KR102192692B1 - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to an organic light emitting compound employed as a hole injection or hole transport material of an organic light emitting device, or used as a doping material thereof, and the organic light emitting compound according to the present invention has a characteristic having a deep LUMO value When used alone or as a doping material for an organic material layer of an organic light-emitting device, a low-voltage driving and high-efficiency organic light-emitting device can be implemented, so that it can be usefully used in various display devices.

Description

An electroluminescent compound and an electroluminescent device comprising the same}

The present invention relates to an organic light-emitting compound, and more specifically, an organic light-emitting compound employed as a hole injection or hole transport material for an organic light-emitting device, or used as a doping material thereof, and an organic light-emitting compound that is used as a doping material thereof, and can exhibit low voltage driving and high efficiency. It relates to an organic electroluminescent device.

Organic light emitting devices can not only form devices on a transparent substrate, but also can drive a low voltage of 10 V or less compared to plasma display panels or inorganic electroluminescent (EL) displays, and consume relatively little power. In addition, it has the advantage of excellent color sense, and can display three colors of green, blue, and red, which has recently attracted much attention as a next-generation display device.

However, in order for such an organic light emitting device to exhibit the above characteristics, the material forming the organic layer in the device, such as hole injection material, hole transport material, light emitting material, electron transport material, electron injection material, etc., is supported by a stable and efficient material. However, the development of a stable and efficient organic material layer material for an organic electroluminescent device has not been sufficiently developed. Therefore, the development of new materials having low voltage driving, high efficiency and long life is still required.

The present invention provides a novel organic light-emitting compound and an organic light-emitting device including the same, which is adopted as a hole injection material, a hole transport material, or a doping material thereof in an organic material layer of an organic light-emitting device to realize low-voltage driving and high-efficiency light-emitting characteristics of the device. I want to provide.

In order to solve the above problems, the present invention is any one organic light-emitting compound selected from compounds represented by the following [Chemical Formula I-1] to [Chemical Formula I-2], [Chemical Formula II-1] to [Chemical Formula II-4] Provides.

[Chemical Formula Ⅰ-1] [Chemical Formula Ⅰ-2]

[Chemical Formula Ⅱ-1] [Chemical Formula Ⅱ-1]

[Chemical Formula Ⅱ-3] [Chemical Formula Ⅱ-4]

In addition, the present invention is an organic material layer employing a compound represented by the following [Chemical Formula I-1] to [Chemical Formula I-2], [Chemical Formula II-1] to [Chemical Formula II-4] alone or as a doping material It provides an electroluminescent device.

Specific structures and substituents of the compounds represented by the following [Chemical Formula I-1] to [Chemical Formula I-2], [Chemical Formula II-1] to [Chemical Formula II-4] will be described later.

Since the organic light-emitting compound according to the present invention has a property of having a deep LUMO value, it is possible to implement a low-voltage driving and high-efficiency organic light-emitting device when it is used alone or as a doping material in the organic material layer of the organic light-emitting device. It can be useful for devices and used.

1 to 5 are cross-sectional views illustrating the structure of an organic light-emitting device according to an embodiment of the present invention.

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

One aspect of the present invention relates to an organic light emitting compound represented by the following [Chemical Formula I-1] to [Chemical Formula I-2], [Chemical Formula II-1] to [Chemical Formula II-4].

[Chemical Formula Ⅰ-1] [Chemical Formula Ⅰ-2]

[Chemical Formula Ⅱ-1] [Chemical Formula Ⅱ-1]

[Chemical Formula Ⅱ-3] [Chemical Formula Ⅱ-4]

In the above [Chemical Formula I-1] to [Chemical Formula I-2], [Chemical Formula II-1] to [Chemical Formula II-4],

X ₁ to X ₅ are the same as or different from each other, and each independently selected from N, O, S, C, CR ₄ , NR ₅ , CR ₆ R ₇ and SiR ₈ R ₉ ,

A ₁ , B ₁ are the same as or different from each other, and are double bonds, each independently CR ₁₉ R ₂₀ , a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms , Is selected from a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms,

A ₂ , B ₂ are the same as or different from each other, and are a single bond, or each independently CR ₂₁ R ₂₂ , a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, a substituted or unsubstituted alkenyl group having 3 to 24 carbon atoms, a substituted Or an unsubstituted C3-C24 alkynyl group, substituted eh is an unsubstituted C5-C50 aryl group, a substituted or unsubstituted C5-C5 substituted or unsubstituted C5-C30 arylamine group, a substituted or unsubstituted Is selected from a C 3 to C 50 heteroaryl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group,

R ₁ to R ₉ are the same as or different from each other, and hydrogen, deuterium, carbonyl group, phosphoryl group, amino group, thiol group, cyano group, hydroxy group, nitro group, halogen group, amide group, substituted or unsubstituted C 1 to 30 Of an alkyl group, a substituted or unsubstituted cycloalkyl group having 3 to 30 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 carbon number 6 To 30 aryloxy group, substituted or unsubstituted C 1 to C 30 alkyl thioxy group, substituted or unsubstituted C 5 to C 30 arylthioxy group, substituted or unsubstituted C 1 to C 30 alkylamine group, substituted Or an unsubstituted C5 to C30 arylamine group, a substituted or unsubstituted C5 to C50 aryl group, a substituted or unsubstituted C3 to C50 heteroaryl group, a substituted or unsubstituted C3 to C30 A substituted or unsubstituted aryl group having 5 to 50 carbon atoms in which at least one cycloalkyl is fused, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms in which one or more substituted or unsubstituted cycloalkyls having 3 to 30 carbon atoms are fused And a substituted or unsubstituted silyl group,

m ₁ to m ₂ , and n ₁ to n ₂ are the same as or different from each other, and each independently an integer of 1 to 4.

Meanwhile, the R ₁ to R ₉ may be further substituted with one or more substituents, and the one or more substituents may be hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted C 2 to 30 alkenyl group, substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted A cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyl thioxy group having 1 to 30 carbon atoms, A substituted or unsubstituted arylthioxy group having 5 to 30 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 5 to 30 carbon atoms 50 aryl group, 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 unsubstituted aluminum group , A carbonyl group, a phosphoryl group, an amino group, a thiol group, a cyano group, a hydroxy group, a nitro group, a halogen group, a selenium group, a tellurium group, an amide group, an ether group, and an ester group.

In the present invention, examples of the substituents are specifically described below, but are not limited thereto.

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 50. 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 alkoxy group may be linear or branched. The number of carbon atoms of the alkoxy group is not particularly limited, but it is preferably 1 to 30, which is a range that does not cause a steric hindrance. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, i-propyloxy group, n-butoxy group, isobutoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group , Neopentyloxy group, isopentyloxy group, n-hexyloxy group, 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group , Benzyloxy group, p-methylbenzyloxy group, and the like, but are not limited thereto.

In the present invention, the alkenyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. Specific examples include vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl 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, and styrenyl group, but are not limited thereto.

In the present invention, the aryl group may be monocyclic or polycyclic, and the number of carbon atoms is not particularly limited, but is preferably 6 to 60. Examples of monocyclic aryl groups include phenyl, biphenyl, terphenyl, and stilbene groups, and examples of polycyclic aryl groups include naphthyl, anthracenyl, phenanthrenyl, pyrenyl, perylenyl, and tetrasenyl groups. , A chrysenyl group, a fluorenyl group, an acenaphthacenyl group, a triphenylene group, a fluoranthrene group, and the like, but the scope of the present invention is not limited to these examples.

In the present invention, the heteroaryl group is a heterocyclic group containing O, N, or S as a heteroatom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heterocyclic groups include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, 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, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group , Indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, dibenzofuranyl group, phenanthroline group, thiazolyl Group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, and the like, but are not limited thereto.

In the present invention, the aryl groups in the aryloxy group, arylthioxy group, arylsulfoxy group, and aralkylamine group are the same as those of the aryl group described above. Specifically, the aryloxy group includes a phenoxy group, p-tolyloxy group, m-tolyloxy group, 3,5-dimethyl-phenoxy group, 2,4,6-trimethylphenoxy group, ptert-butylphenoxy group, 3-biphenyl Oxy 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-phenanthryloxy group, 9-phenanthryloxy group, etc., and the arylthioxy group is phenylthioxy group, 2-methylphenyl There are thioxy group, 4-tert-butylphenyl thioxy group, and the like, and the aryl sulfoxy group includes a benzene sulfoxy group and a p-toluene sulfoxy group, but is not limited thereto.

In the present invention, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and specifically, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 3-methylcyclopentyl group, a 2,3-dimethylcyclopentyl group, and a cyclohexyl group. Sil group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2,3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclo There are octyl groups and the like, but are not limited thereto.

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

In the present invention, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group 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.

Specific examples of the arylamine group include phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 3-methyl-phenylamine group, 4-methyl-naphthylamine group, 2-methyl-biphenyl An amine group, a 9-methyl-anthracenylamine group, a diphenyl amine group, a phenyl naphthyl amine group, a ditolyl amine group, a phenyl tolyl amine group, a carbazole group and a triphenyl amine group, and the like, but are not limited thereto.

In the present invention, the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.

In the present invention, the heteroaryl group in the heteroarylamine group may be selected from the examples of the heterocyclic group described above.

In the present invention, the alkyl group in the alkyl thioxy group and the alkyl sulfoxy group is the same as the example of the alkyl group described above. Specifically, the alkyl thioxy group includes a methyl thioxy group, an ethyl thioxy group, a tert-butyl thioxy group, a hexyl thioxy group, an octyl thioxy group, and the alkyl sulfoxy group is mesyl, ethyl sulfoxy group, propyl sulfoxy group, butyl sulfoxy group. And the like, but are not limited thereto.

In the present invention, the substituted arylene group is a phenyl group, a biphenyl group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group, and a tetracenyl group. It means that an anthracenyl group or the like is substituted with another substituent.

In the present invention, the substituted heteroarylene group refers to a pyridyl group, a thiophenyl group, a triazine group, a quinoline group, a phenanthroline group, an imidazole group, a thiazole group, an oxazole group, a carbazole group, and a condensed heterocyclic group thereof, For example, it means that a benzquinoline group, a benzimidazole group, a benzoxazole group, a benzthiazole group, a benzcarbazole group, a dibenzothiophenyl group, a dibenzofuran group, and the like are substituted with other substituents.

In the present invention, "substituted or unsubstituted" means deuterium, halogen group, nitrile group, nitro group, hydroxy group, alkyl group, cycloalkyl group, alkoxy group, aryloxy group, alkylthioxy group, arylthioxy group, alkylsulfoxy group , Arylsulfoxy group, alkenyl group, silyl group, boron group, alkylamine group, aralkylamine group, arylamine group, aryl group, fluorenyl group, carbazole group and at least one of N, O and S atoms It means unsubstituted or substituted with at least one substituent among heterocyclic groups.

The organic light emitting compound according to the present invention represented by [Chemical Formula I-1] to [Chemical Formula I-2] and [Chemical Formula II-1] to [Chemical Formula II-4] is an organic material layer of an organic light emitting device due to its structural specificity May be used as, and more specifically, the hole transport material alone or as a doping material for the hole transport material in the organic material layer.

Preferred specific examples of the compounds represented by [Chemical Formula I-1] to [Chemical Formula I-2] according to the present invention include compounds represented by the following compounds 1 to 271, but are not limited thereto.

[Chemical Formula I-1] to [Chemical Formula I-2]

In addition, preferred specific examples of the compounds represented by [Chemical Formula II-1] to [Chemical Formula II-4] according to the present invention include compounds represented by the following compounds 1 to 128, but are not limited thereto.

[Chemical Formula Ⅱ-1] to [Chemical Formula Ⅱ-4]

The organic light emitting compound according to the present invention represented by [Chemical Formula I-1] to [Chemical Formula I-2] and [Chemical Formula II-1] to [Chemical Formula II-4] is an organic material layer of an organic light emitting device due to its structural specificity It may be used as, and more specifically, may be used alone or as a doping material for the hole transport layer or the hole injection layer in the organic material layer.

In particular, according to a preferred embodiment of the present invention, the organic light emitting compound according to the present invention is used alone in the hole transport layer of the organic light emitting device, or as a doping material for the hole transport compound of the conventional hole transport layer, so that low voltage driving of the device and Excellent efficiency can be achieved.

In addition, by introducing various substituents into the core structure of the above-described structure, an organic light-emitting compound having intrinsic characteristics of the introduced substituent can be synthesized. For example, by introducing a hole injection layer material, a hole transport layer material, a light emitting layer material, and a substituent used in the electron transport layer material used in the manufacture of an organic light emitting device into the structure, a material that satisfies the conditions required by each organic material layer can be prepared. I can.

In particular, the organic light-emitting compounds represented by [Chemical Formula I-1] to [Chemical Formula I-2], [Chemical Formula II-1] to [Chemical Formula II-4] according to the present invention are, as described above, in a characteristic core structure As a result of introducing the substituent, it is possible to implement an organic electroluminescent device that exhibits excellent characteristics in terms of efficiency and driving voltage.

The compound of the present invention can be applied to a device according to a conventional manufacturing method of an organic electroluminescent device.

The organic light emitting device according to an embodiment of the present invention may have a structure including a first electrode, a second electrode, and an organic material layer disposed therebetween, and the organic light emitting compound according to the present invention is used in the organic material layer of the device. Except that, it can be manufactured using a conventional device manufacturing method and material.

The organic material 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 material layers are stacked. For example, it may have a structure including a hole injection layer, a hole transport layer, a light emitting 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 of organic material layers.

Therefore, in the organic electroluminescent device of the present invention, the organic material layer is a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, a layer for simultaneously injecting and transporting holes, a layer for simultaneously injecting and transporting electrons, and a light emitting layer. One or more layers may be included, and at least one of the layers includes a compound represented by the above [Chemical Formula I-1] to [Chemical Formula I-2], [Chemical Formula II-1] to [Chemical Formula II-4] can do.

In such a multi-layered organic material layer, the compounds represented by [Chemical Formula I-1] to [Chemical Formula I-2], [Chemical Formula II-1] to [Chemical Formula II-4] are a light emitting layer, hole injection/hole transport and light emission. It may be included in a layer at the same time, a layer that simultaneously transports holes and emits light, or a layer that transports electrons and emits at the same time.

For example, the structure of an organic electronic device according to the present invention is illustrated in FIGS. 1 to 5.

1 shows an organic electronic device in which an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, and a cathode 7 are sequentially stacked on a substrate 1. The structure is illustrated. In such a structure, the compounds represented by [Chemical Formula I-1] to [Chemical Formula I-2], [Chemical Formula II-1] to [Chemical Formula II-4] are the hole injection layer (3), the hole transport layer ( 4), it may be included in the light emitting layer 5 or the electron transport layer 6.

FIG. 2 illustrates the structure of an organic electronic device in which an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, and a cathode 7 are sequentially stacked on a substrate 1. In such a structure, the compounds represented by [Chemical Formula I-1] to [Chemical Formula I-2], [Chemical Formula II-1] to [Chemical Formula II-4] are the hole injection layer (3), the hole transport layer ( 4) or may be included in the electron transport layer 6.

3 illustrates a structure of an organic electronic device in which an anode 2, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6 and a cathode 7 are sequentially stacked on a substrate 1. In such a structure, the compounds represented by [Chemical Formula I-1] to [Chemical Formula I-2], [Chemical Formula II-1] to [Chemical Formula II-4] are the hole transport layer (4) and the light emitting layer (5) Alternatively, it may be included in the electron transport layer 6.

4 illustrates a structure of an organic electronic device in which an anode 2, a light emitting layer 5, an electron transport layer 6, and a cathode 7 are sequentially stacked on a substrate 1. In such a structure, the compounds represented by [Chemical Formula I-1] to [Chemical Formula I-2], [Chemical Formula II-1] to [Chemical Formula II-4] are the light-emitting layer (5) or electron transport layer (6) Can be included in

5 illustrates a structure of an organic electronic device in which an anode 2, a light emitting layer 5, and a cathode 7 are sequentially stacked on a substrate 1. In such a structure, the compounds represented by [Chemical Formula I-1] to [Chemical Formula I-2], [Chemical Formula II-1] to [Chemical Formula II-4] may be included in the light-emitting layer 5.

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

In addition to this method, an organic electroluminescent device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, an emission layer, an electron transport layer, and the like, but is not limited thereto and may have a single layer structure. In addition, the organic material layer is made of a variety of polymer materials, and is used in a smaller number of solvent processes, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be made in layers.

As the anode material, a material having a large work function is preferable so that hole injection into the organic material layer can be smoothly performed. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). Metal oxides, combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDT) , Polypyrrole and conductive polymers such as polyaniline, but are not limited thereto.

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

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

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

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

As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer, and a material having high mobility for electrons is suitable. Specific examples include, but are not limited to, an Al complex of 8-hydroxyquinoline, a complex including Alq ₃ , an organic radical compound, and a hydroxyflavone-metal complex.

The organic electroluminescent device according to the present invention may be a top emission type, a bottom emission type, or a double-sided emission type depending on the material used.

In addition, the organic light-emitting compound according to the present invention can act on a principle similar to that applied to an organic light-emitting device in organic electronic devices including organic solar cells, organic photoreceptors, and organic transistors.

Hereinafter, a preferred embodiment is presented to aid the understanding of the present invention. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereby.

Synthesis Example: Synthesis of [Chemical Formula I-1] to [Chemical Formula I-2] compounds according to the present invention

Synthesis Example 1: Synthesis of Compound 82

(One) Manufacturing example 1: Synthesis of Intermediate 82-1

2,2',2''-(cyclopropane-1,2,3-triylidene)trimalononitrile (20 g, 0.087 mol, yurui), sodium azide (17.09 g, 0.262 mol, sigma aldrich), zinc chloride (35.842 g, 0.262 mol, sigma aldrich) was added to 500 mL of toluene and stirred under reflux for 24 hours. After cooling the reaction mixture, hydrochloric acid (1 M, sigma aldirch) was added to make the pH 1.0 (confirmed with litmus paper), followed by stirring for an additional 30 minutes. The resulting precipitate was filtered and washed with methanol and hexane. The obtained solid powder was recrystallized from toluene to obtain 10 g (yield: 28.9%) of <Intermediate 82-1>.

(2) Manufacturing example 2: Synthesis of compound 82

Intermediate 82-1 (5 g, 0.014 mol, sigma aldrich), propiolic acid (1.961 g, 0.028 mol, sigma aldrich), N,N'-Dicyclohexylcarbodiimide (DCC) (5.7 g, 0.028 mol, sima aldrich) toluene 100 mL was added and stirred under reflux for 3 hours. After cooling the reaction mixture, the generated precipitate was filtered and washed with methanol. The obtained solid powder was recrystallized from toluene to obtain 4 g (yield: 66.2%) of compound 82.

LC/MS: m/z=432[(M+1) ⁺ ]

Synthesis example 2: Synthesis of compound 157

(One) Manufacturing example 1: Synthesis of Intermediate 157-1

Pyrazino[2,3-g]quinoxaline-5,10-dione (10 g, 0.047 mol, Yurui) is added to methylenechloride, and the temperature is raised to 50 ℃ to dissolve clearly. After lowering the temperature to 30 ℃ TiCl ₄ (1 M in methylenechloride) (377.07 mL, 0.38 mol, sigma aldirich) was slowly dropped. Then, pyridine (30.38 mL, 0.38 mol, sigma aldrich) was added and stirred under reflux for 1 hour. After cooling the reaction mixture, the precipitate was filtered and washed with 500 mL of methanol. The obtained solid powder was purified by column using silica (EA:Hexane) to obtain 9 g (yield: 62%) of <Intermediate 157-1>.

(2) Manufacturing example 2: Synthesis of Intermediate 157-2

Intermediate 82-1 (20 g, 0.065 mol), sodium azide (12.65 g, 0.19 mol, sigma aldrich), zinc chloride (26.53 g, 0.194 mol, sigma aldrich) was added 500 mL of toluene and stirred under reflux for 24 hours. After cooling the reaction mixture, hydrochloric acid (1M) was added (confirmed with litmus paper) to bring the pH to 1.0, followed by stirring for an additional 30 minutes. The resulting precipitate was filtered and washed with methanol and hexane. The obtained solid powder was recrystallized from toluene to obtain 14 g (yield: 54.7%) of <Intermediate 157-2>.

(3) Manufacturing example 3: Synthesis of Compound 157

In intermediate 157-2 (15 g, 0.038 mol), propiolic acid (5.33 g, 0.076 mol, sigma aldrich), N,N'-Dicyclohexylcarbodiimide (DCC) (15.47 g, 0.076 mol, sigma aldrich), 500 mL of toluene was added. Stir at reflux for 3 hours. After cooling the reaction mixture, the generated precipitate was filtered and washed with methanol. The obtained solid powder was recrystallized from toluene to obtain 12 g (yield: 71%) of compound 157.

H-NMR (200MHz, CDCl3): δ ppm, 4H (8.76/d)

LC/MS: m/z=444[(M+1) ⁺ ]

Synthesis example 3: Synthesis of compound 174

(One) Manufacturing example 1: Synthesis of Intermediate 174-1

2,3,7,8-tetrafluoropyrazino[2,3-g]quinoxaline-5,10-dione (10 g, 0.035 mol, yurui), malononitrile (46.5 g. 0.70 mol, sigma aldrich) was added to methylene chloride and temperature Raise to 50 ℃ to dissolve clearly. After lowering the temperature to 30 ℃ TiCl ₄ (1M in methylenechloride) (281.56 mL, 0.28 mol, sigma aldrich) was slowly dropped. Then, pyridine (22.68 mL, 0.28 mol, sigma aldrich) was added and stirred under reflux for 1 hour. After cooling the reaction mixture, the precipitate was filtered and washed with 500 mL of methanol. The obtained solid powder was purified by column using silica (EA:Hexane) to obtain 9 g (yield: 67.2%) of <Intermediate 174-1>.

(2) Manufacturing example 2: Synthesis of Intermediate 174-2

Intermediate 174-1 (10 g, 0.026 mol), 4-formylcyclopenta-1,3-dienylboronic acid (4.35 g, 0.31 mol, yurui), Pd(PPh ₃ ) ₄ (0.304 g, 0.0002 mol) was added to 200 mL of THF. Then, K ₂ CO ₃ dissolved in water (7.27 g, 0.052 mol) was added and stirred under reflux for 1 hour. The reaction mixture was cooled, extracted using MC/DW, and then purified by column using silica (MC:MeOH) to obtain 6.5 g (yield 47.7%) of <Intermediate 174-2>.

(3) Manufacturing example 3: Synthesis of compound 174

Intermediate 174-2 (7 g, 0.013 mol), NH ₄ OH (1.18 g, 0.034 mol, sigma aldrich), triethylamine (6.833 g, 0.067 mol, sigma aldrich) were added 50 mL each of MC/MeOH and stirred for 3 hours. I did. After cooling the reaction temperature to 0 ℃, trifluoro acetic anhydride (6.24 g, 0.029 mol) was slowly added. After raising the reaction temperature to room temperature, the mixture was stirred for 4 hours. After completion of the reaction, it was referred to as NaHCO ₃ and extracted with MC/DW. The obtained solid powder was purified by column using silica (MC:MeOH) to obtain 4 g (yield 57.8%) of compound 174.

H-NMR (200MHz, CDCl3): δ ppm, 2H (7.2/d, 6.86/d)

LC/MS: m/z=512[(M+1) ⁺ ]

Synthesis Example: Synthesis of [Chemical Formula II-1] to [Chemical Formula II-4] compounds according to the present invention

Synthesis example 4: Synthesis of compound 27

(One) Manufacturing Example 1 : Intermediate 27 Synthesis of -1

10 g (yield: 38.12%) of <Intermediate 27-1> was obtained using the same method as for the synthesis of Intermediate 82-1.

(2) Manufacturing example 2: Synthesis of compound 27

6 g (yield: 52.7%) of compound 27 was obtained using the same method as for the synthesis of compound 82.

LC/MS: m/z=412[(M+1) ⁺ ]

Synthesis example 5: Synthesis of compound 31

(One) Manufacturing example 1: Synthesis of Intermediate 31-1

4 g (yield: 30.5%) of <Intermediate 31-1> was obtained by using the same method as the synthesis of Intermediate 82-1.

(2) Manufacturing example 2: Synthesis of compound 31

8 g (yield: 71.75%) of compound 31 was obtained by using the same method as the synthesis of compound 82.

LC/MS: m/z=412[(M+1) ⁺ ]

Synthesis example 6: Synthesis of compound 56

(One) Manufacturing example 1: Synthesis of Intermediate 56-1

2-bromo-4-iodo-5-methylpyrimidine (10 g, 0.033 mol, yurui) and 2-chloro pyrimidin-4-ylboronic acid (6.34 g, 0.04 mol, yurui), Pd(PPh ₃ ) ₄ (tetrakis (triphenylphosphine) ) palladium(0)) (1.935 g, 0.0017 mol, sigma aldrich) was placed in a reaction flask, dried under vacuum, and then filled with nitrogen gas. 150 mL of toluene was added to the reaction flask to dissolve the compounds, and then 75 mL of ethanol and 75 mL of 2.0MK ₂ CO ₃ aqueous solution were added, followed by refluxing at 120° C. for 3 hours and stirred. After completion of the reaction, the reaction product was washed with distilled water and extracted with ethyl acetic acid to collect an organic layer. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was removed by distillation under reduced pressure. The obtained residue was subjected to silica gel column chromatography to obtain 5.73 g (yield: 60%) of <Intermediate 56-1>.

(2) Manufacturing example 2: Synthesis of Intermediate 56-2

2-bromo-2'-chloro-4,4'-bipyrimidine-5-carboxylic acid (5.2 g, 0.182 mol) quantitatively obtained by reacting Intermediate 56-1 with an aqueous KMnO ₄ solution was added to a reaction flask and polyphosphoric acid (30 g, sigma aldrich) was added to react. After the reaction was completed, the reaction solution was added to a beaker containing an aqueous sodium hydroxide solution (5N), and then stirred at room temperature and filtered. 2.84 g (yield: 58%) of <Intermediate 56-2> as a yellow solid was obtained.

(3) Manufacturing example 3: Synthesis of Intermediate 56-3

7 g (yield: 60.2%) of <Intermediate 56-3> was obtained by using the same method as the synthesis of Intermediate 157-1.

(4) Manufacturing example 4: synthesis of intermediate 56-4

Using the same method as the synthesis of Intermediate 82-1, 8 g (yield: 64%) of <Intermediate 56-4> was obtained.

(5) Manufacturing example 5: synthesis of intermediate 56-5

8 g (yield: 71.7%) of <Intermediate 56-5> was obtained using the same method as for the synthesis of compound 82.

(6) Manufacturing example 6: Synthesis of compound 56

Intermediate 56-5 (7 g, 0.033 mol) and Pd(PPh ₃ ) ₄ (tetrakis(triphenyl phosphine)palladium(0)) (3.359 g, 0.003 mol, sigma aldrich), ZnCN ₂ (4.097 g, 0.034 mol, sigma aldrich) was placed in a reaction flask, dried under vacuum, and then filled with nitrogen gas. 100 mL of N-Methyl-2-phrrolidone was added to the reaction flask to dissolve the compounds, followed by refluxing for 5 hours and stirring. After the reaction was completed, the reaction mixture was cooled, and the resulting precipitate was filtered and washed with methanol. The obtained solid powder was recrystallized after silica/celite filter with toluene to obtain 3.5 g (yield: 57.6%) of compound 56.

H-NMR (200MHz, CDCl3): δ ppm, 2H (8.79/s)

LC/MS: m/z=418[(M+1) ⁺ ]

Synthesis example 7: compound 63 synthesis

(One) Manufacturing example 1: Synthesis of Intermediate 63-1

6.35 g (yield: 65%) of <Intermediate 63-1> was obtained using the same method as for the synthesis of Intermediate 56-1.

(2) Manufacturing example 2: Synthesis of Intermediate 63-2

7 g (yield: 58%) of <Intermediate 63-2> was obtained using the same method as for the synthesis of Intermediate 56-2.

(3) Manufacturing example 3: Synthesis of Intermediate 63-3

Using the same method as the synthesis of Intermediate 56-3, 9 g (yield: 66.9%) of <Intermediate 63-3> was obtained.

(4) Manufacturing example 4: Synthesis of Intermediate 63-4

7.6 g (yield: 60.8%) of <Intermediate 63-4> was obtained using the same method as for the synthesis of Intermediate 56-4.

(5) Manufacturing example 5: synthesis of intermediate 63-5

6.5g (yield: 68.5%) of <Intermediate 63-5> was obtained using the same method as for the synthesis of compound 82.

(6) Manufacturing example 6: Synthesis of Compound 63

8 g (yield: 50.4%) of compound 63 was obtained using the same method as for the synthesis of compound 56.

H-NMR (200MHz, CDCl3): δ ppm, 2H (9.54/s)

LC/MS: m/z=418[(M+1) ⁺ ]

Synthesis example 8: Synthesis of compound 91

(One) Manufacturing example 1: synthesis of intermediate 91-1

8 g (yield: 56%) of <Intermediate 91-1> was obtained using the same method as for the synthesis of Intermediate 157-1.

(2) Manufacturing example 2: Synthesis of Intermediate 91-2

4.5g (yield: 35.4%) of <Intermediate 91-2> was obtained using the same method as for the synthesis of Intermediate 82-1.

(3) Manufacturing example 3: Synthesis of compound 91

8 g (yield: 71.2%) of compound 91 was obtained using the same method as for the synthesis of Intermediate 56-5.

H-NMR (200MHz, CDCl3): δ ppm, 2H (6.3/s)

LC/MS: m/z=456[(M+1) ⁺ ]

P-doped device embodiment

In an embodiment according to the present invention, the ITO transparent electrode is patterned so that the light emitting area is 2 mm × 2 mm on a glass substrate of 25 mm × 25 mm × 0.7 mm using an ITO glass substrate with an ITO transparent electrode attached thereto. After washing. After mounting the substrate in the vacuum chamber, the base pressure was set to 1 × 10 ^-6 torr, and the organic material and metal were deposited on the ITO in the following structure.

Device Examples 1 to 6

Using the compound implemented according to the present invention as a doping compound for a hole transport material, a blue light emitting organic electroluminescent device having the following device structure was manufactured, and light emission characteristics including light emission efficiency were measured.

ITO / hole transport layer (a-NPB: compound doped 100 nm according to the present invention) / electron blocking layer (10 nm) / emitting layer (20 nm) / electron transport layer (201: LiF 30 nm) / LiF (1 nm) / Al (100 nm)

A hole transport layer was formed on the ITO transparent electrode using a-NPB. At this time, 2 to 10% doping of 72, 82, 157 of [Chemical Formula I-1] to [Chemical Formula I-2], 27, 56, 91 of [Chemical Formula II-1] to [Chemical Formula II-4] according to the present invention (5% applied in this device). The hole blocking layer was formed to a thickness of 10 nm using [EBL1]. In addition, [BH1] was used as the host compound for the light emitting layer, and [BD1] was used as the dopant compound to form a film having a thickness of about 20 nm, and an electron transport layer (following [201] compound Liq 50% doped) 30 nm and 1 nm of LiF and 100 nm of aluminum were deposited by a vapor deposition method to prepare an organic light emitting diode.

Device Comparative Example 1

The organic light emitting device for Device Comparative Example 1 was fabricated in the same manner as in Example 1 except that P-doped was not used.

Element Comparative Example 2

The organic electroluminescent device for Device Comparative Example 2 was similarly fabricated using F4TCNQ as a P-doped material in the device structure of Example 1 above.

Experimental Example 1: Light emission characteristics of device Examples 1 to 6

The organic electroluminescent device manufactured according to the above example measured voltage, current and luminous efficiency using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research), and a current density of 10 mA/cm 2 The voltage to be defined as "driving voltage" was compared. The results are shown in Table 1 below.

Example P-doped substance V cd/A QE(%) CIEx CIEy One Formula I-72 4.27 8.14 7.65 0.145 0.153 2 Formula I-82 4.25 8.17 7.72 0.145 0.153 3 Formula I-157 4.28 8.13 7.67 0.145 0.152 4 Formula II-27 4.25 8.15 7.72 0.145 0.152 5 Chemical Formula II-56 4.24 8.19 7.71 0.145 0.152 6 Chemical Formula II-91 4.30 8.10 7.64 0.146 0.153 Comparative Example 1 not used 6.45 4.5 3.8 0.144 0.156 Comparative Example 2 F4TCNQ 4.7 7.5 6.1 0.147 0.156

Looking at the results shown in [Table 1], first, when the P-doped material according to the present invention is applied to a compound device, luminous efficiency, quantum efficiency, etc., despite not using HIL compared to the conventional device (Comparative Example). It can be seen that the luminescence characteristics are remarkably excellent.

[α-NPB] [EBL1] [BH1] [BD1] [201]

Device Examples 7 to 12

Using the compound implemented according to the present invention as a hole transport material, a blue light emitting organic electroluminescent device having the following device structure was manufactured, and light emission characteristics including light emission efficiency were measured.

ITO / fusion hole transport layer (invention compound 60 nm) / electron blocking layer (10 nm) / emitting layer (20 nm) / electron transport layer (201: Liq 30 nm) / LiF (1 nm) / Al (100 nm)

A film was formed on an ITO transparent electrode to a thickness of 60 nm using 143, 174, 192 of [Chemical Formula I] and 31, 63, and 95 of [Chemical Formula II] according to the present invention. The hole blocking layer was formed to a thickness of 10 nm using [EBL1]. In addition, [BH1] was used as the host compound for the light emitting layer, and [BD1] was used as the dopant compound to form a film having a thickness of about 20 nm, and an electron transport layer (following [201] compound Liq 50% doped) 30 nm and 1 nm of LiF and 100 nm of aluminum were deposited by a vapor deposition method to prepare an organic light emitting diode.

Device Comparative Example 1

The organic electroluminescent device for device Comparative Example 1 was fabricated in the same manner using F4TCNQ instead of the compound according to the present invention in the device structure of Example 7 above.

Experimental Example 2: Light emission characteristics of device Examples 7 to 12

The organic electroluminescent device manufactured according to the above example measured voltage, current and luminous efficiency using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research), and a current density of 10 mA/cm 2 The voltage to be defined as "driving voltage" was compared. The results are shown in Table 2 below.

Example Hole transport material V cd/A QE(%) CIEx CIEy One Formula I-143 5.9 5.4 4.6 0.145 0.152 2 Formula I-174 5.6 5.6 4.8 0.145 0.152 3 Formula I-192 6.1 5.2 4.4 0.146 0.151 4 Chemical Formula II-31 5.8 5.7 4.3 0.146 0.153 5 Formula II-63 5.7 5.9 4.7 0.145 0.152 6 Chemical Formula II-95 6.0 5.5 4.2 0.144 0.152 Comparative Example 1 F4TCNQ 7.2 3.8 3.1 0.147 0.156

Looking at the results shown in [Table 1], first, it can be seen that when the compound according to the present invention is applied to the hole transport layer, light emission characteristics such as luminous efficiency and quantum efficiency are remarkably superior compared to the conventional device (Comparative Example).

[α-NPB] [EBL1] [BH1] [BD1] [201]

Claims (8)

An organic light emitting compound, characterized in that any one selected from compounds represented by the following compounds 1 to 271:

delete An organic light emitting compound, characterized in that any one selected from compounds represented by the following compounds 1 to 128:

An organic electroluminescent device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode,
An organic electroluminescent device, wherein at least one of the organic material layers includes any one compound selected from the organic light-emitting compounds according to claim 1 or 3. The method of claim 4,
The organic material layer includes at least one of a hole injection layer, a hole transport layer, a layer for simultaneous hole injection and hole transport, an electron transport layer, an electron injection layer, a layer for simultaneous electron transport and electron injection, and a light emitting layer,
An organic electroluminescent device, wherein at least one of the layers includes any one compound selected from the organic light-emitting compounds according to claim 1 or 3. The method of claim 5,
The organic electroluminescent device, characterized in that the hole injection layer, the hole transport layer, or the layer for simultaneously injecting and transporting holes comprises any one compound selected from the organic light emitting compound according to claim 1 or 3. The method of claim 6,
An organic electroluminescent device, characterized in that the hole transport layer includes any one compound selected from the organic light-emitting compounds according to claim 1 or 3. The method of claim 4,
An organic electroluminescent device, characterized in that it emits white light by further comprising at least one organic light emitting layer emitting red, green, or blue light on the organic material layer.

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