by phenyl, dibenzofuranyl and dibenzothienyl; biphenyl, spirobifluorenyl; fluorenyl, which is unsubstituted or substituted by methyl; pyridyl; dibenzofuranyl; dibenzothienyl; or phenanthroline group, which is unsubstituted or substituted by phenyl.

In one embodiment of the present application, Z2 may be hydrogen; P(=O)RR'; phenyl, which is unsubstituted or substituted by one or more substituents selected from the group consisting of: phenyl, phenanthrenyl, triphenylene, -CN, 9,9'-dimethylfluorenyl, carbazolyl and dibenzofuranyl; biphenyl; triphenylene; fluorenyl, which is unsubstituted or substituted by methyl; phenanthrenyl; pyridyl; carbazolyl; or dibenzofuranyl.

In one embodiment of the present application, R, R' and R" are the same or different from each other, and can be independently hydrogen; deuterium; -CN; substituted or unsubstituted alkyl; substituted or unsubstituted cycloalkyl; substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl.

In another embodiment, R, R' and R" are the same or different from each other, and can each independently be a substituted or unsubstituted aryl group.

In another embodiment, R, R' and R" are the same or different from each other, and can each independently be a substituted or unsubstituted C6 to C60 aryl group.

In another embodiment, R, R' and R" are the same or different from each other, and can each independently be a substituted or unsubstituted C6 to C40 aryl group.

In another embodiment, R, R' and R" are the same or different from each other, and can each independently be a C6 to C40 aryl group.

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

In the heterocyclic compound provided in one embodiment of the present application, Chemical Formula 1 can be represented by any one of the following Chemical Formulas 2 to 9.

[Chemical formula 2]

[Chemical formula 5]

[Chemical formula 8]

In Chemical Formulae 2 to 9, Ra, Ar ₁ , Ar ₂ , R ₂ to R ₅ and n have the same meanings as in Chemical Formula 1.

In the heterocyclic compound provided in one embodiment of the present application, Chemical Formula 1 is represented by any one of the following compounds.

The compound according to one embodiment of the present invention can be prepared according to the following general formula 1.

In Formula 1, R ₁₀ or R ₁₁ has the same definition as Ar ₁ or Ar ₂ in Formula 1.

In addition, by introducing various substituents into the structures of Chemical Formulae 1 to 9, compounds having unique characteristics of the introduced substituents can be synthesized. For example, by introducing substituents (usually used as hole injection layer materials, hole transfer layer materials, light-emitting layer materials, electron transfer layer materials, and charge generation layer materials for manufacturing organic light-emitting devices) into the core structure, materials that meet the required conditions of each organic material layer can be synthesized.

Furthermore, by introducing various substituents into the structures of Chemical Formula 1 to Chemical Formula 9, the energy band gap can be finely controlled, and at the same time, the characteristics at the interface between organic materials can be enhanced, and the material applications can be diversified.

At the same time, the compound has a high glass transition temperature (Tg) and has excellent thermal stability. Such improvement in thermal stability becomes an important factor in providing driving stability to the device.

The heterocyclic compound according to one embodiment of the present application can be prepared through a multi-step chemical reaction. First, some intermediate compounds are prepared, and the compound of Chemical Formula 1 can be prepared from the intermediate compounds. More specifically, the heterocyclic compound according to one embodiment of the present application can be prepared based on the preparation example described later.

Another embodiment of the present application provides an organic light-emitting device, the organic light-emitting device comprising: a first electrode; a second electrode disposed opposite to the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein one or more layers of the organic material layer include a heterocyclic compound according to Chemical Formula 1.

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

In another embodiment, the first electrode may be a cathode and the second electrode may be an anode.

In one embodiment of the present application, the organic light-emitting device may be a blue organic light-emitting device, and the heterocyclic compound according to Chemical Formula 1 may be used as a material for the blue organic light-emitting device.

In one embodiment of the present application, the organic light-emitting device may be a green organic light-emitting device, and the heterocyclic compound according to Chemical Formula 1 may be used as a material for the green organic light-emitting device.

In one embodiment of the present application, the organic light-emitting device may be a red organic light-emitting device, and the heterocyclic compound according to Chemical Formula 1 may be used as a material for the red organic light-emitting device.

The specific description about the heterocyclic compound represented by Chemical Formula 1 is the same as the description provided above.

In addition to using the heterocyclic compound described above to form one or more organic material layers, the organic light-emitting device of the present invention can be manufactured using commonly used organic light-emitting device manufacturing methods and materials.

When manufacturing an organic light-emitting device, the heterocyclic compound can be formed into an organic material layer via a solution coating method and a vacuum deposition method. In this article, the solution coating method means spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating and the like, but is not limited thereto.

The organic material layer of the organic light-emitting device of the present invention may be formed in a single-layer structure, or may also be formed in a multi-layer structure in which two or more organic material layers are laminated. For example, an organic light-emitting device according to an embodiment of the present invention may have a structure including the following as an organic material layer: a hole injection layer, a hole transfer layer, a light-emitting layer, an electron transfer layer, an electron injection layer, and the like. However, the structure of the organic light-emitting device is not limited thereto, and may include a smaller number of organic material layers.

In the organic light-emitting device of the present invention, the organic material layer includes an electron injection layer or an electron transfer layer, and the electron injection layer or the electron transfer layer may include a heterocyclic compound.

In the organic light-emitting device of the present invention, the organic material layer includes an electron transfer layer, and the electron transfer layer may include a heterocyclic compound.

In another organic light-emitting device, the organic material layer includes an electron blocking layer or a hole blocking layer, and the electron blocking layer or the hole blocking layer may include a heterocyclic compound.

In another organic light-emitting device, the organic material layer includes a hole blocking layer, and the hole blocking layer may include a heterocyclic compound.

In another organic light-emitting device, the organic material layer includes an electron transfer layer, a light-emitting layer or a hole blocking layer, and the electron transfer layer, the light-emitting layer or the hole blocking layer may include a heterocyclic compound.

The organic light-emitting device of the present invention may further include one, two or more layers selected from the group consisting of: a light-emitting layer, a hole injection layer, a hole transfer layer, an electron injection layer, an electron transfer layer, an electron blocking layer and a hole blocking layer.

Figures 1 to 3 illustrate the lamination sequence of the electrode and the organic material layer of an organic light-emitting device according to an embodiment of the present application. However, the scope of the present application is not limited to these figures, and the structure of the organic light-emitting device known in the art can also be used in the present application.

FIG. 1 shows an organic light-emitting device in which an anode 200, an organic material layer 300, and a cathode 400 are continuously laminated on a substrate 100. However, the structure is not limited to such a structure, and an organic light-emitting device can also be obtained in which a cathode, an organic material layer, and an anode are continuously laminated on a substrate as shown in FIG. 2.

FIG3 shows a case where the organic material layer is multi-layered. The organic light-emitting device according to FIG3 includes a hole injection layer 301, a hole transfer layer 302, a light-emitting layer 303, a hole blocking layer 304, an electron transfer layer 305, and an electron injection layer 306. However, the scope of this application is not limited to such a laminated structure, and may not include other layers except the light-emitting layer as needed, and may further include other necessary functional layers.

If necessary, the organic material layer including Chemical Formula 1 to Chemical Formula 9 may further include other materials.

In addition, an organic light-emitting device according to an embodiment of the present application includes an anode, a cathode, and two or more stacks disposed between the anode and the cathode, wherein the two or more stacks each independently include a light-emitting layer, a charge generating layer is included between the two or more stacks, and the charge generating 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 may include an anode, a first stack disposed on the anode and including a first light-emitting layer, a charge generation layer disposed on the first stack, a second stack disposed on the charge generation layer and including a second light-emitting layer, and a cathode disposed on the second stack. In this article, the charge generation layer may include a heterocyclic compound represented by Chemical Formula 1. In addition, the first stack and the second stack may each independently further include one or more types of hole injection layers, hole transfer layers, hole blocking layers, electron transfer layers, electron injection layers, and the like described above.

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

For example, an organic light-emitting device according to one embodiment of the present application is schematically illustrated in FIG4 as an organic light-emitting device having a 2-stacked series structure.

In this article, 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.

In an organic light-emitting device according to an embodiment of the present application, materials other than the compounds of Chemical Formulae 1 to 9 are described below, but these materials are only used for the purpose of description and do not limit the scope of the present application, and can be replaced by 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, metal, conductive polymer or the like may 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); combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole and polyaniline and the like, but are not limited thereto.

A material having a relatively small work function may be used as the cathode material, and metal, metal oxide, 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; multilayer structure materials such as LiF/Al or _LiO2 /Al and the like, but are not limited thereto.

As the hole injection material, a known hole injection material can be used, and for example, a phthalocyanine compound such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429 can be used; or a starburst amine derivative such as tris(4-hydrazinemethylyl-9-ylphenyl)amine (TCTA), 4,4',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 Material, 6, p. 677 (1994)]; a conductive polymer having solubility, polyaniline/dodecylbenzene sulfonic acid, poly(3,4-ethylenedioxythiophene)/poly(4-styrene sulfonic acid), polyaniline/camphor sulfonic acid (dodecylbenzene sulfonic acid) acid) or polyaniline/poly(4-styrene-sulfonate); and similar materials.

Pyrazoline derivatives, aromatic amine derivatives, stilbene derivatives, triphenyldiamine derivatives and similar materials can be used as hole transfer materials, and low molecular weight or high molecular weight materials can also be used.

Metal complexes of oxadiazole derivatives, anthraquinone dimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinone dimethane and its derivatives, fluorenone derivatives, diphenyl dicyanoethylene and its derivatives, diphenoquinone derivatives, 8-hydroxyquinoline and its derivatives, and similar materials can be used, and polymer materials and low molecular weight materials can also be used as electron transfer materials.

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

As the light-emitting material, a material emitting red, green or blue light can be used, and two or more light-emitting materials can be mixed and used as needed. In this article, two or more light-emitting materials can be used by depositing as individual supply sources or by pre-mixing and depositing as one supply source. In addition, a fluorescent material can also be used as the light-emitting material, however, a phosphorescent material can also be used. As the light-emitting material, a material that emits light by bonding electrons and holes injected from the anode and the cathode, respectively, can be used alone, however, a material having a main material and a doped material (which simultaneously participates in light emission) can also be used.

When mixing the host of light-emitting materials, the same series of hosts may be mixed, or different series of hosts may be mixed. For example, any two or more types of materials of n-type host materials or p-type host materials may be selected and used as the host material of the light-emitting layer.

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

The heterocyclic compound according to one embodiment of the present application can also be used in organic electronic devices under similar principles as used in organic light-emitting devices, including organic solar cells, organic photoconductors, organic transistors, and the like.

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

<Preparation Example>

<Preparation Example 1> Preparation of Compound 1

1) Preparation of compound 1-1

After (1H-indol-2-yl)boronic acid (100 g, 0.621 mol) and 2-bromoaniline (96 g, 0.558 mol) were dissolved in toluene, EtOH and H ₂ O (1000 ml: 200 ml: 200 ml), Pd(PPh ₃ ) ₄ (35.8 g, 0.031 mol) and NaHCO ₃ (156.5 g, 1.863 mol) were introduced thereto, and the resultant was stirred at 100° C. for 3 hours. After the reaction was completed, methylene chloride (MC) and distilled water were introduced into the reaction solution for extraction. Thereafter, the resultant was dried over anhydrous MgSO ₄ , and the solvent was removed using a rotary evaporator to obtain Compound 1-1 (94 g, 72%) in the form of a liquid.

2) Preparation of compound 1-2

Compound 1-1 (94 g, 0.451 mol) and triethylamine (42 ml, 0.451 mol) were introduced into MC (1200 ml) and dissolved therein. 4-Bromobenzoyl chloride (108.9 g, 0.496 mol) dissolved in MC (300 ml) was slowly added dropwise to the mixture at 0°C. After the reaction was completed, MC and distilled water were introduced into the reaction solution for extraction. Thereafter, the resultant was dried with anhydrous MgSO ₄ , and the solvent was removed using a rotary evaporator to obtain compound 1-2 (150 g, 85%) in liquid form.

3) Preparation of compound 1-3

After compound 1-2 (150 g, 0.383 mol) was dissolved in nitrobenzene (1500 mL), POCl ₃ (35 mL, 0.383 mol) was slowly added dropwise thereto. The resultant was reacted at 140° C. for 15 hours. After the reaction was completed, a solution in which NaHCO ₃ was dissolved in distilled water was slowly introduced into the reaction solution, and the resultant was stirred. The generated solid was filtered and collected. The collected solid was recrystallized with MC and MeOH to obtain compound 1-3 (68 g, 48%) in the form of a solid.

4) Preparation of Compound 1-4

After dissolving compound 1-3 (10 g, 0.026 mol), bis(pinacolato)diboron (9.9 g, 0.039 mol), KOAc (7.6 g, 0.078 mol) and PdCl ₂ (dppf) (0.9 g, 0.0013 mol) in 1,4-dioxane (200 ml), the resultant was reacted at 90° C. for 5 hours. After the reaction was completed, MC and distilled water were introduced into the reaction solution for extraction. Thereafter, the resultant was dried with anhydrous MgSO ₄ , and the solvent was removed using a rotary evaporator to obtain compound 1-4 (10 g, 91%)

5) Preparation of Compound 1-5

After compound 1-4 (10 g, 0.023 mol) and 2-bromo-4,6-diphenyl-1,3,5-triazine (7 g, 0.023 mol) were dissolved in toluene, EtOH and H ₂ O (100 ml: 20 ml: 20 ml), Pd(PPh ₃ ) ₄ (1.3 g, 0.0011 mol) and K ₂ CO ₃ (9.5 g, 0.069 mol) were introduced thereto, and the resultant was stirred at 100° C. for 5 hours. After the reaction was completed, MC and distilled water were introduced into the reaction solution for extraction. Thereafter, the resultant was dried with anhydrous MgSO ₄ , and the solvent was removed using a rotary evaporator to obtain compound 1-5 (9 g, 74%)

6) Preparation of compound 1

After compound 1-5 (9 g, 0.017 mol) and bromobenzene (3.2 g, 0.021 mol) were dissolved in toluene (100 ml), Pd ₂ (dba) ₃ (1.5 g, 0.0017 mol), tri-tert-butylphosphine (0.6 g, 0.034 mol) and sodium tert-butoxide (4.9 g, 0.051 mol) were introduced thereto, and the resultant was stirred at 100° C. for 15 hours. After the reaction was completed, the resultant was cooled to room temperature, and the generated solid was filtered and dried to obtain compound 1 (7.5 g, 73%).

The target compound was synthesized in the same manner as in Preparation Example 1, except that the intermediate A in Table 1 below was used instead of 2-bromo-4,6-diphenyl-1,3,5-triazine.

The target compound was synthesized in the same manner as in Preparation Example 1, except that the intermediate B in Table 2 below was used instead of 4-bromobenzyl chloride and the intermediate C in Table 2 below was used instead of 2-bromo-4,6-diphenyl-1,3,5-triazine.

The target compound was synthesized in the same manner as in Preparation Example 1, except that the intermediate D in Table 3 below was used instead of 2-bromoaniline and the intermediate E in Table 3 below was used instead of 2-bromo-4,6-diphenyl-1,3,5-triazine.

<Preparation Example 2> Preparation of Compound 135

1) Preparation of compound 135-1

After (1H-indol-2-yl)boronic acid (100 g, 0.621 mol) and 2-bromoaniline (96 g, 0.558 mol) were dissolved in toluene, EtOH and H ₂ O (1000 ml: 200 ml: 200 ml), Pd(PPh ₃ ) ₄ (35.8 g, 0.031 mol) and NaHCO ₃ (156.5 g, 1.863 mol) were introduced thereto, and the resultant was stirred at 100° C. for 3 hours. After the reaction was completed, MC and distilled water were introduced into the reaction solution for extraction. Thereafter, the resultant was dried with anhydrous MgSO ₄ , and the solvent was removed using a rotary evaporator to obtain compound 135-1 (94 g, 72%) in liquid form.

2) Preparation of compound 135-2

Compound 135-1 (94 g, 0.451 mol) and triethylamine (42 ml, 0.451 mol) were introduced into MC (1200 ml) and dissolved therein. Benzoyl chloride (69.7 g, 0.496 mol) dissolved in MC (300 ml) was slowly added dropwise to the mixture at 0°C. After the reaction was completed, MC and distilled water were introduced into the reaction solution for extraction. Thereafter, the resultant was dried over anhydrous MgSO ₄ , and the solvent was removed using a rotary evaporator to obtain compound 135-2 (112 g, 80%) in liquid form.

3) Preparation of compound 135-3

After compound 135-2 (112 g, 0.358 mol) was dissolved in nitrobenzene (1000 mL), POCl ₃ (33 mL, 0.358 mol) was slowly added dropwise thereto. The resultant was reacted at 140° C. for 15 hours. After the reaction was completed, a solution in which NaHCO ₃ was dissolved in distilled water was slowly introduced into the reaction solution, and the resultant was stirred. The generated solid was filtered and collected. The collected solid was recrystallized with MC and MeOH to obtain compound 135-3 (54 g, 51%) in the form of a solid.

4) Preparation of compound 135

After compound 135-3 (9 g, 0.030 mol) and 4-(4-bromophenyl)-2,6-diphenylpyrimidine (11.8 g, 0.030 mol) were dissolved in toluene (100 ml), Pd ₂ (dba) ₃ (2.8 g, 0.003 mol), tri-tert-butylphosphine (1.2 g, 0.006 mol) and sodium tert-butoxide (5.7 g, 0.062 mol) were introduced thereto, and the resultant was stirred at 100° C. for 15 hours. After the reaction was completed, the resultant was cooled to room temperature, and the generated solid was filtered and dried to obtain compound 135 (9.4 g, 52%).

The target compound was synthesized in the same manner as in Preparation Example 2, except that the intermediate F in Table 4 below was used instead of 4-(4-bromophenyl)-2,6-diphenylpyrimidine.

The target compound was synthesized in the same manner as in Preparation Example 2, except that the intermediate G in Table 5 below was used instead of benzoyl chloride and the intermediate H in Table 5 below was used instead of 4-(4-bromophenyl)-2,6-diphenylpyrimidine.

The target compound was synthesized in the same manner as in Preparation Example 2, except that the intermediate I in Table 6 below was used instead of 2-bromoaniline and the intermediate J in Table 6 below was used instead of 4-(4-bromophenyl)-2,6-diphenylpyrimidine.

<Preparation Example 3> Preparation of Compound 237

1) Preparation of compound 237-1

After (1H-indol-3-yl)boronic acid (100 g, 0.621 mol) and 2-bromoaniline (96 g, 0.558 mol) were dissolved in toluene, EtOH and H ₂ O (1000 ml: 200 ml: 200 ml), Pd(PPh ₃ ) ₄ (35.8 g, 0.031 mol) and NaHCO ₃ (156.5 g, 1.863 mol) were introduced thereto, and the resultant was stirred at 100° C. for 3 hours. After the reaction was completed, MC and distilled water were introduced into the reaction solution for extraction. Thereafter, the resultant was dried with anhydrous MgSO ₄ , and the solvent was removed using a rotary evaporator to obtain compound 237-1 (94 g, 72%) in liquid form.

2) Preparation of compound 237-2

Compound 237-1 (94 g, 0.451 mol) and triethylamine (42 ml, 0.451 mol) were introduced into MC (1200 ml) and dissolved therein. 4-Bromobenzoyl chloride (108.9 g, 0.496 mol) dissolved in MC (300 ml) was slowly added dropwise to the mixture at 0°C. After the reaction was completed, MC and distilled water were introduced into the reaction solution for extraction. Thereafter, the resultant was dried over anhydrous MgSO ₄ , and the solvent was removed using a rotary evaporator to obtain compound 237-2 (150 g, 85%) in liquid form.

3) Preparation of compound 237-3

After compound 237-2 (150 g, 0.383 mol) was dissolved in nitrobenzene (1500 ml), POCl ₃ (35 ml, 0.383 mol) was slowly added dropwise thereto. The resultant was reacted at 140° C. for 15 hours. After the reaction was completed, a solution in which NaHCO ₃ was dissolved in distilled water was slowly introduced into the reaction solution, and the resultant was stirred. The generated solid was filtered and collected. The collected solid was recrystallized with MC and MeOH to obtain compound 237-3 (68 g, 48%) in the form of a solid.

4) Preparation of compound 237-4

After dissolving compound 237-3 (10 g, 0.026 mol), bis(pinacolato)diboron (9.9 g, 0.039 mol), KOAc (7.6 g, 0.078 mol) and PdCl ₂ (dppf) (0.9 g, 0.0013 mol) in 1,4-dioxane (200 ml), the resultant was reacted at 90° C. for 5 hours. After the reaction was completed, MC and distilled water were introduced into the reaction solution for extraction. Thereafter, the resultant was dried with anhydrous MgSO ₄ , and the solvent was removed using a rotary evaporator to obtain compound 237-4 (10 g, 91%)

5) Preparation of compound 237-5

After compound 237-4 (8 g, 0.019 mol) and 2-bromo-4,6-diphenyl-1,3,5-triazine (5.9 g, 0.019 mol) were dissolved in toluene, EtOH and H ₂ O (80 ml: 10 ml: 10 ml), Pd(PPh ₃ ) ₄ (1.1 g, 0.0009 mol) and K ₂ CO ₃ (7.8 g, 0.057 mol) were introduced thereto, and the resultant was stirred at 100° C. for 5 hours. After the reaction was completed, MC and distilled water were introduced into the reaction solution for extraction. Thereafter, the resultant was dried over anhydrous MgSO ₄ , and the solvent was removed using a rotary evaporator to obtain compound 237-5 (7.4 g, 75%).

6) Preparation of compound 237

After compound 237-5 (7.4 g, 0.014 mol) and bromobenzene (3.2 g, 0.021 mol) were dissolved in toluene (100 ml), Pd ₂ (dba) ₃ (1.2 g, 0.0014 mol), tri-tert-butylphosphine (0.5 g, 0.0028 mol) and sodium tert-butoxide (2.7 g, 0.028 mol) were introduced thereto, and the resultant was stirred at 100° C. for 15 hours. After the reaction was completed, the resultant was cooled to room temperature, and the generated solid was filtered and dried to obtain compound 237 (6.5 g, 77%).

The target compound was synthesized in the same manner as in Preparation Example 3, except that the intermediate K in Table 7 below was used instead of 2-bromo-4,6-diphenyl-1,3,5-triazine.

The target compound was synthesized in the same manner as in Preparation Example 3, except that the intermediate L in Table 8 below was used instead of 4-bromobenzyl chloride and the intermediate M in Table 8 below was used instead of 2-bromo-4,6-diphenyl-1,3,5-triazine.

The target compound was synthesized in the same manner as in Preparation Example 3, except that the intermediate N in Table 9 below was used instead of 2-bromoaniline and the intermediate O in Table 9 below was used instead of 2-bromo-4,6-diphenyl-1,3,5-triazine.

<Preparation Example 4> Preparation of Compound 345

1) Preparation of compound 345-1

After (1H-indol-3-yl)boronic acid (100 g, 0.621 mol) and 2-bromoaniline (96 g, 0.558 mol) were dissolved in toluene, EtOH and H ₂ O (1000 ml: 200 ml: 200 ml), Pd(PPh ₃ ) ₄ (35.8 g, 0.031 mol) and NaHCO ₃ (156.5 g, 1.863 mol) were introduced thereto, and the resultant was stirred at 100° C. for 3 hours. After the reaction was completed, MC and distilled water were introduced into the reaction solution for extraction. Thereafter, the resultant was dried with anhydrous MgSO ₄ , and the solvent was removed using a rotary evaporator to obtain compound 345-1 (94 g, 72%) in liquid form.

2) Preparation of compound 345-2

Compound 345-1 (94 g, 0.451 mol) and triethylamine (42 ml, 0.451 mol) were introduced into MC (1200 ml) and dissolved therein. Benzoyl chloride (69.7 g, 0.496 mol) dissolved in MC (300 ml) was slowly added dropwise to the mixture at 0°C. After the reaction was completed, MC and distilled water were introduced into the reaction solution for extraction. Thereafter, the resultant was dried over anhydrous MgSO ₄ , and the solvent was removed using a rotary evaporator to obtain compound 345-2 (112 g, 80%) in liquid form.

3) Preparation of compound 345-3

After compound 345-2 (112 g, 0.358 mol) was dissolved in nitrobenzene (1000 mL), POCl ₃ (33 mL, 0.358 mol) was slowly added dropwise thereto. The resultant was reacted at 140° C. for 15 hours. After the reaction was completed, a solution in which NaHCO ₃ was dissolved in distilled water was slowly introduced into the reaction solution, and the resultant was stirred. The generated solid was filtered and collected. The collected solid was recrystallized with MC and MeOH to obtain compound 345-3 (54 g, 51%) in the form of a solid.

4) Preparation of compound 345

After compound 345-3 (9 g, 0.030 mol) and 2,4-di([1,1'-biphenyl]-4-yl)-6-(4-bromophenyl)pyrimidine (4.7 g, 0.030 mol) were dissolved in toluene (100 ml), Pd ₂ (dba) ₃ (2.8 g, 0.003 mol), tri-tert-butylphosphine (1.2 g, 0.006 mol) and sodium tert-butoxide (5.7 g, 0.062 mol) were introduced thereto, and the resultant was stirred at 100° C. for 15 hours. After the reaction was completed, the resultant was cooled to room temperature, and the resulting solid was filtered and dried to obtain Compound 345 (15 g, 60%).

The target compound was synthesized in the same manner as in Preparation Example 4, except that the intermediate P in Table 10 below was used instead of 2,4-di([1,1'-biphenyl]-4-yl)-6-(4-bromophenyl)pyrimidine.

The target compound was synthesized in the same manner as in Preparation Example 4, except that the intermediate Q in Table 11 below was used instead of benzoyl chloride and the intermediate R in Table 11 below was used instead of 2,4-di([1,1'-biphenyl]-4-yl)-6-(4-bromophenyl)pyrimidine.

The target compound was synthesized in the same manner as in Preparation Example 4, except that the intermediate S in Table 12 below was used instead of 2-bromoaniline and the intermediate T in Table 12 below was used instead of 2,4-di([1,1'-biphenyl]-4-yl)-6-(4-bromophenyl)pyrimidine.

Compounds other than the compounds described in Tables 1 to 12 were also prepared in the same manner as in the preparation examples described above.

Tables 13 and 14 below present the 1H NMR data and FD-MS data of the synthesized compounds, and the synthesis of the target compound can be identified through the following data.

<Experimental Example 1> Manufacturing of an organic light-emitting device

1) Manufacturing of organic light-emitting devices

Transparent ITO electrode films obtained from glass used for OLED (manufactured by Samsung-Corning Co., Ltd.) were ultrasonically cleaned for 5 minutes each using trichloroethylene, acetone, ethanol, and distilled water, and then stored in isopropyl alcohol and used.

Next, the ITO substrate was mounted in the substrate holder of the vacuum depositor, and the following 4,4',4"-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine (2-TNATA) was introduced into the chamber in the vacuum depositor.

Subsequently, the chamber was evacuated until the vacuum level of the chamber reached 10 ^-6 Torr, and then 2-TNATA was evaporated by applying a current to the chamber to deposit a hole injection layer with a thickness of 600 angstroms on the ITO substrate.

The following N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (NPB) was introduced into another chamber of the vacuum deposition apparatus and evaporated by applying a current to the chamber to deposit a hole transfer layer with a thickness of 300 angstroms on the hole injection layer.

After the hole injection layer and the hole transfer layer are formed as above, a blue light-emitting material having the following structure is deposited thereon as a light-emitting layer. Specifically, in a side chamber of a vacuum depositor, H1 (blue light-emitting main material) with a thickness of 200 angstroms is vacuum deposited, and D1 (blue light-emitting doping material) with a thickness of 5% relative to the main material is vacuum deposited thereon.

Subsequently, a compound described in Table 15 was deposited to a thickness of 300 angstroms as an electron transfer layer.

As an electron injection layer, lithium fluoride (LiF) is deposited to a thickness of 10 angstroms, and an Al cathode with a thickness of 1,000 angstroms is used to manufacture OLEDs.

At the same time, all organic compounds required for OLED manufacturing are purified by vacuum sublimation of each material used for OLED manufacturing at 10 ^-6 to 10 ^-8 torr.

The results of measuring the driving voltage, luminous efficiency, color coordinates (CIE) and life of the blue organic light-emitting device manufactured according to the present invention are shown in Table 15.

As shown in the results of Table 15, compared with Comparative Example 1, the organic light-emitting device using the electron transfer 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 life.

In addition, it is found that the luminous efficiency and life are better than those of Comparative Examples 2 to 4. Specifically, it can be seen that Compound B and Compound C of Comparative Examples 3 and 4 have the core structure of the present application substituted with one substituent. It is found that when substituted with one substituent, the thermal stability is reduced and the life is abnormally reduced compared to the compounds substituted with two similar heterocyclic compounds of Chemical Formula 1 of the present application.

<Experimental Example 2> Manufacturing of an organic light-emitting device

1) Manufacturing of organic light-emitting devices

Transparent ITO electrode films obtained from glass used for OLED (manufactured by Samsung Corning Co., Ltd.) were ultrasonically cleaned for 5 minutes each using trichloroethylene, acetone, ethanol, and distilled water, and then stored in isopropyl alcohol and used.

Next, the ITO substrate was mounted in the substrate holder of the vacuum depositor, and the following 4,4',4"-tris(N,N-(2-naphthyl)-anilino)triphenylamine (2-TNATA) was introduced into the chamber of the vacuum depositor.

Subsequently, the chamber was evacuated until the vacuum level of the chamber reached 10 ^-6 Torr, and then 2-TNATA was evaporated by applying a current to the chamber to deposit a hole injection layer with a thickness of 600 angstroms on the ITO substrate.

The following N,N'-bis(α-naphthyl)-N,N'-diphenyl-4,4'-diamine (NPB) was introduced into another chamber of the vacuum deposition apparatus and evaporated by applying a current to the chamber to deposit a hole transfer layer with a thickness of 300 angstroms on the hole injection layer.

After the hole injection layer and the hole transfer layer are formed as above, a blue light-emitting material having the following structure is deposited thereon as a light-emitting layer. Specifically, in a side chamber of a vacuum depositor, H1 (blue light-emitting main material) with a thickness of 200 angstroms is vacuum deposited, and D1 (blue light-emitting doping material) with a thickness of 5% relative to the main material is vacuum deposited thereon.

Subsequently, a compound of the following structural formula E1 is deposited to a thickness of 300 angstroms as an electron transfer layer.

As an electron injection layer, lithium fluoride (LiF) is deposited to a thickness of 10 angstroms, and an Al cathode with a thickness of 1,000 angstroms is used to manufacture OLEDs.

At the same time, all organic compounds required for OLED manufacturing are purified by vacuum sublimation of each material used for OLED manufacturing at 10 ^-6 to 10 ^-8 torr.

The electroluminescent device was manufactured in the same manner as in Experimental Example 2, except that after forming a 250 angstrom thick compound of the above structural formula E1 as an electron transfer layer, a 50 angstrom thick hole blocking layer was formed on the electron transfer layer using the compound presented in Table 16 below.

The results of measuring the driving voltage, luminous efficiency, color coordinates (CIE) and life of the blue organic light-emitting device manufactured according to the present invention are shown in Table 16.

As shown in the results of Table 16, compared with Comparative Example 5, the organic light-emitting device using the hole blocking 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 life. In addition, compared with Comparative Examples 6 to 8, the light emission efficiency and life are significantly improved. Specifically, it can be seen that Compound B and Compound C of Comparative Examples 7 and 8 have the core structure of the present application substituted with one substituent. It is identified that when substituted with one substituent, the thermal stability is reduced and the life is abnormally reduced compared to the compounds substituted with two similar heterocyclic compounds of Chemical Formula 1 of the present application.

This is because the compound of Chemical Formula 1 in the present application is a bipolar type with p-type and n-type properties, and is able to block hole leakage and effectively capture excitons in the light-emitting layer.

<Experimental Example 3> Manufacturing of an organic light-emitting device

1) Manufacturing of organic light-emitting devices

The glass substrate was ultrasonically cleaned with distilled water, and ITO was coated as a thin film with a thickness of 1500 angstroms on the glass substrate. After cleaning with distilled water, the substrate was ultrasonically cleaned with a solvent (such as acetone, methanol, and isopropyl alcohol), then dried, and UVO treated for 5 minutes in a UV cleaner using UV. Thereafter, the substrate was transferred to a plasma cleaner (PT) and plasma treated under vacuum to remove the ITO work function and residual film, and the substrate was transferred to a thermal deposition equipment for organic deposition.

On a transparent ITO electrode (anode), organic materials are formed in a 2-stack white organic light emitting device (WOLED) structure. For the first stack, TAPC is thermally vacuum deposited to a thickness of 300 angstroms to first form a hole transfer layer. After forming the hole transfer layer, the light emitting layer is thermally vacuum deposited thereon as follows. A 300 angstrom light emitting layer is deposited by doping 8% of FIrpic as a blue phosphorescent dopant into TCz1 (host). After forming a 400 angstrom electron transfer layer using TmPyPB, a 100 angstrom charge generation layer is formed by doping 20% of Cs ₂ CO ₃ into the compounds listed in Table 17 below.

For the second stack, _MoO3 was first thermally vacuum deposited to a thickness of 50 angstroms to form a hole injection layer. A hole transfer layer (common layer) was formed by doping _MoO3 20% with TAPC to 100 angstroms and depositing TAPC to 300 angstroms. A luminescent layer of 300 angstroms was deposited on TCz1 (host) by doping Ir(ppy) ₃ (green phosphorescent dopant) 8% and an electron transfer layer of 600 angstroms was formed using TmPyPB. Finally, an electron injection layer is formed on the electron transfer layer by depositing lithium fluoride (LiF) to a thickness of 10 angstroms, and then an aluminum (Al) cathode is formed on the electron injection layer by depositing a thickness of 1,200 angstroms, thereby manufacturing an organic light-emitting device.

At the same time, all organic compounds required for OLED manufacturing are purified by vacuum sublimation of each material used for OLED manufacturing at 10 ^-6 to 10 ^-8 torr.

The results of measuring the driving voltage, luminous efficiency, color coordinates (CIE) and life (T95) of the white organic light-emitting device manufactured according to the present invention are shown in Table 17 below.

As shown in the results of Table 17, compared with Comparative Examples 9 to 11, 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 luminous efficiency. In addition, compared with Comparative Examples 12 to 14, the driving voltage is similar, but the luminous efficiency and life are significantly improved.

Specifically, it can be seen that Compound B and Compound C of Comparative Example 13 and Comparative Example 14 have the core structure of the present application substituted with one substituent. It is recognized that when substituted with one substituent, the thermal stability is reduced and the lifespan is abnormally reduced compared to the compounds substituted with two similar heterocyclic compounds of Chemical Formula 1 of the present application.

100: Substrate

200: Yang pole

300: Organic material layer

400: cathode

Claims (14)

A heterocyclic compound represented by any one of the following Chemical Formulas 2 to 9:

[Chemical formula 5]

[Chemical formula 8]

Wherein, in Chemical Formulae 2 to 9, _R2 to _R5 are the same or different from each other, and are independently selected from the group consisting of: hydrogen, deuterium, halogen, -CN, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, -SiRR'R", -P(=O)RR', and amino, wherein the amino is unsubstituted or substituted with: substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; Ra is hydrogen; substituted or unsubstituted alkyl; substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl; _Ar1 is represented by (L1)p-(Z1)q; _Ar2 is represented by -(L2)r-(Z2)s; L1 and L2 are the same or different and are each independently a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group; Z1 and Z2 are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, halogen, -CN, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl group, -SiRR'R", -P(=O)RR' and an amine group, wherein the amine group is unsubstituted or substituted with a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group; R, R' and R" are the same as or different from each other and are each independently hydrogen, deuterium, -CN, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group; p and r are integers from 1 to 4; q and s are integers from 1 to 3; and n is an integer from 0 to 4. The heterocyclic compound as described in claim 1, wherein the term "substituted or unsubstituted" means substituted by one or more substituents selected from the group consisting of: C1 to C60 straight chain or branched chain alkyl, C2 to C60 straight chain or branched chain alkenyl, C2 to C60 straight chain or branched chain alkynyl, C3 to C60 monocyclic or polycyclic cycloalkyl, C2 to C60 monocyclic or polycyclic heterocyclic alkyl, C6 to C60 monocyclic or polycyclic Aryl, C2 to C60 monocyclic or polycyclic heteroaryl, -SiRR'R", -P(=O)RR', C1 to C20 alkylamine, C6 to C60 monocyclic or polycyclic aromatic amine and C2 to C60 monocyclic or polycyclic heteroaryl amine, or unsubstituted, or substituted by two or more substituents selected from the substituents shown above, or unsubstituted; and R, R' and R" are defined the same as in Chemical Formulas 2 to 9. The heterocyclic compound as described in claim 1, wherein R ₂ to R ₅ are hydrogen. The heterocyclic compound as described in item 1 of the patent application, wherein L1 and L2 are the same or different and are independently C6 to C40 aryl groups; or C2 to C40 heteroaryl groups, Z1 and Z2 are the same or different and are independently hydrogen; substituted or unsubstituted C6 to C40 aryl groups; substituted or unsubstituted C2 to C40 heteroaryl groups; or P(=O)RR', and the definitions of R and R' are the same as those in chemical formulas 2 to 9. A heterocyclic compound as described in item 1 of the patent application, wherein Ra is hydrogen. The heterocyclic compound as described in claim 1, wherein chemical formulas 2 to 9 are represented by any one of the following compounds:

An organic light-emitting device comprises: a first electrode; a second electrode disposed opposite to the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein one or more of the organic material layers comprises a heterocyclic compound as described in any one of items 1 to 6 of the patent application scope. An organic light-emitting device as described in Item 7 of the patent application, wherein the organic material layer includes a light-emitting layer, and the light-emitting layer includes the heterocyclic compound. An organic light-emitting device as described in Item 7 of the patent application, wherein the organic material layer includes an electron injection layer or an electron transfer layer, and the electron injection layer or the electron transfer layer includes the heterocyclic compound. An organic light-emitting device as described in Item 7 of the patent application, wherein the organic material layer includes an electron blocking layer or a hole blocking layer, and the electron blocking layer or the hole blocking layer includes the heterocyclic compound. The organic light-emitting device as described in Item 7 of the patent application further includes one layer, two layers or more layers selected from the group consisting of the following: a light-emitting layer, a hole injection layer, a hole transfer layer, an electron injection layer, an electron transfer layer, an electron blocking layer and a hole blocking layer. The organic light-emitting device as described in item 7 of the patent application scope comprises: a first electrode; a first stack disposed on the first electrode and comprising a first light-emitting layer; a charge generating layer disposed on the first stack; a second stack disposed on the charge generating layer and comprising a second light-emitting layer; and a second electrode disposed on the second stack. An organic light-emitting device as described in claim 12, wherein the charge generating layer includes the heterocyclic compound. An organic light-emitting device as described in item 12 of the patent application, wherein the charge generating layer is an N-type charge generating layer, and the charge generating layer includes the heterocyclic compound.

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