KR20200060243A - Indolocarbazole derivatives and organoelectroluminescent device using the same - Google Patents

Abstract

The present invention relates to a polycyclic aromatic indolocarbazole derivative compound using a structure comprising boron that can be employed in various organic substrate layers in an organic light emitting device; and a high-efficiency, long-life organic light emitting device having significantly improved luminous efficiency by including the compound. An organic light emitting compound is represented by chemical formula A.

Description

Indolocarbazole derivatives and organoelectroluminescent device using the same}

The present invention relates to an indolocarbazole derivative compound and a high-efficiency, long-life organic light emitting device having significantly improved luminous efficiency using the same.

In the organic light emitting device, electrons injected from an electron injection electrode (cathode electrode) and holes injected from a hole injection electrode (anode electrode) combine in the light emitting layer to form an exiton, and the excitons generate energy. It is a self-emission type device that emits light while emitting, and such an organic light-emitting device is receiving attention as a next-generation light source because of its low driving voltage, high brightness, wide viewing angle, and fast response speed, and is applicable to a full-color flat panel light emitting display. .

In order for such an organic light emitting device to exhibit the above characteristics, the structure of the organic layer in the device is optimized, and a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, and an electron blocking material that constitute each organic layer It should be preceded that the back is supported by a stable and efficient material, but still, the structure of the organic layer for a stable and efficient organic light emitting device and the development of each material are still in need.

In addition, in recent years, as well as research to improve the characteristics of organic light emitting devices by changing the performance of each organic material, as well as to improve color purity and improve luminous efficiency by optimized optical thickness between anode and cathode. It is considered as one of the important factors for improving performance, and as an example of such a method, a desired light efficiency and excellent color purity are obtained by using a capping layer (optical efficiency improving layer, capping layer) on an electrode.

Thus, there is a need to develop a structure of a device capable of improving the luminescence properties of the organic light emitting device and a new material supporting the device.

Therefore, the present invention is to be employed in the organic layer of the device to provide an organic light emitting compound and an organic light emitting device comprising the same that can realize a high efficiency, long life organic light emitting device.

In order to solve the above problems, the present invention provides an organic light-emitting compound represented by the following [Formula A].

[Formula A]

The more specific structure of the above [Formula A] and the definition of each substituent, and the specific compound of the indolocarbazole derivative according to the present invention embodied in [Formula A] will be described later.

In addition, the present invention includes a first electrode, a second electrode facing the first electrode, and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer is an indole represented by [Formula A] It provides an organic light emitting device comprising at least one carbazole derivative compound.

The indolocarbazole derivative compound according to the present invention is employed in an organic layer in a device to realize a high efficiency and long life organic light emitting device.

1 is a representative view showing the structure of an indolocarbazole derivative compound according to the present invention.

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

The present invention is included in an organic light emitting device, and relates to an indolocarbazole derivative compound represented by the following [Formula A], characterized by being capable of realizing an organic light emitting device having high efficiency and long life.

[Formula A]

In the above [Formula A],

R ₁ to R ₁₇ are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms. , Substituted or unsubstituted cycloalkenyl group having 5 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted carbon number 1 to Alkyl thioxy group of 20, substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, substituted or Unsubstituted aryl group having 6 to 50 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms, substituted or unsubstituted silyl group, substituted or unsubstituted germanium group, substituted or unsubstituted boron group, substituted Or any one selected from the group consisting of an unsubstituted aluminum group, carbonyl group, phosphoryl group, amino group, nitrile group, hydroxy group, nitro group, halogen group, selenium group, tellurium group, amide group and ester group.

The R ₁ to R ₁₇ and their substituents may form a condensed ring of an aliphatic, aromatic, aliphatic heteroaromatic or aromatic group with an adjacent group.

On the other hand, the term 'substituted or unsubstituted' in the present invention, R ₁ to R ₁₇ and the like deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group, alkoxy group, alkylamino group, arylamino group, heteroarylamino group, respectively , An alkylsilyl group, an arylsilyl group, an aryloxy group, an aryl group, a heteroaryl group, one or two or more substituents selected from the group consisting of germanium, phosphorus, boron, hydrogen, and deuterium, or two or more substituents among the substituents It means that it is substituted with a linked substituent or does not have any substituent.

In addition, the range of the carbon number of the alkyl group or the aryl group in the 'substituted or unsubstituted alkyl group having 1 to 10 carbon atoms', 'substituted or unsubstituted aryl group having 6 to 30 carbon atoms', etc., considers the part in which the substituent is substituted. It does not mean the total number of carbon atoms constituting the alkyl portion or the aryl portion when viewed as unsubstituted. For example, the phenyl group substituted with a butyl group in the para position means that it corresponds to an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

In addition, in the present invention, the meaning of combining with adjacent groups to form a ring means combining with adjacent groups to form a substituted or unsubstituted alicyclic, aromatic ring, and 'adjacent substituents' is applicable. It may mean a substituent substituted on an atom directly connected to a substituted atom with a substituent, a substituent positioned closest to the corresponding substituent and three-dimensionally, or another substituent substituted on the atom in which the substituent is substituted. For example, two substituents substituted at the ortho position on the benzene ring and two substituents substituted on the same carbon in the aliphatic ring may be interpreted as 'adjacent substituents' to each other.

In the present invention, the alkyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 1 to 20. Specific examples are methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1- Ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl- 2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert -Octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group , Isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, and the like, but are not limited to these.

In the present invention, the alkenyl group includes a straight chain or a branched chain, and may be further substituted by other substituents, specifically, a vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butene Neil group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 3-methyl-1-butenyl group, 1,3-butadienyl group, allyl group, 1-phenylvinyl-1-yl group , 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2- (naphthyl-1-yl) vinyl-1-yl group, 2,2-bis (diphenyl -1-yl) vinyl-1-yl group, styrenyl group, styrenyl group, and the like, but are not limited to these.

In the present invention, the alkynyl group also includes a straight chain or a branched chain, and may be further substituted by other substituents, including, but not limited to, ethynyl, 2-propynyl, and the like. Does not work.

In the present invention, the cycloalkyl group includes a monocyclic or polycyclic group, and may be further substituted by another substituent, and a polycyclic group refers to a group in which a cycloalkyl group is directly connected or condensed with another ring group, and the other ring group is a cycloalkyl group. It may be, but may be another type of ring group, such as a heterocycloalkyl group, an aryl group, a heteroaryl group, and the like. Specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2 , 3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, and the like, but is not limited thereto.

In the present invention, the heterocycloalkyl group includes heteroatoms such as O, S, Se, N, or Si, and also includes monocyclic or polycyclic, and may be further substituted by other substituents, and polycyclic is heterocyclo The alkyl group means a group directly connected to or condensed with another ring group, and the other ring group may be a heterocycloalkyl group, but may also be a different type of ring group, such as a cycloalkyl group, an aryl group, a heteroaryl group, and the like.

In the present invention, the aryl group may be monocyclic or polycyclic, and examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group, a stilbene group, etc. , Phenanthrenyl group, pyrenyl group, perylene group, tetrasenyl group, chrysenyl group, fluorenyl group, acenaphthacenyl group, triphenylene group, fluoranthrene group, etc., but the scope of the present invention It is not limited to these examples.

In the present invention, the heteroaryl group is a heterocyclic group containing a heteroatom, for example, thiophene group, furan group, pyrrol group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, Bipyridyl group, pyrimidyl group, triazine group, triazole group, acridil group, pyridazine group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyridyl group Pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzo Furanyl group, dibenzofuranyl group, phenanthroline group, thiazolyl group, isooxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, and the like, but is not limited thereto. .

In the present invention, the alkoxy group may be specifically methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, and the like, but is not limited thereto.

In the present invention, the silyl group means a silyl group substituted with alkyl or aryl group substituted with aryl, and specific examples of the silyl group include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, and dimethoxyphenylsilyl , Diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, dimethylfurylsilyl, and the like.

In the present invention, the amine group may be -NH ₂ , an alkylamine group, an arylamine group, etc., the arylamine group means an amine substituted with aryl, and the alkylamine group means an amine substituted with alkyl, and an arylamine group Examples of the 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, c It may be a cyclic aryl group, the arylamine group containing 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. In addition, the aryl group in the arylamine group may be selected from the examples of the aryl group described above.

In the present invention, the aryl group in the aryloxy group and aryl thioxy group is the same as the exemplified aryl group described above, and specifically, the aryloxy group is a phenoxy group, p-tolyloxy group, m-tolyloxy group, 3,5- Dimethyl-phenoxy group, 2,4,6-trimethylphenoxy group, p-tert-butylphenoxy group, 3-biphenyloxy group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4 -Methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthryloxy group, 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenan Triyloxy group, 9-phenanthryloxy group, and the like, and arylthioxy groups include, but are not limited to, phenylthioxy group, 2-methylphenylthioxy group, and 4-tert-butylphenylthioxy group.

In the present invention, examples of the halogen group include fluorine, chlorine, bromine or iodine.

More specifically, the indolocarbazole derivative compound represented by [Chemical Formula A] according to the present invention may be any one selected from compounds represented by the following formula, and through this, specific substituents can be clearly identified. Thereby, the scope of [Formula A] according to the present invention is not limited.

As can be seen from the specific compound, while forming a hetero polycyclic aromatic structure including a boron atom in the indolocarbazole skeleton, various substituents can be introduced into the organic light emitting material having unique properties of the substituents, For example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an electron blocking layer, and a hole blocking layer used in the manufacture of an organic light emitting device are introduced into the above structures, and thus required by each organic layer. It is possible to manufacture a material that satisfies the conditions, and through this, a high efficiency organic light emitting device can be realized. In addition, the compound according to the present invention may be useful alone or in combination with other compounds as various organic material layer materials, or may be used in a capping layer (CPL).

In addition, another aspect of the present invention relates to an organic light emitting device comprising a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layer is represented by [Formula A] It may include at least one organic light-emitting compound according to the present invention represented by.

That is, the organic light emitting device according to an embodiment of the present invention may be made of a structure including a first electrode and a second electrode and an organic material layer disposed between the organic light emitting compound of [Chemical Formula A] according to the present invention. Except for use in the organic material layer of the device, it can be manufactured using a conventional device manufacturing method and material.

The organic layer of the organic light emitting device according to the present invention may have a single layer structure, but may have a multi-layer structure in which two or more organic layers are stacked. For example, it may have a structure including a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron blocking layer, an electron transport layer, an electron injection layer, and the like. However, the present invention is not limited thereto, and may include a smaller number or a larger number of organic layers, and the organic material layer structure of the preferred organic light emitting device according to the present invention will be described in more detail in the following embodiments.

In addition, the organic electroluminescent device according to an embodiment of the present invention includes a substrate, a first electrode (anode), an organic material layer, a second electrode (cathode) and a light efficiency improving layer, wherein the light efficiency improving layer is a lower electrode ( Bottom emission) or a second electrode (Top emission).

In the method formed on the top of the second electrode (Top emission), the light formed from the light emitting layer is emitted toward the cathode, while the light emitted toward the cathode passes through the light efficiency improving layer (CPL) formed of the compound according to the present invention having a relatively high refractive index. The wavelength of is amplified and thus the light efficiency is increased. In addition, the method formed on the bottom of the first electrode (Bottom emission) also adopts the compound according to the present invention to the light efficiency improving layer by the same principle, thereby improving the light efficiency of the organic electric device.

Hereinafter, an embodiment of the organic light emitting device according to the present invention will be described in more detail.

The organic light emitting device according to the present invention includes an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode, and if necessary, may further include a hole injection layer between the anode and the hole transport layer, and also an electron between the electron transport layer and the cathode It may further include an injection layer, in addition, it is also possible to further form an intermediate layer of one layer or two layers, a hole blocking layer or an electron blocking layer may be further formed, and as described above, a device such as a light efficiency improving layer, etc. Depending on the characteristics of the may further include an organic layer having a variety of functions.

First, the organic light emitting device according to the present invention is characterized in that it comprises an anthracene derivative represented by the following [Chemical Formula C] in the light emitting layer as a host compound.

[Formula C]

In the above [Formula C],

R ₂₁ to R ₂₈ are each the same or different, and are the same as defined in R ₁ to R ₁₇ of [Formula A].

Ar ₉ and Ar ₁₀ are the same or different from each other, and independently of each other, hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, substituted or unsubstituted Alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, substituted or Unsubstituted heteroaryl group having 2 to 50 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms Oxy group, substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, substituted or unsubstituted arylthiooxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted It may be any one selected from arylamine groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 1 to 30 carbon atoms, and substituted or unsubstituted arylsilyl groups having 6 to 30 carbon atoms.

L ₁₃ is a single bond, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms, preferably a single bond, or It may be a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, k is an integer of 1 to 3, when k is 2 or more, each L ₁₃ is the same or different from each other.

In addition, Ar ₉ of [Chemical Formula C] is characterized in that it is a substituent represented by the following [Chemical Formula C-1].

[Chemical Formula C-1]

In the above [Chemical Formula C-1],

Each of R ₃₁ to R ₃₅ is the same or different, and is the same as defined in R ₁ to R ₁₇ of claim 1 above, and may combine with adjacent substituents to form a saturated or unsaturated ring.

The [Chemical Formula C] employed in the organic light emitting device according to the present invention may be any one selected from the following [Chemical Formula C1] to [Chemical Formula C48].

In addition, the organic light emitting device according to the present invention may further include a hole transport layer, an electron blocking layer, and a light efficiency improving layer, respectively, and a compound represented by the following [Formula D] in the hole transport layer, the electron blocking layer and the light efficiency improving layer, respectively It is characterized by including.

[Formula D]

In the above [Formula D],

R ₄₁ to R ₄₃ are the same or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted carbon number 7 to 50 arylalkyl groups, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 30 carbon atoms, and halogen groups It is any one selected from.

L ₃₁ to L ₃₄ are the same as or different from each other, and each independently a single bond, a substituted or unsubstituted arylene group having 6 to 50 carbon atoms and a substituted or unsubstituted heteroarylene group having 2 to 50 carbon atoms.

Ar ₃₁ to Ar ₃₄ are the same or different from each other, and each independently selected from a substituted or unsubstituted aryl group having 6 to 50 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms.

n is an integer from 0 to 4, and when n is 2 or more, each aromatic ring containing R ₄₃ is the same or different from each other, m ₁ to m ₃ are integers from 0 to 4, and when they are each 2 or more, Each R ₄₁ , R ₄₂ , or R ₄₃ is the same or different from each other.

The carbon atom of the aromatic ring to which R ₄₁ to R ₄₃ is not bonded is bonded to hydrogen or deuterium.

In addition, at least one of the Ar ₃₁ to Ar ₃₄ is characterized in that it is a substituent represented by the following [Formula E].

[Formula E]

In the above [Formula E],

R ₅₁ to R ₅₄ are the same or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted carbon number 2 to 30 alkenyl groups, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl groups having 5 to 30 carbon atoms, substituted or unsubstituted Substituted heteroaryl group having 2 to 50 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryl oxide having 6 to 30 carbon atoms Timing, substituted or unsubstituted alkyl thioxy group having 1 to 30 carbon atoms, substituted or unsubstituted arylthio group having 5 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted carbon number Any one selected from 5 to 30 arylamine groups, substituted or unsubstituted alkylsilyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl groups having 5 to 30 carbon atoms, nitro groups, cyano groups, and halogen groups , These can each be connected to each other to form a ring.

Y is a carbon atom or a nitrogen atom, Z is a carbon atom, an oxygen atom, a sulfur atom or a nitrogen atom.

Ar ₃₅ to Ar ₃₇ are the same or different from each other, and each independently selected from a substituted or unsubstituted aryl group having 5 to 50 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms.

When Z is an oxygen atom or a sulfur atom, Ar ₃₇ is not present, and when Y and Z are nitrogen atoms, only one of Ar ₃₅ , Ar ₃₆ and Ar ₃₇ is present, and when Y is a nitrogen atom and Z is a carbon atom, Ar ₃₆ is does not exist.

However, one of R ₅₁ to R ₅₄ and Ar ₃₅ to Ar ₃₇ is a single bond connected to one of the linking groups L ₃₁ to L ₃₄ in the above [Formula D].

The [Chemical Formula D] employed in the organic light emitting device according to the present invention may be any one selected from [Chemical Formula D1] to [Chemical Formula D79].

In addition, the [Chemical Formula D] employed in the organic light emitting device according to the present invention may be any one selected from the following [Chemical Formula D101] to [Chemical Formula D145].

In addition, the organic light emitting device according to the present invention may further include a hole transport layer, an electron blocking layer, and a light efficiency improving layer, respectively, and a compound represented by the following [Formula F] in the hole transport layer, the electron blocking layer and the light efficiency improving layer, respectively It is characterized by including.

[Formula F]

In the above [Formula F],

R ₆₁ to R ₆₃ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted carbon number 2 to 30 alkenyl groups, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl groups having 5 to 30 carbon atoms, substituted or unsubstituted Substituted heteroaryl group having 2 to 50 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryl oxide having 6 to 30 carbon atoms Timing, substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, substituted or unsubstituted arylthiooxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted carbon number 6 to 30 arylamine group, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyl germanium group having 1 to 30 carbon atoms, It is any one selected from substituted or unsubstituted aryl germanium groups having 1 to 30 carbon atoms, cyano groups, nitro groups, and halogen groups.

r ₅₁ to Ar ₅₄ are the same or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

 The [Formula F] employed in the organic light emitting device according to the invention may be any one selected from the following [Formula F1] to [Formula F33].

Meanwhile, a detailed structure of the organic light emitting device according to an embodiment of the present invention and a manufacturing method thereof are as follows.

First, an anode is formed by coating a material for the anode electrode on the substrate. Here, as a substrate, a substrate used in a conventional organic light emitting device is used, but an organic substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and water resistance is preferable. In addition, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), and zinc oxide (ZnO) are used as the anode electrode material, which is transparent and has excellent conductivity.

A hole injection layer is formed by vacuum thermal evaporation or spin coating of a hole injection layer material on the anode electrode, and then a hole transport layer material is vacuum heat deposited or spin coated on the hole injection layer to form a hole transport layer. .

The hole injection layer material can be used without particular limitation as long as it is commonly used in the art, and as a specific example, 2-TNATA [4,4 ', 4 "-tris (2-naphthylphenyl-phenylamino) -triphenylamine] , NPD [N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine)], TPD [N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'- biphenyl-4,4'-diamine], DNTPD [N, N'-diphenyl-N, N'-bis- [4- (phenyl-m-tolyl-amino) -phenyl] -biphenyl-4,4'-diamine ] Etc. can be used.

In addition, the hole transport layer material is also not particularly limited as long as it is commonly used in the art, for example, N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1- Biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalen-1-yl) -N, N'-diphenylbenzidine (α-NPD) or the like can be used.

Subsequently, a hole auxiliary layer and a light emitting layer may be sequentially stacked on the hole transport layer, and a hole blocking layer may be selectively deposited on the light emitting layer to form a thin film as a vacuum deposition method or a spin coating method. The hole blocking layer serves to prevent this problem by using a material with a very low level of HOMO (Highest Occupied Molecular Orbital) because the life and efficiency of the device is reduced when holes pass through the organic light emitting layer and enter the cathode. . At this time, the hole-blocking material used is not particularly limited, but has an electron transporting ability and has a higher ionization potential than the light emitting compound, and typically BAlq, BCP, TPBI, etc. can be used.

As the material used for the hole blocking layer, any one selected from BAlq, BCP, Bphen, TPBI, NTAZ, BeBq ₂ , OXD-7, Liq and [Chemical Formula 501] to [Chemical Formula 507] may be used, but is not limited thereto. It does not work.

BAlq BCP Bphen

TPBI NTAZ BeBq ₂

OXD-7 Liq

[Chemical Formula 501] [Chemical Formula 502] [Formula 503]

[Chemical Formula 504] [Chemical Formula 505] [Formula 506]

[Formula 507]

By depositing an electron transport layer on the hole blocking layer through a vacuum deposition method or a spin coating method, an electron injection layer is formed and a metal for forming a cathode is vacuum-deposited on the top of the electron injection layer to form a cathode electrode. An organic light emitting device according to an embodiment of the is completed.

Here, the cathode forming metals include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver ( Mg-Ag) and the like, and a transmissive cathode using ITO and IZO can be used to obtain a front light emitting device.

As the electron transport layer material, a function of stably transporting electrons injected from the cathode, a known electron transport material can be used. Examples of known electron transport materials include quinoline derivatives, in particular tris (8-quinolinorate) aluminum (Alq3), TAZ, Balq, beryllium bis (benzoquinolin-10-noate) (beryllium bis (benzoquinolin-10- olate: Bebq2), ADN, [Chemical Formula 401], [Chemical Formula 402], oxadiazole derivatives such as PBD, BMD, BND and the like may also be used.

TAZ BAlq

[Compound 401] [Compound 402] BCP

Further, in the electron transport layer used in the present invention, the organometallic compound represented by the following [Chemical Formula C] may be used alone or in combination with the electron transport layer material.

[Formula C]

In the above [Formula C],

Y is a portion selected from C, N, O, and S directly bonded to M to form a single bond, and a portion selected from C, N, O, and S forming a coordination bond to M. And a ligand chelated by the single bond and coordination bond. M is an alkali metal, alkaline earth metal, aluminum (Al) or boron (B) atom.

OA is a monovalent ligand capable of single bond or coordination with the M, wherein O is oxygen, and A is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, Substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkyl having 5 to 30 carbon atoms It is any one selected from an alkenyl group and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having O, N or S as a hetero atom.

Further, when M is one metal selected from alkali metals, m is 1, n is 0, and when M is one metal selected from alkaline earth metals, m is 1, n is 1, or m Silver 2, n is 0, and when M is boron or aluminum, m is any one of 1 to 3, n is any one of 0 to 2, and m + n satisfies 3.

The 'substituted' in the 'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group, alkoxy group, alkylamino group, arylamino group, hetero arylamino group, alkylsilyl group, arylsilyl group, It means substituted with one or more substituents selected from the group consisting of aryloxy group, aryl group, heteroaryl group, germanium, phosphorus and boron.

In addition, each of Y is the same or different, and may be any one selected from the following [Structural C1] to [Structural C39] independently of each other, but is not limited thereto.

[Structural Formula C1] [Structural Formula C2] [Structural Formula C3]

[Structural Formula C4] [Structural Formula C5] [Structural Formula C6]

[Structural Formula C7] [Structural Formula C8] [Structural Formula C9] [Structural Formula C10]

[Structural Formula C11] [Structural Formula C12] [Structural Formula C13]

[Structural Formula C14] [Structural Formula C15] [Structural Formula C16]

[Structural Formula C17] [Structural Formula C18] [Structural Formula C19] [Structural Formula C20]

[Structural Formula C21] [Structural Formula C22] [Structural Formula C23]

[Structural Formula C24] [Structural Formula C25] [Structural Formula C26]

[Structural Formula C27] [Structural Formula C28] [Structural Formula C29] [Structural C30]

[Structural Formula C31] [Structural Formula C32] [Structural Formula C33]

[Structural Formula C34] [Structural Formula C35] [Structural Formula C36]

[Structural Formula C37] [Structural Formula C38] [Structural Formula C39]

In the above [Structural Formula C1] to [Structural Formula C39],

R is the same or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted Heteroaryl group having 3 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or Unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and substituted or unsubstituted arylsilyl having 6 to 30 carbon atoms. It is selected from groups, and may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or fused ring.

L is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted 5 to 30 carbon atoms Heteroaryl group and a substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms, L is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, 3 to 20 carbon atoms It is further substituted with one or more substituents selected from heteroaryl groups, cyano groups, halogen groups, deuterium and hydrogen, and may be connected to adjacent substituents with alkylene or alkenylene to form a spiro ring or fused ring.

In addition, the organic light emitting device according to the present invention includes a light emitting layer, the light emitting layer may further include one or more dopant compounds, and the light emitting dopant compound applied to the organic electroluminescent device of the present invention is not particularly limited. However, it may be one or more compounds selected from compounds represented by the following [General Formula A-1] to [General Formula J-1].

[General Formula A-1]

The M is selected from the group consisting of metals of Groups 7, 8, 9, 10, 11, 13, 14, 15, and 16, preferably Ir, Pt, Pd, Rh, Re , Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au and Ag. In addition, the L ₁ , L ₂ and L ₃ are the same as or different from each other as a ligand, and each independently selected from the following [Structural D], but is not limited thereto. In addition, * in the following structural formula D represents a site that binds to the metal ion M.

[Structural Formula D]

In the above [Formula D],

R are different or the same as each other, and each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 50 carbon atoms, substituted or unsubstituted carbon number Heteroaryl group of 5 to 50, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted Substituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylamino group having 6 to 30 carbon atoms and substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms. It may be any one selected from.

Each R is independently selected from alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, aryl groups having 6 to 40 carbon atoms, heteroaryl groups having 3 to 20 carbon atoms, cyano groups, halogen groups, deuterium, and hydrogen. It may be further substituted with one or more substituents.

In addition, R may be connected to each adjacent substituent by alkylene or alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring.

The L may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or fused ring.

As an example, the dopant represented by [General Formula A-1] may be any one selected from the following compounds, but is not limited thereto.

[General Formula B-1]

In the above [General Formula B-1],

M ^A1 represents the same metal ion as defined in [General Formula A-1], and Y ^A11 , Y ^A14 , Y ^A15 and Y ^A18 each independently represent a carbon atom or a nitrogen atom, Y ^A12 , Y ^A13 , Y ^A16 and Y ^A17 each independently represent a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom, and a sulfur atom, and L ^A11 , L ^A12 , L ^A13 , and L ^A14 are each a linking group as previously defined. And Q ^A11 and Q ^A12 represent partial structures containing atoms that bind to M ^A1 .

The exemplary structure of the compound represented by [General Formula B-1] is as follows, but is not limited thereto.

[General Formula C-1]

In the above [General Formula C-1],

M ^B1 represents the same metal ion as defined in [General Formula A-1], Y ^B11 , Y ^B14 , Y ^B15 and Y ^B18 each independently represent a carbon atom or a nitrogen atom, Y ^B12 , Y ^B13 , Y ^B16 And Y ^B17 each independently represents a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom, and a sulfur atom, L ^B11 , L ^B12 , L ^B13 , and L ^B14 represent a linking group, and Q ^B11 , Q ^B12 are It shows the partial structure containing the atom couple | bonded with M ^B1 .

The exemplary structure of the compound represented by [General Formula C-1] is as follows, but is not limited thereto.

[General Formula D-1]

In the above [General Formula D-1],

M ^C1 represents a metal ion as the same metal ion as defined in [General Formula A-1], and R ^C11 and R ^C12 are each independently a hydrogen atom, a substituent that connects to each other, and forms a 5-membered ring. Represents a substituent, R ^C13 , R ^C14 each independently represents a hydrogen atom, a substituent that connects to each other to form a 5-membered ring, or a substituent that does not have anything to connect to each other, G ^C11 , G ^C12 each independently represents a nitrogen atom, a substitution Or represents an unsubstituted carbon atom, L ^C11 , L ^C12 represents a linking group, and Q ^C11 , Q ^C12 represents a partial structure containing an atom bound to M ^C1 .

The exemplary structure of the compound represented by [General Formula D-1] is as follows, but is not limited thereto.

[General Formula E-1]

In the above [General Formula E-1],

M ^D1 represents the same metal ion as defined in [General Formula A-1], G ^D11 and G ^D12 each independently represent a nitrogen atom, a substituted or unsubstituted carbon atom, and J ^D11 , J ^D12 , J ^D13 and J ^D14 represents a group of atoms required to form a 5-membered ring independently of each other, and L ^D11 and L ^D12 represent linking groups.

The exemplary structure of the compound represented by [General Formula E-1] is as follows, but is not limited thereto.

[General Formula F-1]

In the above [General Formula F-1],

M ^E1 represents the same metal ion as defined in [General Formula A-1], and J ^E11 and J ^E12 each independently represent a group of atoms necessary to form a 5-membered ring, G ^E11 , G ^E12 , G ^E13 and G ^E14 each independently represents a nitrogen atom, a substituted or unsubstituted carbon atom, and Y ^E11 , Y ^E12 , Y ^E13 and Y ^E14 each independently represent a nitrogen atom, a substituted or unsubstituted carbon atom.

The exemplary structure of the compound represented by [General Formula F-1] is as follows, but is not limited thereto.

[General formula G-1]

In the above [General Formula G-1],

M ^F1 represents the same metal ion as defined in [General Formula A-1].

L ^F11 , L ^F12 and L ^F13 represent a linking group, R ^F11 , R ^F12 , R ^F13 and R ^F14 represent a substituent, and R ^F11 and R ^F12 , R ^F12 and R ^F13 , R ^F13 and R ^F14 are connected to each other The ring formed by R ^F1 and R ^F12 , R ^F13 and R ^F14 is a 5-membered ring. In addition, Q ^F11 and Q ^F12 represent partial structures containing atoms that bind to M ^F1 .

The exemplary structure of the compound represented by [General Formula G-1] is as follows, but is not limited thereto.

[General Formula H-1] [General Formula H-2] [General Formula H-3]

In the above [General Formula H-1] to [General Formula H-3],

R ¹¹ , R ¹² are alkyl, aryl or heteroaryl substituents; In addition, a fused ring with a substituent adjacent to each other may be formed, and q11 and q12 are integers of 0 to 4, preferably 0 to 2.

In addition, when q11 and q12 are 2 to 4, a plurality of R11 and R12 may be the same or different, respectively.

L ¹ is a ligand that binds to platinum, and is preferably a ligand capable of forming an ortho metalized platinum complex, a nitrogen-containing heterocyclic ligand, a diketone ligand, or a halogen ligand, and more preferably an ortho metal. It is a ligand forming a platinum complex, a bipyridyl ligand, or a phenanthroline ligand.

n ¹ is an integer from 0 to 3, preferably 0, m ¹ is 1 or 2, and preferably 2.

Moreover, it is preferable that n ¹ and m ¹ are such that the metal complex represented by the general formula H-1 is a neutral complex.

In the above [General Formula H-2],

R ²¹ , R ²² , n ² , m ² , q ²² , L ² are the same as R ¹¹ , R ¹² , n ¹ , m ¹ , q ¹² , L ¹ , respectively, and q ²¹ is an integer from 0 to 2 , 0 is preferred.

In the above [General Formula H-3],

R ³¹ , n ³ , m ³ , L ³ are the same as R ¹¹ , n ¹ , m ¹ , L ¹ , respectively, q ³¹ represents an integer from 0 to 8, 0 to 2 is preferable, and 0 is more desirable.

Examples of the specific compounds of [General Formula H-1] to [General Formula H-3] are as follows, but are not limited thereto.

[Formula I-1]

In the above [General Formula I-1],

Ring A, Ring B, Ring C and Ring D represent a nitrogen-containing heterocycle in which any two rings of Rings A to D may have substituents, and the other two rings are aryl or heterocycles in which rings may have substituents It represents an aryl ring, represents, and may form a condensed ring with ring A and ring B, ring A and ring C, and / or ring B and ring D. X ¹ , X ² , X ³ and X ⁴ represent a nitrogen atom in which two of them are coordinated to a platinum atom, and the other two represent a carbon atom or a nitrogen atom. Q ¹ , Q ² and Q ³ each independently represent a divalent atom (mono) or bond, but Q ¹ , Q ² and Q ³ do not simultaneously represent a bond. Z ¹ , Z ² , Z ³ and Z ⁴ are two coordination bonds, and the other two are covalent bonds, oxygen atoms or sulfur atoms.

Examples of the specific compound of [General Formula I-1] are as follows, but are not limited thereto.

[General Formula J-1]

In the above [General Formula J-1],

M represents the same metal ion as defined in [General Formula A-1], Ar1 represents a substituted or unsubstituted ring structure, and two azomethine bonds (-C = N-) that bind to the M In, the nitrogen atom (N) each binds to the M, and as a whole forms a tridentate ligand bonded to the M at three loci.

In addition, in Ar1, C represents a carbon atom constituting the ring structure represented by Ar1. In addition, R1 and R2 may be the same as or different from each other, and each represents a substituted or unsubstituted alkyl group or aryl group, and L represents a monodentate ligand.

In the above [General Formula J-1], it is preferable that M is Pt. Moreover, as said Ar1, it is preferable to select from 5-membered ring, 6-membered ring, and these condensed ring groups.

Examples of the specific compound of [General Formula J-1] are as follows, but are not limited thereto.

In addition, the light emitting layer may further include various host materials and various dopant materials in addition to the dopant.

In addition, each of the organic layers may be formed by a single molecule deposition method or a solution process, wherein the deposition method evaporates a material used as a material for forming each layer through heating in a vacuum or a low pressure state. It means a method of forming a thin film, and the solution process mixes a material used as a material for forming each layer with a solvent and ink-jet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating. It means a method of forming a thin film through a method such as.

In addition, the organic light emitting device according to the present invention can be used in a device selected from a flat panel display device, a flexible display device, a monochrome or white flat lighting device, and a monochrome or white flexible lighting device.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are intended to illustrate the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited thereby.

Synthetic example  1: Synthesis of Compound 1

(One) Synthetic example  1-1. Synthesis of <Formula 1-a>

<Formula 1-a>

1,5-dichloro-2,4-dinitrobenzene (40.0 g, 0.123 mol), phenylboronic acid (44.9 g, 0.368 mol), tetrakistriphenylphosphine palladium (2.8) in a 1000 mL round bottom flask g, 0.0025 mol), potassium carbonate (50.9 g, 0.368 mol), 120 mL of ethanol, 200 mL of toluene and 120 mL of water were added to reflux. When the reaction is complete, the organic layer obtained by extraction with water and ethyl acetate is anhydrously treated with magnesium sulfate, concentrated under reduced pressure, and separated by column chromatography using hexane and ethyl acetate as a developing solvent to <Formula 1-a> to 27.5. g was obtained (yield 70.0%).

(2) Synthetic example  1-2. Synthesis of <Formula 1-b>

<Formula 1-a> <Formula 1-b>

In a 1000 mL round bottom flask, <Formula 1-a> (27.5 g, 0.086 mmol), triethylphosphite (57.8 g, 0.348 mol), and tertbutylbenzene 550 mL were added and stirred under reflux. After completion of the reaction, dichloromethane, methanol It was recrystallized using to obtain 10.8 g of <Formula 1-b> (yield 49.0%).

(3) Synthetic example  1-3. Synthesis of <Formula 1-c>

<Formula 1-b> <Formula 1-c>

To a 250 mL round bottom flask <Formula 1-b> (12 g, 0.047 mol), 1-bromo-2-fluoro-4-iodobenzene (56.4 g, 0.187 mol), cesium carbonate (61.0 g, 0.187 mol) was added in order, 300 mL of dimethylformamide was added, and the mixture was refluxed at 153 ° C for 1 day. When the reaction was completed, extraction was performed using 500 mL of methylene chloride and 300 mL of distilled water. The organic layer was concentrated under reduced pressure to obtain 32.2 g of <Formula 1-c> by column chromatography with methylene chloride: hexane = 1: 5 (yield 84%).

(4) Synthetic example  1-4. Synthesis of <Formula 1-d>

<Formula 1-c> <Formula 1-d>

In a 500 mL round bottom flask <Formula 1-c> (32.2 g, 0.039 mol), N-phenyl-2-naphthalenamine (13.3 g, 0.079 mol), tris (dibenzylideneacetone) dipalladium (0) (1.4 g, 0.0016 mol), sodium tert-butoxide (7.6 g, 0.079 mol), toluene 320 mL was added and refluxed. After the reaction was completed, the mixture was filtered in a hot state, concentrated under reduced pressure, and subjected to column chromatography with methylene chloride and hexane as a developing solvent to obtain 21.2 g of <Formula 1-d> (yield 60%).

(5) Synthesis Example 1-5. Synthesis of <Compound 1>

<Formula 1-d> <Compound 1>

In a 500 mL round-bottom flask, 160 mL of <Formula 1-d> (21.3 g, 0.024 mol), tert-butylbenzene was added under nitrogen flow, lowered to minus 40 ° C, and 44.2 mL of normal-butyllithium was added dropwise and added dropwise. When was completed, the hexane was removed by raising to 60 ° C. Again, the reaction temperature was lowered to 40 ° C., and boron tribromide (11.8 g, 0.047 mol) was added dropwise. When the dropwise addition was completed, the temperature was raised to room temperature and stirred for 30 minutes. The reaction temperature was again cooled to 0 ° C, diisopropylethylamine (6.1 g, 0.047 mol) was added dropwise, and when the dropwise addition was completed, the reaction temperature was raised to 120 ° C and stirred for 3 hours. After the reaction was completed, 100 mL of sodium acetate aqueous solution was added dropwise. Extracted with ethyl acetate and water, the organic layer was concentrated under reduced pressure, and separated by column chromatography using hexane and methylene chloride as a developing solvent to obtain 2.3 g of <Compound 1> (yield 13%).

MS (MALDI-TOF): m / z 851.3 [M ⁺ ]

Synthetic example  2: Synthesis of Compound 3

(One) Synthetic example  2-1. Synthesis of <Formula 2-a>

<Formula 1-b> <Formula 2-a>

In a 500 mL round bottom flask <Formula 1-b> (7.96 g, 0.031 mol), 4-bromo-3-fluoro-1,1'-biphenyl (7.8 g, 0.031 mol), cesium carbonate (10.12 g, 0.031 mol) was added, 159.2 mL of dimethylformamide was added, and the mixture was refluxed at 150 ° C for 1 day. When the reaction was completed, it was extracted using methylene chloride and distilled water. The organic layer was concentrated under reduced pressure, and column chromatography was performed with methylene chloride and heptane to obtain 7.28 g of <Formula 2-a> (yield 48%).

(2) Synthetic example  2-2. Synthesis of <Formula 2-b>

<Formula 2-b>

1-bromo-2-fluoro-4-iodobenzene (30 g, 0.11 mol), bis (4- (tert-butyl) phenyl) amine (25.25 g, 0.090 mol), tris (di) in a round bottom flask Benzylidene acetone) dipalladium (0) (4.57 g, 0.005 mol), sodium tert-butoxide (13.42 g, 0.140 mol), Dppf (5.53 g, 0.010 mol), toluene 360 mL was added and refluxed. After the reaction was completed, the mixture was filtered in a hot state, concentrated under reduced pressure, and subjected to column chromatography with methylene chloride and heptane to obtain 18.55 g of <Formula 2-b> (yield 40.5%).

(3) Synthetic example  2-3. Synthesis of <Formula 2-c>

<Formula 2-c>

In a round bottom flask <Formula 2-a> (7.69 g, 0.0158 mol), <Formula 2-b> (10.75 g, 0.024 mol), Tris (dibenzylideneacetone) dipalladium (0) (1.4 g, 0.0016 mol ), Cesium carbonate (7.71 g, 0.024 mol) was added, 153.8 mL of dimethylformamide was added, and the mixture was refluxed at 150 ° C for 1 day. When the reaction was completed, extraction was performed using ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure, and column chromatography was performed with methylene chloride and heptane to obtain 14.54 g of <Formula 2-c> (yield 99%).

(4) Synthesis Example 2-4. Synthesis of <Compound 3>

<Formula 2-c> <Compound 3>

In a round-bottom flask, 218 mL of <Formula 2-c> (14.54 g, 0.016 mol), tert-butylbenzene was added under nitrogen flow, the temperature was lowered to minus 40 ° C, and 29.58 mL of normal-butyllithium was added dropwise. Hexane was removed by raising to 60 ° C. The reaction temperature was again lowered to minus 40 ° C., and boron tribromide (7.9 g, 0.032 mol) was added dropwise. When the dropwise addition was completed, the temperature was raised to room temperature and stirred for 1 hour. The reaction temperature was again cooled to 0 ° C, diisopropylethylamine (4.08 g, 0.032 mol) was added dropwise, and when the dropwise addition was completed, the reaction temperature was raised to 120 ° C and stirred for 3 hours. After the reaction was completed, a solution of sodium acetate was added dropwise. Extracted with ethyl acetate and water, the organic layer was concentrated under reduced pressure, and separated by column chromatography with hexane and methylene chloride to obtain 1 g of <Compound 3> (yield 8.2%).

MS (MALDI-TOF): m / z 772.5 [M ⁺ ]

Synthetic example  3: Synthesis of Compound 5

In Synthesis Example 1-1, instead of phenylboronic acid, B- [3- (diphenylamino) phenylboronic acid and B- [3- (diphenylboryl) phenylboronic acid are used, and Synthesis Example 1-3 In the same manner as in Synthesis Example 1, using 1-bromo-2-fluorobenzene and 2-bromo-3-fluoronaphthalene instead of 1-bromo-2-fluoro-4-iodobenzene 4.5 g of 5> were obtained (yield 17%).

MS (MALDI-TOF): m / z 798.3 [M ⁺ ]

Synthetic example  4: Synthesis of Compound 7

In Synthesis Example 1-1, phenylboronic acid and 1-naphthylboronic acid are used instead of phenylboronic acid, and in Synthesis Example 1-4, carbazole is used instead of N-phenyl-2-naphthalenamine. 3.4 g of <Compound 7> was obtained by the same method as (Yield 26%).

MS (MALDI-TOF): m / z 797.3 [M ⁺ ]

Synthetic example  5: Synthesis of Compound 8

In Synthesis Example 1-4, instead of N-phenyl-2-naphthalenamine, N-phenyl-2-dibenzofuranamine was used to obtain 2.9 g of <Compound 8> in the same manner as in Synthesis Example 1 (yield 25%).

MS (MALDI-TOF): m / z 1083.4 [M ⁺ ]

Synthetic example  6: Synthesis of Compound 9

In Synthesis Example 1-4, instead of N-phenyl-2-naphthalenamine, 4- (1-naphthalenyl) -N- [4- (2-naphthalenyl) phenyl] benzeneamine was used, which is the same as Synthesis Example 1. 2.7 g of <Compound 8> was obtained by the method (yield 21%).

MS (MALDI-TOF): m / z 1255.6 [M ⁺ ]

Examples 1 to 6: Preparation of organic light emitting device

The ITO glass was patterned to have a light emitting area of 2 mm × 2 mm and then washed. After the ITO glass was mounted in a vacuum chamber, the base pressure was 1 × 10 ^-7 torr, and then DNTPD (700 kPa) and [Formula H] (250 kPa) were deposited on the ITO in this order. The light-emitting layer was formed by mixing the host (BH1) described below with the compound of the present invention (3 wt%) (250 Å), and then using the electron transport layer [Formula E-1] and [Formula E-2] 1 An organic light-emitting device was manufactured by depositing 300 로 of a ratio of 1 and 5 Å and Al (1000 Å) in the order of [Formula E-1] with an electron injection layer. The luminescence properties of the organic light emitting device were measured at 0.4 mA.

[DNTPD] [Formula H]

[Formula E-1] [Formula E-2]

[BH1]

Comparative Examples 1 to 3

An organic light emitting device was manufactured in the same manner except that the following [BD1] to [BD3] were used in place of the compound of the present invention used in Example 1, and the light emission characteristics of the organic light emitting device were measured at 0.4 mA. The structures of [BD1] to [BD3] are as follows.

[BD1] [BD2] [BD3]

For the organic light-emitting device manufactured according to Examples 1 to 6 and Comparative Examples 1 to 3, voltage, luminance, color coordinates, and life were measured, and the results are shown in Table 1 below.

division Dopant Current density External quantum efficiency (%) T90 (hr) Example 1 Compound 1 10 7.9 141 Example 2 Compound 3 10 8.1 150 Example 3 Compound 5 10 8.2 139 Example 4 Compound 6 10 8.2 157 Example 5 Compound 7 10 8.5 162 Example 6 Compound 9 10 8.1 165 Comparative Example 1 BD1 10 4.9 63 Comparative Example 2 BD2 10 5.3 83 Comparative Example 3 BD3 10 5.2 77

As can be seen from [Table 1], the organic light emitting device employing the organic light emitting compound according to the present invention has significantly improved high efficiency and long life characteristics compared to the device employing the compounds of Comparative Examples 1 to 3 Device implementation is possible.

Claims (16)

An organic light-emitting compound represented by the following [Formula A]:
[Formula A]

In the above [Formula A],
R ₁ to R ₁₇ are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms. , Substituted or unsubstituted cycloalkenyl group having 5 to 20 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted carbon number 1 to Alkyl thioxy group of 20, substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, substituted or Unsubstituted aryl group having 6 to 50 carbon atoms, substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms, substituted or unsubstituted silyl group, substituted or unsubstituted germanium group, substituted or unsubstituted boron group, substituted Or an unsubstituted aluminum group, carbonyl group, phosphoryl group, amino group, nitrile group, hydroxy group, nitro group, halogen group, selenium group, tellurium group, amide group and ester group.
The R ₁ to R ₁₇ and their substituents may form a condensed ring of an aliphatic, aromatic, aliphatic heteroaromatic or aromatic group with an adjacent group. According to claim 1,
[Formula A] is an organic light-emitting compound, characterized in that any one selected from compounds represented by the following formula:

A first electrode, a second electrode opposite the first electrode, and an organic layer interposed between the first electrode and the second electrode,
An organic light-emitting device in which the organic layer comprises at least one compound represented by [Formula A] according to claim 1. According to claim 3,
The organic layer includes at least one of an electron injection layer, an electron transport layer, a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer and a light emitting layer,
At least one of the layers of the organic light emitting device, characterized in that it comprises an organic light emitting compound represented by the [Formula A]. According to claim 3,
Further comprising a light efficiency improving layer formed on at least one side opposite to the organic material layer from the top or bottom of the first electrode and the second electrode,
The light efficiency improving layer is an organic light emitting device, characterized in that it comprises a compound represented by [Formula A]. The method of claim 5,
The light efficiency improving layer is formed on at least one of the lower portion of the first electrode or the upper portion of the second electrode. The method of claim 4,
The light emitting layer is an organic light emitting device comprising an anthracene derivative represented by the following [Chemical Formula C] as a host compound:
[Formula C]

In the above [Formula C],
R ₂₁ to R ₂₈ are the same as or different from each other, and are the same as defined in R ₁ to R ₁₇ of claim 1 above,
Ar ₉ and Ar ₁₀ are the same as or different from each other, and independently of each other, hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, substituted or unsubstituted Alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, substituted or Unsubstituted heteroaryl group having 2 to 50 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms Oxy group, substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, substituted or unsubstituted arylthiooxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted Any one selected from arylamine groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 1 to 30 carbon atoms, and substituted or unsubstituted arylsilyl groups having 6 to 30 carbon atoms,
L ₁₃ is a single bond, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms,
k is an integer of 1 to 3, and when k is 2 or more, each L ₁₃ is the same or different from each other. The method of claim 7,
Ar ₉ of the [Chemical Formula C] is an organic light emitting device, characterized in that the substituent represented by the following [Chemical Formula C-1]:
[Chemical Formula C-1]

In the above [Chemical Formula C-1],
Each of R ₃₁ to R ₃₅ is the same or different, and is the same as defined in R ₁ to R ₁₇ of claim 1 above, and may combine with adjacent substituents to form a saturated or unsaturated ring. The method of claim 8,
The [Chemical Formula C] is an organic light emitting device, characterized in that any one selected from the following [Chemical Formula C1] to [Chemical Formula C48]:

The method of claim 5,
The hole transport layer, the electron blocking layer and the light efficiency improving layer, each of the organic light emitting device comprising a compound represented by the following [Formula D]:
[Formula D]

In the above [Formula D],
R ₄₁ to R ₄₃ are the same or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted carbon number 7 to 50 arylalkyl groups, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 30 carbon atoms, and halogen groups Any one selected from
L ₃₁ to L ₃₄ are the same or different from each other, and each independently a single bond, a substituted or unsubstituted arylene group having 6 to 50 carbon atoms and a substituted or unsubstituted heteroarylene group having 2 to 50 carbon atoms, and any one ,
Ar ₃₁ to Ar ₃₄ are the same as or different from each other, and each independently selected from a substituted or unsubstituted aryl group having 6 to 50 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms,
n is an integer of 0 to 4, and when n is 2 or more, each aromatic ring containing R ₄₃ is the same or different from each other,
m ₁ to m ₃ are integers from 0 to 4, and when they are 2 or more, each of R ₄₁ , R ₄₂ , or R ₄₃ is the same or different from each other,
The carbon atom of the aromatic ring to which R ₄₁ to R ₄₃ is not bonded is bonded to hydrogen or deuterium. The method of claim 10,
At least one of the Ar ₃₁ to Ar ₃₄ is an organic light emitting device characterized in that the substituent represented by the following [Formula E]:
[Formula E]

In the above [Formula E],
R ₅₁ to R ₅₄ are the same or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted carbon number 2 to 30 alkenyl groups, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl groups having 5 to 30 carbon atoms, substituted or unsubstituted Substituted heteroaryl group having 2 to 50 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryl oxide having 6 to 30 carbon atoms Timing, substituted or unsubstituted alkyl thioxy group having 1 to 30 carbon atoms, substituted or unsubstituted arylthio group having 5 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted carbon number Any one selected from 5 to 30 arylamine groups, substituted or unsubstituted alkylsilyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl groups having 5 to 30 carbon atoms, nitro groups, cyano groups and halogen groups , Each of which can be connected to each other to form a ring,
Y is a carbon atom or a nitrogen atom, Z is a carbon atom, an oxygen atom, a sulfur atom or a nitrogen atom,
Ar ₃₅ to Ar ₃₇ are the same as or different from each other, and each independently selected from a substituted or unsubstituted aryl group having 5 to 50 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms,
When Z is an oxygen atom or a sulfur atom, Ar ₃₇ is not present, and when Y and Z are nitrogen atoms, only one of Ar ₃₅ , Ar ₃₆ and Ar ₃₇ is present, and when Y is a nitrogen atom and Z is a carbon atom, Ar ₃₆ is Does not exist,
However, one of R ₅₁ to R ₅₄ and Ar ₃₅ to Ar ₃₇ is a single bond connected to one of the linking groups L ₃₁ to L ₃₄ in the above [Formula D]. The method of claim 10,
[Formula D] is an organic light emitting device, characterized in that any one selected from the following [Formula D1] to [Formula D79]:

The method of claim 10,
The [Formula D] is an organic light emitting device, characterized in that any one selected from the following [Formula D101] to [Formula D145]:

The method of claim 5,
The hole transport layer, the electron blocking layer and the light efficiency improving layer, each of the organic light emitting device characterized in that it comprises a compound represented by [Formula F]:
[Formula F]

In the above [Formula F],
R ₆₁ to R ₆₃ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted carbon number 2 to 30 alkenyl groups, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl groups having 5 to 30 carbon atoms, substituted or unsubstituted Substituted heteroaryl group having 2 to 50 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryl oxide having 6 to 30 carbon atoms Timing, substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, substituted or unsubstituted arylthiooxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted carbon number 6 to 30 arylamine group, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyl germanium group having 1 to 30 carbon atoms, A substituted or unsubstituted aryl germanium group having 1 to 30 carbon atoms, any one selected from cyano, nitro and halogen groups,
Ar ₅₁ to Ar ₅₄ are the same or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms. The method of claim 14,
At least one of the Ar ₅₁ to Ar ₅₄ is an organic light emitting device characterized in that the substituent represented by the following [Formula E]:
[Formula E]

In the above [Formula E],
R ₅₁ to R ₅₄ are the same or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted carbon number 2 to 30 alkenyl groups, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl groups having 5 to 30 carbon atoms, substituted or unsubstituted Substituted heteroaryl group having 2 to 50 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryl oxide having 6 to 30 carbon atoms Timing, substituted or unsubstituted alkyl thioxy group having 1 to 30 carbon atoms, substituted or unsubstituted arylthio group having 5 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted carbon number Any one selected from 5 to 30 arylamine groups, substituted or unsubstituted alkylsilyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl groups having 5 to 30 carbon atoms, nitro groups, cyano groups, and halogen groups , Each of which can be connected to each other to form a ring,
Y is a carbon atom or a nitrogen atom, Z is a carbon atom, an oxygen atom, a sulfur atom or a nitrogen atom,
Ar ₃₅ to Ar ₃₇ are the same as or different from each other, and each independently selected from a substituted or unsubstituted aryl group having 5 to 50 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms,
When Z is an oxygen atom or a sulfur atom, Ar ₃₇ is not present, and when Y and Z are nitrogen atoms, only one of Ar ₃₅ , Ar ₃₆ and Ar ₃₇ is present, and when Y is a nitrogen atom and Z is a carbon atom, Ar ₃₆ is Does not exist,
However, one of R ₅₁ to R ₅₄ and Ar ₃₅ to Ar ₃₇ is a single bond connected to one of Ar ₅₁ to Ar ₅₄ in [Formula F]. The method of claim 14,
[Formula F] is an organic light emitting device, characterized in that any one selected from the following [Formula F1] to [Formula F33]:

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