KR102202111B1 - Indolocarbazole derivatives and organoelectroluminescent device using the same - Google Patents

Abstract

The present invention relates to an indolocarbazole polycyclic aromatic derivative compound using a structure containing 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 including the same. .

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 with remarkably improved luminous efficiency using the same.

In the organic light emitting diode, electrons injected from the electron injection electrode (cathode electrode) and holes injected from the hole injection electrode (anode electrode) are combined in the emission layer to form excitons, and the excitons generate energy. It is a self-luminous device that emits light while emitting, and such an organic light emitting device is in the spotlight as a next-generation light source because of its advantage that it can be applied to full-color flat panel light emitting displays with low driving voltage, high brightness, wide viewing angle, and fast response speed. .

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 the material constituting each organic layer is a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, an electron blocking material. It should be preceded that the back is supported by a stable and efficient material, but there is still a need for a stable and efficient organic layer structure for an organic light emitting device and the development of each material.

In addition, in recent years, not only researches to improve the characteristics of organic light-emitting devices by changing the performance of each organic material layer material, but also technology to improve color purity and luminous efficiency by the optical thickness optimized between the anode and the cathode have been developed. It is being conceived as one of the important factors in improving the performance, and as an example of such a method, a capping layer (a capping layer) is used on the electrode to achieve desired light efficiency and excellent color purity.

As described above, the development of a structure of a device capable of improving the light emitting characteristics of an organic light emitting device and a new material supporting the device is continuously required.

Accordingly, an object of the present invention is to provide an organic light-emitting compound and an organic light-emitting device including the same, which is employed in an organic layer of a device to realize a high-efficiency and long-life organic light-emitting device.

The present invention provides an organic light emitting compound represented by the following [Chemical Formula A] in order to solve the above problems.

[Formula A]

A more specific structure of the [Chemical Formula A] and the definition of each substituent, and a specific compound of the indolocarbazole derivative according to the present invention implemented by [Chemical Formula A] will be described later.

In addition, the present invention includes a first electrode, a second electrode opposite to the first electrode, and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer is represented by the [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 can be employed in an organic layer in a device to implement a high-efficiency, long-life organic light-emitting device.

1 is a representative diagram showing the structure of the 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, relates to an indolocarbazole derivative compound represented by the following [Chemical Formula A], characterized in that it can implement a high-efficiency, long-life organic hair removal device.

[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 , A substituted or unsubstituted cycloalkenyl group having 5 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted carbon number of 1 to 20 alkylthioxy group, 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 C6-C50 aryl group, substituted or unsubstituted C3-C50 heteroaryl group, substituted or unsubstituted silyl group, substituted or unsubstituted germanium group, substituted or unsubstituted boron group, substituted Or an unsubstituted aluminum group, a carbonyl group, a phosphoryl group, an amino group, a nitrile group, a hydroxy group, a nitro group, a halogen group, a selenium group, a tellurium group, an amide group, and an ester group.

The R ₁ to R ₁₇ and the substituents thereof may form a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero with a group adjacent to each other.

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

In addition, the range of carbon atoms of the alkyl group or aryl group in the'substituted or unsubstituted alkyl group having 1 to 10 carbon atoms' and'substituted or unsubstituted aryl group having 6 to 30 carbon atoms' consider the portion where the substituent is substituted It does not mean the total number of carbon atoms constituting the alkyl moiety or the aryl moiety when viewed as unsubstituted. For example, a phenyl group in which a butyl group is substituted in the para position 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 forming a ring by bonding with an adjacent group means that a substituted or unsubstituted alicyclic or aromatic ring can be formed by bonding with an adjacent group, and'adjacent substituent' refers to the corresponding The substituent may mean a substituent substituted on an atom directly connected to the substituted atom, a substituent positioned three-dimensionally closest to the substituent, or another substituent substituted on an atom where the substituent is substituted. For example, two substituents substituted at the ortho position in the benzene ring and two substituents substituted on the same carbon in the aliphatic ring may be interpreted as'adjacent substituents'.

In the present invention, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 20. Specific examples include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1- Ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl- 2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cycloheptylmethyl 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 thereto.

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

In the present invention, the alkynyl group also includes a straight chain or a branched chain, and may be further substituted by other substituents, ethynyl, 2-propynyl, etc., but limited thereto. It doesn't work.

In the present invention, the cycloalkyl group includes monocyclic or polycyclic, and may be further substituted by other substituents, and polycyclic refers to a group in which a cycloalkyl group is directly connected or condensed with another ring group, and the other ring group refers to a cycloalkyl group. It may be, but other types of cyclic groups, such as heterocycloalkyl group, aryl group, heteroaryl group, and the like. 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, cyclooctyl group, and the like, but are 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 means heterocyclo An alkyl group refers to a group in which an alkyl group is directly connected or condensed with another ring group, and the other ring group may be a heterocycloalkyl group, but may be another 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, examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group, a stilbene group, and examples of the polycyclic aryl group include a naphthyl group, an anthracenyl group. , Phenanthrenyl group, pyrenyl group, perylenyl 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 heteroatoms, examples of which include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, Bipyridyl group, pyrimidyl group, triazine group, triazole group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyri Do 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, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, etc., but are not limited thereto. .

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

In the present invention, the silyl group means a silyl group substituted with an alkyl or a silyl group substituted with an aryl, and specific examples of the silyl group include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, 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 an aryl, the alkylamine group means an amine substituted with an alkyl, and an arylamine group Examples of a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group, and the aryl group in the arylamine group may be a monocyclic aryl group, and It may be a cyclic aryl group, and 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. 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 　 arylthioxy group is the same as the example of the 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-phenane There are a toryloxy group, a 9-phenanthryloxy group, and the like, and the arylthioxy group includes a phenylthioxy group, a 2-methylphenylthioxy group, and a 4-tert-butylphenylthioxy group, but is not limited thereto.

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, through which a specific substituent group can be clearly identified. By this, the scope of [Formula A] according to the present invention is not limited.

As can be seen from the above specific compounds, it is possible to synthesize an organic light-emitting material having intrinsic properties of the substituents by introducing various substituents thereto while forming a heteropolycyclic aromatic structure including a boron atom in the indolocarbazole skeleton. , 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, a hole blocking layer material used in the manufacture of an organic light emitting device, etc. A material that satisfies the conditions can be manufactured, and through this, a highly efficient organic light emitting device can be implemented. In addition, the compound according to the present invention may be used alone or together with other compounds as a material for various organic layers, or may be used for a light efficiency improvement 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 includes the [Formula A] It may contain at least one or more organic light-emitting compounds according to the present invention represented by.

That is, the organic light-emitting device according to an embodiment of the present invention may have a structure including a first electrode and a second electrode, and an organic material layer disposed therebetween, and the organic light-emitting compound of [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 multilayer 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 structure of the organic material layer of the organic light emitting device according to the present invention will be described in more detail in the following examples.

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 improvement layer, and the light efficiency improvement layer is a lower portion of the first electrode ( It may be formed on the bottom emission or the top emission of the second electrode.

In the method of forming the top emission of the second electrode, light formed in the light emitting layer is emitted toward the cathode, and the light emitted toward the cathode passes through the light efficiency improvement layer (CPL) formed of the compound according to the present invention having a relatively high refractive index. The wavelength of is amplified, thus increasing the light efficiency. In addition, the method formed under the first electrode (Bottom emission) also adopts the compound according to the present invention in the light efficiency improvement layer according to 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, a hole injection layer may be further included between the anode and the hole transport layer. An injection layer may be further included, and in addition, one or two intermediate layers may be further formed, a hole blocking layer or an electron blocking layer may be further formed, and as described above, a device such as a light efficiency improvement layer It may further include an organic layer having various functions according to the characteristics of.

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

[Formula C]

In [Chemical 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 [Chemical Formula A].

Ar ₉ and Ar ₁₀ are each 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, a 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 C2-C50 heteroaryl group, substituted or unsubstituted C2-C30 heterocycloalkyl group, substituted or unsubstituted C1-C30 alkoxy group, substituted or unsubstituted C6-C30 aryl An oxy group, a substituted or unsubstituted C1-C30 alkylthioxy group, a substituted or unsubstituted C6-C30 arylthioxy group, a substituted or unsubstituted C1-C30 alkylamine group, a substituted or unsubstituted It may be any one selected from an arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms.

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

In addition, Ar ₉ of the [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 [Chemical Formula C-1],

R ₃₁ to R ₃₅ are the same or different, respectively, are the same as defined in R ₁ to R ₁₇ of claim 1 [Chemical Formula A], and may be combined with a substituent adjacent to each other to form a saturated or unsaturated ring.

[Chemical Formula C] employed in the organic light emitting device according to the present invention may be specifically 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 improvement layer, respectively, and a compound represented by the following [Chemical Formula D] is added to the hole transport layer, the electron blocking layer, and the light efficiency improving layer, respectively. It characterized in that it includes.

[Formula D]

In the above [Formula D],

R ₄₁ to R ₄₃ are the same as 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 group, substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or unsubstituted C 1 to C 30 alkylsilyl group, substituted or unsubstituted C 6 to C 30 arylsilyl group and halogen group It is any one selected from among.

L ₃₁ to L ₃₄ are the same as or different from each other, and each independently is any one selected from 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 as or different from each other, and each independently is any one 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, when n is 2 or more, each aromatic ring containing R ₄₃ is the same as or different from each other, m ₁ to m ₃ is an integer of 0 to 4, when each of them is 2 or more Each of R ₄₁ , R ₄₂ , or R ₄₃ is the same as or different from each other.

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

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

[Formula E]

In the above [Formula E],

R ₅₁ to R ₅₄ 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 group, substituted or unsubstituted C 2 to C 20 alkynyl group, substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or unsubstituted C 5 to C 30 cycloalkenyl group, substituted or unsubstituted A substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 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 Group, substituted or unsubstituted C1-C30 alkylthioxy group, substituted or unsubstituted C5-C30 arylthioxy group, substituted or unsubstituted C1-C30 alkylamine group, substituted or unsubstituted C1-C30 Any one selected from a 5 to 30 arylamine group, a substituted or unsubstituted C1 to C30 alkylsilyl group, a substituted or unsubstituted C5 to C30 arylsilyl group, a nitro group, a cyano group, and a halogen group , These can each be linked to each other to form a ring.

Y is a carbon atom or a nitrogen atom, and 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 is any one 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 does not exist, 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].

[Chemical Formula D] employed in the organic light emitting device according to the present invention may be specifically 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 specifically selected from [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 improvement layer, respectively, and a compound represented by the following [Chemical Formula F] is added to the hole transport layer, the electron blocking layer, and the light efficiency improving layer, respectively. It characterized in that it includes.

[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 group, substituted or unsubstituted C 2 to C 20 alkynyl group, substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or unsubstituted C 5 to C 30 cycloalkenyl group, substituted or unsubstituted A substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 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 Group, substituted or unsubstituted C1-C30 alkylthioxy group, substituted or unsubstituted C6-C30 arylthioxy group, substituted or unsubstituted C1-C30 alkylamine group, substituted or unsubstituted C1-C12 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 a substituted or unsubstituted aryl germanium group having 1 to 30 carbon atoms, a cyano group, a nitro group, and a halogen group.

r ₅₁ to Ar ₅₄ are the same as 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.

[Chemical Formula F] employed in the organic light emitting device according to the present invention may be specifically selected from [Chemical Formula F1] to [Chemical Formula F33].

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

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

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 thermally evaporated or spin coated on the hole injection layer to form a hole transport layer. .

The hole injection layer material may 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) and 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 formed on the light emitting layer to form a thin film by a vacuum deposition method or a spin coating method. The hole blocking layer plays a role of preventing this problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level because when holes pass through the organic light emitting layer and flow into the cathode, the life and efficiency of the device are reduced. . In this case, the hole blocking material to be used is not particularly limited, but must have an electron transport ability and an ionization potential higher than that of the light emitting compound, and representatively, BAlq, BCP, TPBI, etc. may 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 [Formula 501] to [Formula 507] may be used, but limited thereto It does not become.

BAlq BCP Bphen

TPBI NTAZ BeBq ₂

OXD-7 Liq

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

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

[Chemical Formula 507]

The present invention by forming a cathode electrode by depositing an electron transport layer on the hole blocking layer through a vacuum deposition method or a spin coating method, and then forming an electron injection layer and vacuum thermally depositing a cathode-forming metal on the electron injection layer. The organic light emitting device according to an embodiment of is completed.

Here, the cathode-forming metal is lithium (Li), magnesium (Mg), aluminum (Al), aluminum-ridium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver ( Mg-Ag) or the like may be used, and in order to obtain a top light emitting device, a transmissive cathode using ITO or IZO may be used.

The electron transport layer material has a function of stably transporting electrons injected from the cathode, and a known electron transport material may 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], and oxadiazole derivatives such as PBD, BMD, BND, and the like may be used.

TAZ BAlq

[Compound 401] [Compound 402] BCP

In addition, as for the electron transport layer used in the present invention, an 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 [Chemical Formula C],

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

OA is a monovalent ligand capable of a single bond or coordination bond with 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, A substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms 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.

In addition, when M is a metal selected from alkali metals, m is 1, n is 0, and when M is a metal selected from alkaline earth metals, m is 1, n is 1, or m Is 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.

'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 independently selected from the following [Structural Formula C1] to [Structural Formula C39], 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 Formula 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 [Structural Formula C1] to [Structural Formula C39],

R is the same as 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 A heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or Unsubstituted C1-C30 alkylamino group, substituted or unsubstituted C1-C30 alkylsilyl group, substituted or unsubstituted C6-C30 arylamino group, and substituted or unsubstituted C6-C30 arylsilyl It is selected from groups, and may be connected to an adjacent substituent with alkylene or alkenylene to form a spiro ring or a 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 C 5 to 30 carbon atom Selected from a heteroaryl group and a substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms, wherein 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, and 3 to 20 carbon atoms It is further substituted with one or more substituents selected from a heteroaryl group, a cyano group, a halogen group, deuterium and hydrogen, and may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring.

In addition, the organic light-emitting device according to the present invention includes a light-emitting layer, and the light-emitting layer may further include one or more dopant compounds, and the light-emitting dopant compound applied to the organic light-emitting 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 may be the same as or different from each other as a ligand, and may each independently include any one selected from the following [Structural Formula 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 [Structural Formula D],

R is different from each other or the same, 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 5 to 50 heteroaryl group, substituted or unsubstituted C 1 to C 30 alkoxy group, substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or unsubstituted C 2 to C 30 alkenyl group, substituted or unsubstituted A substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms It may be any one selected from among.

Each of R is independently selected from 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, a heteroaryl group having 3 to 20 carbon atoms, a cyano group, a halogen group, deuterium and hydrogen It may be further substituted with one or more substituents.

In addition, the R may be connected to each of the adjacent substituents 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 with alkylene or alkenylene to form a spiro ring or a 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 , L ^A14 are each a linking group as previously defined. And Q ^A11 and Q ^A12 represent a partial structure containing an atom bonded to M ^A1 .

An 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, and 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 , L ^B14 represent a linking group, and Q ^B11 , Q ^B12 are It shows a partial structure containing an atom bonded to M ^B1 .

An 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 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 to form a 5-membered ring, and does not have any Represents a substituent, and R ^C13 and R ^C14 are each independently a hydrogen atom, a substituent that connects to each other to form a five-membered ring, and represents a substituent that does not have anything that connects to each other, and G ^C11 and G ^C12 are each independently a nitrogen atom, substituted Or an unsubstituted carbon atom, L ^C11 and L ^C12 represent a linking group, and Q ^C11 and Q ^C12 represent a partial structure containing an atom bonded to M ^C1 .

An 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 Each of J ^D14 represents an atomic group required to form a five-membered ring independently, and L ^D11 and L ^D12 represent a linking group.

An 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 an atomic group required to form a 5-membered ring, and 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.

An 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 A ring may be formed, wherein the ring formed by R ^F1 and R ^F12 and R ^F13 and R ^F14 is a 5-membered ring. In addition, Q ^F11 and Q ^F12 represent a partial structure containing an atom bonded to M ^F1 .

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

Further, 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, a halogen ligand, and more preferably an ortho metal. It is a ligand, a bipyridyl ligand or a phenanthroline ligand that forms a )-plated platinum complex.

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

In addition, it is preferable that n ¹ and m ¹ make the metal complex represented by the general formula H-1 become 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 and L ¹ , respectively, and q ²¹ is an integer of 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 , and L ¹ , respectively, and q ³¹ represents an integer of 0 to 8, preferably 0 to 2, and more than 0 desirable.

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

[General 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 a substituent, and the other two rings are an aryl ring or heterocycle that may have a substituent. Represents and represents an aryl ring, and a condensed ring can be formed by 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 any 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 (term) or a bond, but Q ¹ , Q ² and Q ³ do not represent a bond at the same time. Z ¹ , Z ² , Z ³ and Z ⁴ are any two representing a coordination bond, and the other two represent a covalent bond, an oxygen atom or a sulfur atom.

Examples of specific compounds of the [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-) bound to the M In this case, the nitrogen atom (N) is each bonded to the M, and as a whole, forms a tridentate ligand that is 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. In addition, it is preferable that Ar1 is selected from a 5-membered ring, a 6-membered ring and a condensed ring group thereof.

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

In addition, the emission 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 monomolecular 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 low pressure state. It refers to a method of forming a thin film, and in the solution process, a material used as a material for forming each layer is mixed with a solvent, and inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating It refers to a method of forming a thin film through a method such as the like.

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

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are for describing the present invention in more detail, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited thereto.

Synthesis example 1: synthesis of compound 1

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

<Formula 1-a>

In a 1000 mL round bottom flask, 1,5-dichloro-2,4-dinitrobenzene (40.0 g, 0.123 mol), phenylboronic acid (44.9 g, 0.368 mol), tetrakistriphenylphosphinepalladium (2.8 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 and refluxed. When the reaction is complete, the organic layer obtained by extraction with water and ethyl acetate was anhydrous treated with magnesium sulfate and concentrated under reduced pressure, and separated by column chromatography using hexane and ethyl acetate as developing solvents, and <Formula 1-a> was 27.5. g (yield 70.0%) was obtained.

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

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

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

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

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

In 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 sequentially added, and 300 mL of dimethylformamide was added, followed by refluxing 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 and subjected to column chromatography with methylene chloride: hexane = 1: 5 to obtain 32.2 g of <Formula 1-c> (yield 84%).

(4) Synthesis 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), and 320 mL of toluene were added and refluxed. When the reaction was completed, it was filtered in a hot state, and concentrated under reduced pressure, followed by column chromatography using 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, add <Chemical Formula 1-d> (21.3 g, 0.024 mol) and 160 mL of tert-butylbenzene, lower to -40°C, add 44.2 mL of normal-butyllithium dropwise, dropwise addition After completion, the mixture was raised to 60° C. to remove hexane. 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 mixture was raised to room temperature and stirred for 30 minutes. Again, the reaction temperature was 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 an aqueous sodium acetate 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 developing solvents to obtain 2.3 g of <Compound 1> (yield 13%).

MS (MALDI-TOF): m/z 851.3 [M ⁺ ]

Synthesis example 2: synthesis of compound 3

(One) Synthesis 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 then refluxed at 150° C. for 1 day. When the reaction was completed, extraction was performed using methylene chloride and distilled water. The organic layer was concentrated under reduced pressure and subjected to column chromatography with methylene chloride and heptane to obtain 7.28 g of <Formula 2-a> (yield 48%).

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

<Formula 2-b>

In a round bottom flask, 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 Benzylideneacetone) dipalladium (0) (4.57 g, 0.005 mol), sodium tert-butoxide (13.42 g, 0.140 mol), Dppf (5.53 g, 0.010 mol), and 360 mL of toluene were added and refluxed. When the reaction was completed, it was filtered in a hot state, concentrated under reduced pressure, and subjected to column chromatography using methylene chloride and heptane to obtain 18.55 g of <Formula 2-b> (yield 40.5%).

(3) Synthesis 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, and 153.8 mL of dimethylformamide was added, followed by refluxing 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, followed by column chromatography 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 under nitrogen stream, <Formula 2-c> (14.54 g, 0.016 mol) and 218 mL of tert-butylbenzene were added, lowered to -40°C, and 29.58 mL of normal-butyllithium was added dropwise. When the dropwise addition was completed, Raised to 60 ℃ to remove hexane. Again, the reaction temperature was lowered to -40 °C and boron tribromide (7.9 g, 0.032 mol) was added dropwise. When the dropwise addition was completed, the mixture was raised to room temperature and stirred for 1 hour. Again, the reaction temperature was 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, an aqueous sodium acetate solution 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 give 1 g of <Compound 3> (yield 8.2%).

MS (MALDI-TOF): m/z 772.5 [M ⁺ ]

Synthesis example 3: Synthesis of compound 5

In Synthesis Example 1-1, B-[3-(diphenylamino)phenylboronic acid and B-[3-(diphenylboryl)phenylboronic acid were used instead of phenylboronic acid, 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 <Compound 4.5 g of 5> was obtained (yield 17%).

MS (MALDI-TOF): m/z 798.3 [M ⁺ ]

Synthesis example 4: Synthesis of compound 7

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

MS (MALDI-TOF): m/z 797.3 [M ⁺ ]

Synthesis example 5: synthesis of compound 8

In Synthesis Example 1-4, N-phenyl-2-dibenzofuranamine was used instead of N-phenyl-2-naphthalenamine 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 ⁺ ]

Synthesis example 6: synthesis of compound 9

The same as in Synthesis Example 1 using 4-(1-naphthalenyl)-N-[4-(2-naphthalenyl)phenyl]benzeneamine instead of N-phenyl-2-naphthalenamine in Synthesis Example 1-4. 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: Manufacturing of organic light emitting device

The ITO glass was patterned so that the light emitting area was 2 mm × 2 mm, and washed. After mounting the ITO glass in a vacuum chamber, the base pressure was 1 × 10 ^-7 torr, and then DNTPD (700 Å), [Chemical Formula H] (250 Å) were sequentially deposited on the ITO. The light emitting layer is formed by mixing the host (BH1) described below and the compound of the present invention (3 wt%) (250 Å), and then, [Formula E-1] and [Formula E-2] as 1 : 300 Å in a ratio of 1, [Chemical Formula E-1] was formed as an electron injection layer in the order of 5 Å, and Al (1000 Å) to prepare an organic light-emitting device. The emission characteristics 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 as the following [BD1] to [BD3] instead of the compound of the present invention used in Example 1, and the luminescence 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 devices manufactured according to Examples 1 to 6 and Comparative Examples 1 to 3, voltage, luminance, color coordinates, and lifetime 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 in the related art. The device can be implemented.

Claims (16)

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 , A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted 6 to carbon number It is any one selected from the group consisting of a 50 aryl group, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms, a substituted or unsubstituted silyl group, and a substituted or unsubstituted boron group,
The R ₁ to R ₁₇ and their substituents may form a condensed ring of a group adjacent to each other and an aliphatic, aromatic, aliphatic hetero or aromatic hetero,
In the definition of R ₁ to R ₁₇ ,'substituted or unsubstituted' means that R ₁ to R ₁₇ are each independently deuterium, halogen group, alkyl group, alkoxy group, alkylamino group, arylamino group, heteroarylamino group, alkylsilyl It means that it is substituted with one or two or more substituents selected from the group consisting of a group, an arylsilyl group, an aryl group, and a heteroaryl group, or is substituted with a substituent to which two or more substituents are connected, or does not have any substituents. The method of claim 1,
[Chemical 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 facing 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 includes at least one compound represented by [Chemical Formula A] according to claim 1. The method of 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,
An organic light-emitting device, characterized in that at least one of the layers includes an organic light-emitting compound represented by [Chemical Formula A]. The method of claim 3,
Further comprising a light efficiency improvement layer formed on at least one side opposite to the organic material layer among upper or lower portions of the first electrode and the second electrode,
The organic light emitting device, characterized in that the light efficiency improvement layer comprises a compound represented by the [Chemical Formula A]. The method of claim 5,
The light efficiency improvement layer is an organic light emitting device, characterized in that formed on at least one of a lower portion of the first electrode or an 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 [Chemical 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 claim ₁ [Chemical Formula A],
Ar ₉ and Ar ₁₀ are each 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, a 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 C2-C50 heteroaryl group, substituted or unsubstituted C2-C30 heterocycloalkyl group, substituted or unsubstituted C1-C30 alkoxy group, substituted or unsubstituted C6-C30 aryl An oxy group, a substituted or unsubstituted C1-C30 alkylthioxy group, a substituted or unsubstituted C6-C30 arylthioxy group, a substituted or unsubstituted C1-C30 alkylamine group, a substituted or unsubstituted Any one selected from an arylamine group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms,
L ₁₃ is a single bond, or is any one selected from 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 of 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 it is a substituent represented by the following [Chemical Formula C-1]:
[Chemical Formula C-1]

In the [Chemical Formula C-1],
R ₃₁ to R ₃₅ are the same or different, respectively, are the same as defined in R ₁ to R ₁₇ of claim 1 [Chemical Formula A], and may be combined with a substituent adjacent to each other to form a saturated or unsaturated ring. The method of claim 8,
[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 are an organic light emitting device, characterized in that each comprises a compound represented by the following [Formula D]:
[Formula D]

In the above [Formula D],
R ₄₁ to R ₄₃ are the same as 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 group, substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or unsubstituted C 1 to C 30 alkylsilyl group, substituted or unsubstituted C 6 to C 30 arylsilyl group and halogen group Is any one selected from,
L ₃₁ to L ₃₄ are the same as or different from each other, each independently selected from 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 ,
Ar ₃₁ to Ar ₃₄ are the same as or different from each other, and each independently is any one 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 of the aromatic rings including R ₄₃ is the same as or different from each other,
m ₁ to m ₃ are integers of 0 to 4, and when each of them is 2 or more, each of R ₄₁ , R ₄₂ , or R ₄₃ is the same as or different from each other,
The carbon atom of the aromatic ring to which R ₄₁ to R ₄₃ are 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 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 group, substituted or unsubstituted C 2 to C 20 alkynyl group, substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or unsubstituted C 5 to C 30 cycloalkenyl group, substituted or unsubstituted A substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 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 Group, substituted or unsubstituted C1-C30 alkylthioxy group, substituted or unsubstituted C5-C30 arylthioxy group, substituted or unsubstituted C1-C30 alkylamine group, substituted or unsubstituted C1-C30 Any one selected from a 5 to 30 arylamine group, a substituted or unsubstituted C1 to C30 alkylsilyl group, a substituted or unsubstituted C5 to C30 arylsilyl group, a nitro group, a cyano group, and a halogen group , These can each be linked 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 is any one 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 does not exist, 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,
[Chemical 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,
[Chemical 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 improvement layer each include a compound represented by the following [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 group, substituted or unsubstituted C 2 to C 20 alkynyl group, substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or unsubstituted C 5 to C 30 cycloalkenyl group, substituted or unsubstituted A substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 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 Group, substituted or unsubstituted C1-C30 alkylthioxy group, substituted or unsubstituted C6-C30 arylthioxy group, substituted or unsubstituted C1-C30 alkylamine group, substituted or unsubstituted C1-C12 6 to 30 arylamine group, a substituted or unsubstituted C 1 to C 30 alkylsilyl group, a substituted or unsubstituted C 6 to C 30 arylsilyl group, a substituted or unsubstituted C 1 to C 30 alkyl germanium group, A substituted or unsubstituted aryl germanium group having 1 to 30 carbon atoms is any one selected from a cyano group, a nitro group and a halogen group,
Ar ₅₁ to Ar ₅₄ are the same as 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 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 group, substituted or unsubstituted C 2 to C 20 alkynyl group, substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or unsubstituted C 5 to C 30 cycloalkenyl group, substituted or unsubstituted A substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 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 Group, substituted or unsubstituted C1-C30 alkylthioxy group, substituted or unsubstituted C5-C30 arylthioxy group, substituted or unsubstituted C1-C30 alkylamine group, substituted or unsubstituted C1-C30 Any one selected from a 5 to 30 arylamine group, a substituted or unsubstituted C1 to C30 alkylsilyl group, a substituted or unsubstituted C5 to C30 arylsilyl group, a nitro group, a cyano group, and a halogen group , These can each be linked 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 is any one 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 does not exist, 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 [Chemical Formula F]. The method of claim 14,
The [Chemical Formula F] is an organic light emitting device, characterized in that any one selected from the following [Chemical Formula F1] to [Chemical Formula F33]:

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