KR102262698B1 - Hetero cyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

The present specification relates to a heterocyclic compound of Formula 1 and an organic light emitting device including the same.

Description

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

The present invention claims the benefit of the filing date of Korean Patent No. 10-2018-0095448 submitted to the Korean Intellectual Property Office on August 16, 2018, the entire contents of which are incorporated herein by reference.

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

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

Korean Patent Application Publication No. 2016-0119683

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

According to an exemplary embodiment of the present specification, there is provided a heterocyclic compound represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1,

X is a direct bond, O, S, CR _a R _b or NR,

A ₁ and A ₂ are the same as or different from each other, and each independently is a direct bond, O, S or CR'R'',

R' and R" are the same as or different from each other, and are each independently hydrogen, deuterium, or a substituted or unsubstituted alkyl group,

R, R _a , R _b and R ₁ to R ₃ are the same as or different from each other, and each independently represent hydrogen, deuterium, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted alkoxy group. , a substituted or unsubstituted silyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted arylamine group, or a substituted or unsubstituted hydrocarbon ring by bonding adjacent groups, or to form a substituted or unsubstituted heterocycle,

a is an integer from 0 to 9, and when a is plural, R1 are the same as or different from each other,

b is an integer from 0 to 6, and when b is plural, R2 are the same as or different from each other,

c is an integer from 0 to 8, and when c is plural, R3 is the same as or different from each other.

In addition, the present specification is a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the heterocyclic compound. .

The heterocyclic compound according to an exemplary embodiment of the present specification may be used as a material for an organic material layer of an organic light emitting device, and by using the same, high luminous efficiency and/or high color purity can be obtained in the organic light emitting device.

1 and 2 show an organic light emitting device according to an exemplary embodiment of the present specification.

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

The present specification provides a heterocyclic compound represented by Formula 1 above.

The heterocyclic compound represented by Chemical Formula 1 of the present specification is characterized in that a ring is formed by binding all rotatable bonds to a compound structure having boron and nitrogen. This can reduce the vibrational energy of the material, so that most of the light emission of this material occurs at the 0-0 transition, and the spectrum has a narrower half maximum width. Therefore, when the heterocyclic compound represented by Formula 1 is applied to an organic electroluminescent device, a device having high efficiency and high color purity can be obtained.

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

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

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

The term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, a position where the substituent is substitutable, is substituted. , two or more substituents may be the same as or different from each other.

As used herein, the term "substituted or unsubstituted" refers to deuterium; nitrile group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted aryl group; And it means that it is substituted with one or two or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group, is substituted with a substituent to which two or more of the above-exemplified substituents are connected, or does not have any substituents. For example, "a substituent in which two or more substituents are connected" may be an aryl group substituted with an aryl group, an aryl group substituted with a heteroaryl group, a heterocyclic group substituted with an aryl group, an aryl group substituted with an alkyl group, and the like.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specifically, it is preferably 1 to 20 carbon atoms. More specifically, it is preferable that it has 1-10 carbon atoms. Specific examples include a methyl group; ethyl group; Profile group; n-propyl group; isopropyl group; butyl group; n-butyl group; isobutyl group; tert-butyl group; sec-butyl group; 1-methylbutyl group; 1-ethylbutyl group; pentyl group; n-pentyl group; isopentyl group; neopentyl group; tert-pentyl group; hexyl group; n-hexyl group; 1-methylpentyl group; 2-methylpentyl group; 4-methyl-2-pentyl group; 3,3-dimethylbutyl group; 2-ethylbutyl group; heptyl group; n-heptyl group; 1-methylhexyl group; cyclopentylmethyl group; cyclohexylmethyl group; octyl group; n-octyl group; tert-octyl group; 1-methylheptyl group; 2-ethylhexyl group; 2-propylpentyl group; n-nonyl group; 2,2-dimethylheptyl group; 1-ethylpropyl group; 1,1-dimethylpropyl group; isohexyl group; 2-methylpentyl group; 4-methylhexyl group; 5-methylhexyl group, and the like, but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms. Specifically, a cyclopropyl group; cyclobutyl group; cyclopentyl group; 3-methylcyclopentyl group; 2,3-dimethylcyclopentyl group; cyclohexyl group; 3-methylcyclohexyl group; 4-methylcyclohexyl group; 2,3-dimethylcyclohexyl group; 3,4,5-trimethylcyclohexyl group; 4-tert-butylcyclohexyl group; cycloheptyl group; There is a cyclooctyl group and the like, but is not limited thereto.

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C30. Specifically, it is preferably 1 to 20 carbon atoms. More specifically, it is preferable that it has 1 to 10 carbon atoms. Specifically, a methoxy group; ethoxy group; n-propoxy group; isopropoxy group; i-propyloxy group; n-butoxy group; isobutoxy group; tert-butoxy group; sec-butoxy group; n-pentyloxy group; neopentyloxy group; isopentyloxy group; n-hexyloxy group; 3,3-dimethylbutyloxy group; 2-ethylbutyloxy group; n-octyloxy group; n-nonyloxy group; n-decyloxy group; benzyloxy group; It may be a p-methylbenzyloxy group, but is not limited thereto.

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

In the present specification, the silyl group may be represented by the formula of -SiReRfRg, wherein Re, Rf and Rg are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group. The silyl group is specifically a trimethylsilyl group; triethylsilyl group; t-butyldimethylsilyl group; vinyl dimethyl silyl group; propyldimethylsilyl group; triphenylsilyl group; diphenylsilyl group; There is a phenylsilyl group, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms. The aryl group may be monocyclic or polycyclic. When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but preferably 6 to 30 carbon atoms. More specifically, it is preferable that it has 6-20 carbon atoms. Specifically, the monocyclic aryl group includes a phenyl group; biphenyl group; It may be a terphenyl group, but is not limited thereto. When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it has 10-30 carbon atoms, and more specifically, it is preferable that it has 10-20 carbon atoms. Specifically, the polycyclic aryl group includes a naphthyl group; anthracenyl group; phenanthryl group; triphenyl group; pyrenyl group; phenalenyl group; perylenyl group; chrysenyl group; It may be a fluorenyl group, but is not limited thereto.

As used herein, "adjacent" group means a substituent substituted on an atom directly connected to the atom in which the substituent is substituted, a substituent sterically closest to the substituent, or another substituent substituted on the atom in which the substituent is substituted. can For example, two substituents substituted at an ortho position in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring may be interpreted as "adjacent" groups.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group including two or more aryl groups may include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time. For example, the aryl group in the arylamine group may be selected from the examples of the aryl group described above.

In the present specification, the heteroaryl group includes one or more atoms other than carbon, that is, heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se and S, and the like. The number of carbon atoms is not particularly limited, but preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heteroaryl group include a thiophene group; furanyl group; pyrrole group; imidazolyl group; thiazolyl group; oxazolyl group; oxadiazolyl group; pyridyl group; bipyridyl group; pyrimidyl group; triazinyl group; triazolyl group; acrydyl group; pyridazinyl group; pyrazinyl group; quinolinyl group; quinazolinyl group; quinoxalinyl group; phthalazinyl group; pyrido pyrimidyl group; pyrido pyrazinyl group; pyrazino pyrazinyl group; isoquinolinyl group; indolyl group; carbazolyl group; benzoxazolyl group; benzimidazolyl group; benzothiazolyl group; benzocarbazolyl group; benzothiophene group; dibenzothiophene group; benzofuranyl group; phenanthroline; isoxazolyl group; thiadiazolyl group; There is a phenothiazinyl group and a dibenzofuranyl group, but is not limited thereto.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroarylamine group including two or more heteroaryl groups may include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group at the same time. For example, the heteroaryl group in the heteroarylamine group may be selected from the examples of the heteroaryl group described above.

In an exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of Chemical Formulas 2 to 6 below.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In Formulas 2 to 6, R _a , R _b and R ₁ to R ₃ , A ₁ , A ₂ , a, b, and c are as defined in Formula 1 above.

In an exemplary embodiment of the present specification, X is a direct bond.

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

In an exemplary embodiment of the present specification, X is S.

In an exemplary embodiment of the present specification, X is CR _a R _b .

In an exemplary embodiment of the present specification, X is NR.

In an exemplary embodiment of the present specification, A ₁ and A ₂ are the same as or different from each other, and each independently represents a direct bond, O, S, or CR'R''.

In an exemplary embodiment of the present specification, A ₁ and A ₂ are a direct bond.

In the exemplary embodiment of the present specification, A ₁ and A ₂ are O.

In the exemplary embodiment of the present specification, A ₁ and A ₂ are S.

In the exemplary embodiment of the present specification, A ₁ and A ₂ are CR′R″.

In an exemplary embodiment of the present specification, A ₁ and A ₂ are different from each other and each independently represent a direct bond, O, S, or CR'R''.

In an exemplary embodiment of the present specification, the R, R _a , R _{b ,} R', R" and R ₁ to R ₃ are the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, 6 carbon atoms to 30 aryl group, a heteroaryl group containing at least one of N, S, or O having 3 to 30 carbon atoms, or a substituted or unsubstituted hydrocarbon ring, or a substituted or unsubstituted hetero form a ring

In an exemplary embodiment of the present specification, R' and R" are the same as or different from each other, and each independently represent hydrogen, deuterium, or a substituted or unsubstituted alkyl group.

In an exemplary embodiment of the present specification, R' and R" are the same as or different from each other, and each independently represent hydrogen, deuterium, or an alkyl group having 1 to 10 carbon atoms.

In an exemplary embodiment of the present specification, R′ and R″ are the same as or different from each other, and each independently represent hydrogen or an alkyl group having 1 to 10 carbon atoms.

In an exemplary embodiment of the present specification, R' and R" are the same as or different from each other, and each independently represent hydrogen, a straight-chain alkyl group having 1 to 10 carbon atoms, or a branched-chain alkyl group having 1 to 10 carbon atoms.

In an exemplary embodiment of the present specification, R' and R" are the same as or different from each other, and each independently hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a terbutyl group, a pentyl group or a hexyl group.

In an exemplary embodiment of the present specification, R' and R" are methyl groups.

In an exemplary embodiment of the present specification, the R, R _a , R _b and R ₁ to R ₃ are the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, It is a heteroaryl group containing at least one of N, S, or O having 3 to 30 carbon atoms, or adjacent groups are bonded to each other to form a substituted or unsubstituted hydrocarbon ring, or a substituted or unsubstituted heterocycle.

In an exemplary embodiment of the present specification, R _a and R _b are the same as or different from each other, and each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, N having 3 to 30 carbon atoms, S, or a heteroaryl group containing at least one of O, or adjacent groups are bonded to each other to form a substituted or unsubstituted hydrocarbon ring, or a substituted or unsubstituted heterocycle.

In an exemplary embodiment of the present specification, R _a and R _b are the same as or different from each other, and each independently hydrogen, a methyl group, an ethyl group, a propyl group, a butyl group, a terbutyl group, a phenyl group, a biphenyl group, a terphenyl group, naphthyl group, anthracene group, phenanthrene group, dibenzofuran group, dibenzothiophene group, carbazole group, pyridine group, pyrimidine group, or triazine group.

In an exemplary embodiment of the present specification, R is a heteroaryl group comprising any one or more of hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, N, S, or O having 3 to 30 carbon atoms Or, adjacent groups combine to form a substituted or unsubstituted hydrocarbon ring, or a substituted or unsubstituted heterocycle.

In an exemplary embodiment of the present specification, R is an aryl group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, R is a monocyclic aryl group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, R is a polycyclic aryl group having 10 to 30 carbon atoms.

In an exemplary embodiment of the present specification, R is a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracene group, a phenanthrene group, a triphenylene group, or a fluorene group.

In an exemplary embodiment of the present specification, R is _{combined with R 3} to form a substituted or unsubstituted hydrocarbon ring, or a substituted or unsubstituted heterocycle.

In an exemplary embodiment of the present specification, the R ₁ to R ₃ are the same as or different from each other, and are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 30 carbon atoms, or adjacent groups are bonded to each other, A substituted or unsubstituted hydrocarbon ring, or a substituted or unsubstituted heterocycle is formed.

In an exemplary embodiment of the present specification, R ₁ is hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, heteroaryl including any one or more of N, S, or O having 3 to 30 carbon atoms group or adjacent groups combine to form a substituted or unsubstituted hydrocarbon ring, or a substituted or unsubstituted heterocycle.

In an exemplary embodiment of the present specification, R ₁ is hydrogen; methyl group; ethyl group; Profile group; isopropyl group; butyl group; terbutyl group; pentyl group; a silyl group substituted with a methyl group, an ethyl group, or a phenyl group; or an amine group substituted with a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracene group, or a fluorene group.

In an exemplary embodiment of the present specification, R ₁ is hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a terbutyl group, a pentyl group, a silyl group substituted with a methyl group, or an amine group substituted with a phenyl group to be.

In an exemplary embodiment of the present specification, R ₁ is hydrogen, a methyl group, a terbutyl group, a trimethylsilyl group, or a diphenylamine group.

In an exemplary embodiment of the present specification, R ₂ is hydrogen.

In an exemplary embodiment of the present specification, R ₃ is hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a terbutyl group, or a pentyl group.

In an exemplary embodiment of the present specification, R ₃ is hydrogen, a methyl group, or a terbutyl group.

In an exemplary embodiment of the present specification, R ₃ is hydrogen or a terbutyl group.

In an exemplary embodiment of the present specification, Chemical Formula 1 is any one selected from the following compounds.

The organic light emitting device of the present invention includes a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein one or more of the organic material layers may include the above-described heterocyclic compound.

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

1 illustrates a structure of an organic light emitting device in which a first electrode 2 , an organic material layer 3 , and a second electrode 4 are sequentially stacked on a substrate 1 . The heterocyclic compound of Formula 1 is preferably included in the organic material layer.

1 illustrates an organic light emitting device, but is not limited thereto.

2 shows a first electrode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 8, an electron injection layer 9, an electron injection layer on the substrate 1 The structure of the organic light emitting device in which (10) and the second electrode 4 are sequentially stacked is exemplified. The heterocyclic compound of Formula 1 may be included in the hole injection layer (5), the hole transport layer (6), the electron blocking layer (7), the light emitting layer (8), the electron injection layer (9), the electron injection layer (10) , preferably included in the light emitting layer, but is not limited thereto.

In an exemplary embodiment of the present invention, the organic material layer includes a light emitting layer, and the light emitting layer includes the heterocyclic compound of Formula 1 above.

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

The organic light emitting device of the present invention includes an emission layer, and the emission layer includes a host and a dopant in a mass ratio of 99:1 to 60:40.

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

In an exemplary embodiment of the present invention, the organic material layer includes an emission layer, and the emission layer includes the heterocyclic compound of Formula 1 as a dopant.

In an exemplary embodiment of the present invention, the organic material layer may include an emission layer, and the emission layer may include an organic compound as a host.

In one embodiment of the present invention, the light emitting layer may include a material represented by the following formula (A) as a host.

[Formula A]

In Formula A, R ₁ to R ₁₀ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or an unsubstituted silyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted arylamine group.

In an exemplary embodiment of the present invention, R ₁ to R ₄ and R ₆ to R ₉ are hydrogen.

In an exemplary embodiment of the present invention, R ₅ and R ₁₀ are a substituted or unsubstituted aryl group.

In an exemplary embodiment of the present invention, R ₅ and R ₁₀ are a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present invention, R ₅ and R ₁₀ are a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted anthracene group, a substituted or unsubstituted a substituted or unsubstituted triphenylene group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted pyrene group.

In an exemplary embodiment of the present invention, R ₅ and R ₁₀ are a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, or a substituted or unsubstituted naphthyl group.

In an exemplary embodiment of the present invention, R ₅ and R ₁₀ are a phenyl group or a naphthyl group.

In an exemplary embodiment of the present invention, R ₅ and R ₁₀ are a phenyl group, a 1-naphthyl group, or a 2-naphthyl group.

In an exemplary embodiment of the present invention, R ₅ and R ₁₀ are a phenyl group or a 1-naphthyl group.

In an exemplary embodiment of the present invention, the organic material layer includes a hole injection layer, a hole transport layer, or a hole injection and transport layer, and the hole injection layer, the hole transport layer, or the hole injection and transport layer is a heterocyclic compound of Formula 1 may include

In an exemplary embodiment of the present invention, the organic material layer includes an electron injection layer, an electron transport layer, or an electron injection and transport layer, and the electron injection layer, the electron transport layer, or the electron injection and transport layer is a heterocyclic compound of Formula 1 may include

In an exemplary embodiment of the present invention, the organic material layer may include an electron blocking layer or a hole blocking layer, and the electron blocking layer or the hole blocking layer may include the heterocyclic compound of Formula 1 above.

For example, the organic light emitting device according to the present invention uses a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to form a metal or a conductive metal oxide or an alloy thereof on a substrate. to form an anode, and an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an organic material layer including the heterocyclic compound of Formula 1 thereon, a material that can be used as a cathode thereon It can be prepared by vapor deposition. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

As the anode material, a material having a large work function is generally preferable to facilitate hole injection into the organic material layer. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO:Al or SnO ₂ : a combination of a metal such as Sb and an oxide; Poly(3-methyl compound), poly[3,4-(ethylene-1,2-dioxy) compound] (PEDT), polypyrrole and polyaniline and 7 are conductive polymers, but are not limited thereto .

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

The hole injection material is a material capable of well injecting holes from the anode at a low voltage, and it is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, and conductive polymers based on polyaniline and polycompounds, but is not limited thereto.

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

The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene, rubrene, and the like, but is not limited thereto.

When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

The organic light emitting device of the present specification may be manufactured using materials and methods known in the art, except that at least one layer of the organic material layer is formed using the heterocyclic compound.

The present specification also provides a method of manufacturing an organic light emitting device formed using the heterocyclic compound.

Examples of the dopant material include an aromatic heterocyclic compound, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic heterocyclic compound is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periflanthene, and the like, having an arylamino group. A compound in which at least one arylvinyl group is substituted with a cyclic arylamine, wherein one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports them to the light emitting layer. As an electron transport material, a material that can receive electrons from the cathode and transfer them to the light emitting layer is suitable. Do. Specific examples include Al complex of 8-hydroxyquinoline; complexes containing Alq _{3 ;} organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.

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

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. It is not limited to this.

The hole blocking layer is a layer that blocks the holes from reaching the cathode, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complex, and the like, but is not limited thereto.

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

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

[ Synthesis example ]

Synthesis example a: synthesis of intermediate a

Step 1) Synthesis of intermediate a-1

In a flask, 1,5-dibromo-2,4-dinitrobenzene (25.0 g, 76.7 mmol), 2-(3-(terbutyl)phenyl)-4,4,5,5-tetramethyl-1, 3,2-dioxaborolein (43.9 g, 168.8 mmol), tetrakis (triphenylphosphine) palladium (0) (4.4 g, 3.8 mmol), potassium carbonate (63.6 g, 460.3 mmol), THF (tetrahydro Furan) 375ml, H ₂ O 125ml were added, and the mixture was stirred for 8 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, the reaction solution was transferred to a separatory funnel and extracted with dichloromethane. After drying the extract with MgSO ₄ , filtration and concentration, the sample was purified by silica gel column chromatography to obtain 27.5 g of intermediate a-1. (Yield 83%, MS[M+H]+= 432)

Step 2) Synthesis of intermediate a-2

Intermediate a-1 (27.0g, 62.4mmol), triphenylphosphine (25.9g, 187.3mmol), 270ml of o-dichlorobenzene were placed in a flask and stirred under reflux conditions for 24 hours. Upon completion of the reaction, the mixture was cooled to room temperature, distilled under reduced pressure to remove the solvent, and extracted with dichloromethane. The extract _{was dried over MgSO 4} , filtered and concentrated, and the sample was purified by silica gel column chromatography to obtain 13.3 g of an intermediate a-2. (Yield 58%, MS[M+H]+=368)

Step 3) Synthesis of intermediate a

Intermediate a-2 (13.0g, 35.3mmol), N-bromosuccinimide (6.5g, 36.3mmol), and 260ml of dichloromethane were placed in a flask and stirred at room temperature for 8 hours. After completion of the reaction, the reaction solution was concentrated, and the sample was purified by silica gel column chromatography to obtain 12.5 g of intermediate a. (yield 79%, MS[M+H] ⁺ = 447)

Synthesis example b: synthesis of intermediate b

In Synthesis Example a, 2- (3- (terbutyl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolein was mixed with trimethyl (3- (4,4,5, Except for using 5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)silane, it was synthesized by the same preparation method as the preparation method of intermediate a to obtain intermediate b . (MS[M+H] ⁺ = 479)

Synthesis example 1: Synthesis of compound 1

Step 1) Synthesis of compound 1-1

In a flask, Intermediate a (12.0 g, 26.8 mmol), Intermediate A (13.4 g, 28.2 mmol), Bis(tri-ter-butylphosphine)palladium(0) (0.3g, 0.5mmol), Sodium terbutoxide (3.9 g, 40.2 mmol), 360 ml of toluene were added, and the mixture was stirred for 6 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, H ₂ O was added, and the reaction solution was transferred to a separatory funnel for extraction. The extract _{was dried over MgSO 4} , and concentrated, and the sample was purified by silica gel column chromatography to obtain 8.8 g of compound 1-1. (Yield 43%, MS[M+H]+=761)

Step 2) Synthesis of compound 1

Compound 1-1 (8.0 g, 10.5 mmol) was dissolved in 160 ml of terbutylbenzene in a flask and cooled to 0 °C. Under a nitrogen atmosphere, 1.7 M of terbutyllithium in pentane (9.3ml, 15.8mmol) was added and stirred at 60°C for 2 hours. After that, the reactant was cooled to 0 °C again, boron tribromide (1.5 ml, 15.8 mmol) was added thereto, and the mixture was stirred at room temperature for 0.5 hours. The reaction mass was again cooled to 0 °C, and N,N-diisopropylethylamine (2.7ml, 15.8mmol) was added thereto, followed by stirring at 60 °C for 2 hours. After the reaction was completed, the mixture was cooled to room temperature, and extracted from a separatory funnel using _{ethyl acetate and H 2 O.} The extract _{was dried over MgSO 4} , concentrated, and the sample was purified by silica gel column chromatography to obtain compound 1 (0.8 g) through sublimation purification. (Yield 11%, MS[M+H]+=690)

Synthesis example 2: Synthesis of compound 2

In Synthesis Example 1, except that the intermediate A was changed to the intermediate B and used, it was synthesized in the same manner as in the preparation method of compound 1 to obtain compound 2. (MS[M+H] ⁺ = 706)

Synthesis example 3: Synthesis of compound 3

In Synthesis Example 1, except that the intermediate A was changed to the intermediate C and used, it was synthesized by the same preparation method as the preparation method of compound 1 to obtain compound 3 . (MS[M+H] ⁺ = 722)

Synthesis example 4: Synthesis of compound 4

In Synthesis Example 1, except that the intermediate a was changed to the intermediate b and used, it was synthesized in the same manner as in the preparation method of compound 1 to obtain compound 4. (MS[M+H] ⁺ = 722)

[ Example ]

< Example 1>

A glass substrate coated with a thin film of ITO (Indium Tin Oxide) to a thickness of 1,400 Å was placed in distilled water dissolved in detergent and washed with ultrasonic waves. At this time, Decon™ CON705 of Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a 0.22㎛ sterilizing filter manufactured by Millipore Co. was used as distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed for 10 minutes each with a solvent of isopropyl alcohol, acetone, and methanol, and then transported to a plasma cleaner after drying. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

On the thus prepared ITO transparent electrode, the following HI-A and LG-101 were sequentially thermally vacuum deposited to a thickness of 650 Å and 50 Å, respectively, to form a hole injection layer. After vacuum deposition of HT-A as a hole transport layer to a thickness of 600 Å, HT-B as an electron blocking layer was thermally vacuum-deposited to a thickness of 50 Å. Subsequently, BH-A and Compound 1 were vacuum-deposited to a thickness of 200 Å in a weight ratio of 96:4 as a light emitting layer. Then, as the electron transport layer, ET and a compound represented by Liq were thermally vacuum-deposited at a weight ratio of 1:1 to a thickness of 360 Å, and then the compound represented by the following Liq was vacuum-deposited to a thickness of 5 Å to form an electron injection layer. On the electron injection layer, magnesium and silver were sequentially deposited at a weight ratio of 10:1 to a thickness of 220 Å and aluminum to a thickness of 1000 Å to form a cathode, thereby manufacturing an organic light emitting device.

Example 2 to Example 4 and comparative example 1 to comparative example 2

Organics of Examples 2 to 4 and Comparative Examples 1 to 2 using the same method as in Example 1, except that the compounds listed in Table 1 were used instead of Compound 1 as the dopant material in Example 1 Each of the light emitting devices was fabricated.

By applying a current to the organic light emitting devices manufactured in Examples 1 to 6 and Comparative Examples 1 to 2, voltage and efficiency were measured, and the results are shown in Table 1 below. Here, voltage and efficiency were ^{measured by applying a current density of 10 mA/cm 2} , and FWHM (full width at half maximum) was obtained from the spectrum measured at this time.

dopant @ 10mA/cm ² V QE FWHM(nm) Example 1 compound 1 3.93 7.73 20 Example 2 compound 2 3.91 7.75 21 Example 3 compound 3 3.95 7.70 23 Example 4 compound 4 3.92 7.79 21 Comparative Example 1 BD-A 3.98 7.50 25 Comparative Example 2 BD-B 3.99 7.43 54

The boron compound such as BD-A applied to Comparative Example 1 has a narrower half maximum width than the dopant such as BD-B. However, it has a structure in which the structure is distorted due to the repulsive force of two hydrogen atoms in the ortho position of boron.

The structures of [Formula 1] of the present invention have a structure in which the benzene ring attached to the amine of BD-A is bound while taking structural stability by linking the two hydrogen positions. As shown in Table 1, when these materials are applied as dopants for organic light-emitting devices, a device with high color purity and high efficiency can be obtained.

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

Claims (8)

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

In Formula 1,
X is a direct bond, O, or S;
A ₁ and A ₂ are the same as or different from each other, and each independently is a direct bond, O, S or CR'R'',
R' and R" are the same as or different from each other, and are each independently hydrogen, deuterium, or an alkyl group;
R ₁ to R ₃ are the same as or different from each other, and each independently represent hydrogen, deuterium, an alkyl group, a silyl group unsubstituted or substituted with an alkyl group, or an arylamine group,
a is an integer from 0 to 9, and when a is plural, R1 are the same as or different from each other,
b is an integer from 0 to 6, and when b is plural, R2 are the same as or different from each other,
c is an integer from 0 to 8, and when c is plural, R3 is the same as or different from each other. The method according to claim 1, wherein Formula 1 is a heterocyclic compound represented by any one of Formulas 2, 3 and 6:
[Formula 2]

[Formula 3]

[Formula 6]

In Formulas 2, 3 and 6, R _{One To} R ₃ , A ₁ , A ₂ , a, b, and c are as defined in Formula 1 above. The heterocyclic compound according to claim 1, wherein R ₁ to R ₃ are the same as or different from each other, and each independently hydrogen or an alkyl group having 1 to 10 carbon atoms. The heterocyclic compound of claim 1, wherein A ₁ and A ₂ are the same as each other. The heterocyclic compound according to claim 1, wherein Formula 1 is any one selected from the following compounds:

a first electrode; a second electrode provided to face the first electrode; And an organic light emitting device comprising one or more organic material layers provided between the first and second electrodes, wherein at least one of the organic material layers comprises the heterocyclic compound of any one of claims 1 to 5 Phosphorus organic light emitting device. The organic light emitting device of claim 6 , wherein the organic material layer includes a light emitting layer, and the light emitting layer includes a host and a dopant in a mass ratio of 99:1 to 80:20. The organic light emitting device according to claim 6, wherein the organic material layer includes a light emitting layer, and the light emitting layer includes the heterocyclic compound as a dopant.

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