KR20200104042A - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to an organic light-emitting compound capable of forming a single hole layer of multi-functional hole transportation layer (HTL) as a compound that is a p-doping material for a hole transport material represented by chemical formula I or chemical formula II, or a multi-functional HTL compound of a fused structure which can combine p-doping and hole transport functions, and to an organic light-emitting device having significantly improved luminous efficiency and service life characteristics while being possible to drive a low voltage by employing the same.

Description

An organic light emitting compound and an organic light emitting device comprising the same {An electroluminescent compound and an electroluminescent device comprising the same}

The present invention relates to an organic light-emitting compound employed in a hole layer of an organic light-emitting device, and more particularly, a compound that is a p-doping material for a hole transport material, or a fused compound capable of acquiring p-doping and hole transport functions together. As a structured multifunctional HTL (Multi functional HTL) compound, an organic light emitting compound capable of constituting a single hole layer of a multifunctional HTL (Multi Functional Hole Transportation Layer), and low voltage driving by adopting it, and the luminous efficiency and lifespan characteristics are remarkably improved. It relates to an organic light emitting device.

Recently, organic light-emitting devices capable of low voltage driving by self-luminous type have superior viewing angles and contrast ratios compared to liquid crystal displays, which are the mainstream of flat panel display devices, do not require a backlight, are lightweight and thin, are advantageous in terms of power consumption, and color reproduction range Is attracting attention as a next-generation display device.

An organic light-emitting device is a device that emits light as electrons and holes form a pair and then disappear when electric charges are injected into the organic light-emitting layer formed between the electron injection electrode (cathode) and the hole injection electrode (anode). In addition to being able to form a device on a substrate, it is possible to drive at a lower voltage of 10 V or less compared to a plasma display panel or an inorganic light emitting display, consumes relatively little power, and has an excellent color. In addition, the organic light emitting device is capable of displaying three colors of green, blue, and red, and thus is a subject of much interest as a next-generation rich color display device.

In the organic light emitting device, the processes for emitting light, that is, charge injection, charge transport, photoexcitation formation, and light generation, are divided into roles using different organic layers. Accordingly, an organic light-emitting device having a structure subdivided into layers including a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc. between the anode and the cathode is used, and the organic light-emitting device has the above-described characteristics. In order to demonstrate this, it must first be supported by a stable and efficient material such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, an electron blocking material, etc., which constitute the organic layer in the device. The development of an efficient and efficient organic material layer material for an organic light-emitting device has not been made sufficiently.

Therefore, in order to realize a more stable organic light emitting device, and to achieve high efficiency, long life, and large size of the device, additional improvement is required in terms of efficiency and lifespan characteristics. In this regard, recently, a hole transport layer among the structures of the organic light emitting device For materials, research has been conducted to further provide a layer containing a p-type material between the electrode and the hole transport layer by doping or subdividing the layer with a p-type material to improve the mobility of the existing organic material. Is losing.

In particular, when doping with organic materials, negative conductivity is formed, so that even a thick transport layer can lower a voltage drop in the transport layer, and a thin space charge layer formed by increasing the doping level enables charge injection by tunneling effectively. By doping the hole transport layer, it is possible to control the high conductivity of the hole transport layer and the charge density of the charge carrier, and as a result, the conductivity of the organic material layer is improved to improve the characteristics of the device, thereby realizing a device with low driving voltage and high efficiency.

However, there are still problems such as poor process efficiency due to the application of additional organic materials and organic layers, and it is difficult to implement low voltage driving due to the thickness of the organic layer.

Accordingly, the present invention is to solve the above problem, provides a p-type doping material for the hole transport material, and does not separately perform p-doping for the hole transport material, and can be collected together with p-doping and hole transport. By providing a multifunctional HTL (Multi functional HTL) compound with a fused structure, an organic light emitting device constituting a single hole layer of a multifunctional HTL (Multi Functional Hole Transportation Layer) is provided, while stably realizing characteristics such as improved luminous efficiency and long life. It is intended to provide an organic light emitting device capable of implementing low voltage driving at a level equal to or higher than that of a conventional device.

In order to solve the above problems, the present invention comprises an organic light emitting compound represented by the following [Chemical Formula I] or [Chemical Formula II] and at least one light emitting compound represented by the following [Chemical Formula I] or [Chemical Formula II] in an organic layer. It provides an organic light emitting device.

The compound of [Chemical Formula I] or [Chemical Formula II] according to the present invention may be a p-type doping material for a hole transport material, and furthermore, each moiety having a p-doping function and a hole transport property has one structure It is characterized in that it is a multifunctional HTL (Multi functional HTL) compound that is introduced into, that is, a hole transport moiety (Hole Transportation Unit) and a p-doped moiety (p-Dopant Unit) fused to contain.

[Chemical Formula Ⅰ] [Chemical Formula Ⅱ]

Specific structures and substituents of the compound represented by [Chemical Formula I] or [Chemical Formula II] will be described later.

In addition, the present invention provides an organic light-emitting device comprising an anode, a cathode, and a plurality of organic layers that are placed in contact with the anode and the cathode, and include the organic light-emitting compound according to the present invention in the plurality of organic layers. do.

In particular, the plurality of organic layers are composed of a plurality of layers having various characteristics such as an electron layer, a light emitting layer, and a hole layer, and according to an embodiment of the present invention, the hole layer is a multifunctional HTL (multi functional hole transportation layer), It is characterized by employing a multifunctional HTL (Multi functional HTL) compound according to the present invention including a transport moiety (Hole Transportation Unit) and a p-doped moiety (p-Dopant Unit).

When the organic light-emitting compound according to the present invention is used as a p-type doping material in the hole transport layer of an organic light-emitting device, it can realize remarkably excellent light-emitting characteristics such as light efficiency and quantum efficiency, and thus can be usefully used in various display devices.

In addition, the organic light-emitting compound according to the present invention is a multi-functional HTL (Multi functional HTL) compound that combines p-doping function and hole transport characteristics into one, and is characterized in that it can be composed of a single hole layer (multifunctional HTL). Therefore, compared to the conventional device, the device that introduced it can improve hole transport without additional p-doping, and thus realize improved luminous efficiency and low-voltage driving equivalent to that of the conventional device, so that it is useful for various display devices. In addition, compared to a conventional device, a process including a separate p-type layer or a p-doping process is not required, and thus the efficiency of a device manufacturing process may be improved.

1 is a representative diagram showing the structure of an organic light emitting compound according to 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] or [Chemical Formula II].

[Chemical Formula Ⅰ] [Chemical Formula Ⅱ]

In the above [Formula I] or [Formula II],

X ₁ is any one selected from O, S, R ₁₃ -CR ₁₄ , R ₁₅ -Si-R ₁₆ and NR ₁₇ , X ₂ is CR ₁₉ or N, and X ₃ and X ₄ are each independently O, It may be any one selected from S, R ₂₀ -CR ₂₁ , R ₂₂ -Si-R ₂₃ and NR ₂₄ .

A and B may be the same as or different from each other, and each independently may be any one selected from the following [Structural Formula 1].

[Structural Formula 1]

In [Structural Formula 1],

R ₁ to R ₄ are each independently a halogen group, cyano group, nitro group, sulfonyl group (SO ₂ R'), sulfoxide group (SO ₃ ), carbonyl group (COR'), carboxyl group (CO ₂ R'), sorghum , Deuterium, a substituted or unsubstituted silyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted halogenated alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and Any one selected from a substituted or unsubstituted C2 to C30 heteroaryl group.

R'is hydrogen, deuterium, cyano group, halogen group, amino group, thiol group, hydroxy group, nitro group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl group having 1 to 24 carbon atoms, alkenyl group having 2 to 24 carbon atoms, 6 carbon atoms It is selected from an aryl group having 2 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, and an arylsilyl group having 1 to 24 carbon atoms.

R is hydrogen, deuterium, cyano group, halogen group, substituted or unsubstituted silyl group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted It is selected from a substituted or unsubstituted C6-C50 arylamine group, and a substituted or unsubstituted C3-C50 heteroarylamine group.

R ₅ to R ₂₄ are each independently hydrogen, deuterium, halogen group, cyano group, substituted or unsubstituted silyl group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted C6 to C30 It is selected from an aryl group, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 50 carbon atoms, and a substituted or unsubstituted heteroarylamine group having 3 to 50 carbon atoms.

In addition, according to an embodiment of the present invention, the two R in the [Chemical Formula I] are the same as or different from each other, and are each selected from the following [Structural Formula 2] and [Structural Formula 3], and preferably each It is characterized by represented by the following [Structural Formula 2].

[Structural Formula 2]

[Structural Formula 3]

In the [Structural Formula 2] and [Structural Formula 3],

L ₁ and L ₂ are each a single bond, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, n and m are each 0 to 4 It is an integer, and when n and m are each 2 or more, a plurality of L ₁ and L ₂ are each the same or different from each other.

Ar ₁ to Ar ₃ are the same as or different from each other, and each independently selected from a substituted or unsubstituted aryl group having 5 to 50 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms.

The Ar ₁ and Ar ₂ may be bonded to each other or linked with an adjacent substituent to form an alicyclic, aromatic monocyclic or polycyclic ring, and carbon atoms of the formed alicyclic, aromatic monocyclic or polycyclic ring are N, S and O may be substituted with one or more heteroatoms selected from.

o, p, and q are each an integer of 1 to 3, and when o, p, and q are each 2 or more, a plurality of Ar ₁ to Ar ₃ are the same or different from each other.

In addition, according to an embodiment of the present invention, at least any one of R ₅ to R ₈ and at least one of R ₉ to R ₁₂ in [Formula II] are the same as or different from each other, and each of the [Structural Formula 2] ] And [Structural Formula 3], preferably each represented by the following [Structural Formula 2].

On the other hand, R, R ₁ to R ₂₄ , L ₁ , L ₂ and Ar ₁ to Ar ₃ may each be further substituted with one or more substituents, and the substituents are hydrogen, deuterium, amino group, cyano group, hydroxy group, nitro group , A halogen group, an amide group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a heterocycloalkyl group having 2 to 20 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, 1 A to 20 alkoxy group, a C6 to C30 aryloxy group, a C1 to C30 alkylthioxy group, a C5 to C30 arylthioxy group, a C1 to C30 alkylamine group, a C5 to C30 arylamine group , An aryl group having 6 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, an aryl group having 6 to 50 carbon atoms in which one or more cycloalkyls having 3 to 20 carbon atoms are fused, and one or more cycloalkyl having 3 to 20 carbon atoms It may be selected from a heteroaryl group having 6 to 50 carbon atoms and a silyl group.

The organic light-emitting compound represented by [Chemical Formula I] or [Chemical Formula II] according to the present invention may be employed in various organic material layers in the organic light-emitting device, but according to a preferred embodiment, it is a material used for the hole transport layer in the organic light-emitting device alone. It can be utilized, and it can also be used as a p-type dopant doping a compound having a hole transport function.

The p-type refers to the characteristics of a p-type semiconductor, and the p-type is a property of injecting or transporting holes through the highest occupied molecular orbital (HOMO) energy level, which is a property of a material whose hole mobility is greater than that of electrons. Is defined as P-type doping means that it is doped to have these p-type properties.

In particular, conventionally, in order to control the high conductivity of the hole transport layer formed on the ITO substrate and the charge density of the charge carrier, doping with a p-type dopant, or a layer made of a p-type dopant between the ITO substrate and the hole transport layer However, in an embodiment of the present invention, a single hole transport layer made of a compound represented by [Chemical Formula I] or [Chemical Formula II] may be applied without a separate p-type dopant process or insertion.

That is, the compound represented by [Chemical Formula I] or [Chemical Formula II] is a multifunctional HTL (multi functional HTL) compound, including both a hole transport structure and a p-doped structure, and a moiety having a hole transport function and a hole injection function It means to have both, and by using it, the hole injection function and the hole transport function are fused, without forming a hole transport layer and a hole injection layer, respectively, and organic light emission composed of a single hole layer of a multifunctional HTL (Multi Functional Hole Transportation Layer). The device can be implemented, and the low voltage driving and high efficiency characteristics of the organic light emitting device can be satisfied.

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 a straight chain or branched chain, and specific examples are methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group , sec-butyl group, 1-methyl-butyl group, 1-ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1 -Methylpentyl group, 2-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentyl Methyl 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. 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 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 heterocyclic group is a heterocyclic group containing O, N or S as a heteroatom, a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a 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 pyrimidi Nyl 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, etc., but limited to these It does not become.

In the present invention, the aryl group in the aryloxy group and the arylthioxy group is the same as the example 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 specifically, a cyclopropyl group, a cyclobutyl group, a 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. Does not.

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 alkylthioxy group is the same as the example of the aforementioned alkyl group. 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.

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

In addition, conventionally, in order to control the high conductivity of the hole transport layer formed on the ITO substrate and the charge density of the charge carrier, it is doped with a p-type dopant, or a layer made of a p-type dopant between the ITO substrate and the hole transport layer. However, it is possible to implement a single layer of a multifunctional HTL hole layer made of a multifunctional HTL compound represented by [Chemical Formula I] or [Chemical Formula II] without a separate p-type dopant process or insertion. .

Preferred examples of the doping material or multifunctional HTL (Multifunctional HTL) compound of the hole transport material represented by [Chemical Formula I] or [Chemical Formula II] according to the present invention include compounds represented by the following compounds 1 to 100, but these It is not limited to

The organic light-emitting compound according to the present invention represented by [Chemical Formula I] or [Chemical Formula II] may be used as an organic material layer of an organic light-emitting device due to its structural specificity, and more specifically, a p-type in the hole transport layer or the hole injection layer in the organic material layer. It may be used as a doping material, and the like, and according to a preferred embodiment of the present invention, the organic light emitting compound according to the present invention is used as a doping material for the hole transport compound of the conventional hole transport layer, so that excellent light emitting characteristics of the device can be realized.

In addition, the organic light-emitting compound according to the present invention introduces each moiety having a p-doping function and a hole transport property into one structure, and is a multifunctional HTL having the intrinsic characteristics of each introduced substituent. functional HTL) compound, as a result, it is possible to implement a single hole layer of a multifunctional HTL (Multi Functional Hole Transportation Layer), thereby implementing an organic light-emitting device having excellent light-emitting characteristics with further improved low-voltage driving characteristics, luminous efficiency and lifetime characteristics.

The compound of the present invention can be applied to a device according to a conventional manufacturing method of an organic light emitting 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 for the organic material layer of the device. Except for 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 light emitting 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 multi-functional HTL layer, a layer that simultaneously injects and transports electrons, and a light emitting layer. One or more layers may be included, and one or more of the layers may include a compound represented by [Chemical Formula I] or [Chemical Formula II].

In addition, the organic light emitting device according to the present invention may have a structure including a first electrode and a second electrode, and a plurality of organic layers including an electronic layer, a light emitting layer, a hole layer, etc. disposed therebetween, and a hole injection function and By fusion of the hole transport function, the hole transport layer and the hole injection layer are not formed separately, but the multi-functional HTL layer is formed as a single layer, and formed without forming a separate p-type layer. Except for one, it can be manufactured using conventional device manufacturing methods and materials.

The organic layer of the organic light emitting device according to the present invention may be made of a multilayer structure in which two or more organic layers are stacked, except that the hole injection layer and the hole transport layer are composed of a multifunctional HTL single layer, and the number is not limited thereto. It may also contain a large number of organic layers.

The organic layer structure of the organic light-emitting device according to the present invention will be described in more detail in Examples to be described later.

The organic light emitting device according to the present invention is characterized in that the electrical conductivity of the multifunctional HTL is 1 × 10 ^-3 S/m to 1 × 10 ^-1 S/m.

In the organic light-emitting device according to the present invention, the multifunctional HTL, that is, the HOMO energy level of the single hole layer composed of the multifunctional HTL compound is in the range of-4.5 eV to-7.0 eV when expressed as an absolute scale indicating zero vacuum energy level. And, according to an embodiment, the HOMO energy level of the multifunctional HTL may be in the range of -5.0 eV to -6.0 eV when the vacuum energy level is expressed as an absolute scale indicating 0.

In the organic light emitting device according to the present invention, the multifunctional HTL, that is, the LUMO energy level of the single hole layer composed of the multifunctional HTL compound is in the range of-4.0 eV to-6.0 eV when expressed on an absolute scale indicating the vacuum energy level is 0. And, according to an embodiment, the LUMO energy level of the multifunctional HTL may be in the range of -4.4 eV to -5.5 eV when the vacuum energy level is expressed as an absolute scale indicating 0.

In the organic light emitting device according to the present invention, a band gap of the multifunctional HTL is characterized in that the absolute value is 2 or less, and according to an embodiment, the absolute value may be 0.3 to 1.0.

In the organic light-emitting device according to the present invention, the work function of the anode is multifunctional HTL, that is, the highest LUMO energy level of a single hole layer composed of multifunctional HTL compounds, and is characterized in that the absolute value is 1 or less, and according to one embodiment, it may be 0.5 or less. .

The multifunctional HTL of the organic light emitting device according to the present invention may have a thickness of 20 to 1,000 Å, and through this, it is possible to obtain the electrical conductivity properties and voltage drop effect required for the multi-functional HTL, and at the same time, the multi-functional HTL thickness can be up to 1,000 Å. The mechanical properties of HTL can also be improved.

The organic light-emitting device according to the present invention deposits a metal or a conductive metal oxide or an alloy thereof on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. 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 light-emitting 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 light-emitting device according to the present invention may be of 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, preferred embodiments are presented to aid in understanding 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 1: Synthesis of Compound 4

(1) Preparation Example 1: Synthesis of Intermediate 4-1

2,5-dimethoxybenzene-1,4-diol (10 g, 0.059 mol, Mascot.), 100 mL of acetic acid, stirred, 30 mL of nitric acid at room temperature, and stirred at 80 °C for 0.5 hours to react. After the reaction was completed, cooled to room temperature, cold water was added, and the resulting solid was filtered, and 13 g (yield 85%) of <Intermediate 4-1> was obtained through column purification.

(2) Preparation Example 2: Synthesis of Intermediate 4-2

Intermediate 4-1 (10 g, 0.029 mol), Pd/C, 200 mL of EtOH was added, stirred at 0 ℃ using an ice bath in nitrogen state, and then hydrazine hydrate (6.16 g, 0.192 mol, sigma aldrich) was slowly added dropwise. Then, the mixture was stirred under reflux for 30 minutes to react. After the reaction was completed, extraction was performed and 6.8 g (yield 88.3%) of <Intermediate 4-2> was obtained through column purification.

(3) Preparation Example 3: Synthesis of Intermediate 4-3

Intermediate 4-2 (10 g, 0.05 mol), triethyl orthoformate (74 g, 0.5 mol, sigma aldrich), yttrium(III) trifluoromethanesulfonate (1.34 g, 0.0025 mol, sigma aldrich), 300 mL of DMSO and 4 hours at 60 ℃ It was stirred and reacted. After completion of the reaction, extraction was performed and column purification was performed to give 8.3 g (yield 75.4%) of <Intermediate 4-3>.

(4) Preparation Example 4: Synthesis of Intermediate 4-4

Add 250 mL of dimethylformamide to intermediate 4-1 (10 g, 0.045 mol), tetrabromomethane (33.14 g, 0.1 mol, sigma aldrich), sodium tert-butoxide (34.92 g, 0.363 mol, sigma aldrich), and stir at room temperature for 6 hours And reacted. After the reaction was completed, extraction was performed and column purification was performed to obtain 13 g (75.7% yield) of <Intermediate 4-4>.

(5) Preparation Example 5: Synthesis of Intermediate 4-5

Intermediate 4-4 (10 g, 0.025 mol), phenylboronic acid (7.10 g, 0.058 mol), potassium carbonate (10.97 g, 0.079 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (1.53 g, 0.0013 mol, sigma aldrich ), 200 mL of Tol, 40 mL of EtOH, and 20 mL of H ₂ O were added and stirred under reflux for 12 hours to react. After completion of the reaction, extraction was performed and column purification was performed to give 7 g (71% yield) of <Intermediate 4-5>.

(6) Preparation Example 6: Synthesis of Intermediate 4-6

200 mL of dichloromethane was added to Intermediate 4-5 (10 g, 0.027 mol), borontribromide, and stirred for 6 hours to react. After completion of the reaction, extraction was performed and column purification was performed to give 5 g (54% yield) of <Intermediate 4-6>.

(7) Preparation Example 7: Synthesis of Intermediate 4-7

Intermediate 4-6 (10 g, 0.027 mol), an excess of MnO ₂ , methylene chloride 150 mL was added, stirred under reflux, and stirred for 24 hours to react. After completion of the reaction, extraction was performed and column purification was performed to obtain 8.4 g (yield 84.4%) of <Intermediate 2-2>.

(8) Preparation Example 8: Synthesis of Compound 4

Intermediate 4-7 (10 g, 0.029 mol), malononitrile (11.58 g, 0.175 mol, sigma aldrich), methylene chloride 300 mL, cooled in an ice-bath, and TiCl ₄ (33.25 g, 0.175 mol, sigma aldrich) was slowly dropped and pyridine (20.8 g, 0.263 mol) was added dropwise very slowly. After 1 hour, the ice bath was removed and stirred for 24 hours to react. After the reaction was completed, extraction was performed with an aqueous hydrochloric acid solution, followed by column purification to obtain 8.6 g (67.1% yield) of compound 4.

H-NMR (200MHz, CDCl3): δppm, 2H(7.41/m) 4H(8.05/d, 7.51/d)

LC/MS: m/z=438[(M+1) ⁺ ]

Synthesis Example 2: Synthesis of Compound 20

(1) Preparation Example 1: Synthesis of Intermediate 20-1

Gallium trichloride (0.51 g, 0.0029 mol, sigma aldrich) was added to 150 mL of 1,2-dichloroethane, intermediate 4-6 (10 g, 0.029 mol), cyanic bromide (6.77 g, 0.064 mol, sigma aldrich) was added and then 120 The reaction was carried out by stirring at °C for 5 hours. After completion of the reaction, extraction was performed and column purification was performed to give 5.8 g (yield 55.1%) of <Intermediate 20-1>.

(2) Preparation Example 2: Synthesis of Intermediate 20-2

Intermediate 20-1 (10 g, 0.028 mol) was added to 150 mL of dichloromethane, cooled to -78° C., DIBAL (1.0 M in THF) was slowly added dropwise, stirred for 1 hour, and then stirred at room temperature for 1 hour. Then, after cooling to 0° C., acetic acid and H ₂ O were added for extraction, followed by column purification to give 7.5 g (yield 73.8%) of <Intermediate 20-2>.

(3) Preparation Example 3: Synthesis of Intermediate 20-3

Intermediate 20-2 (10 g, 0.027 mol), oxalaldehyde (3.94 g, 0.068 mol, sigma aldrich), ammonium acetate (12.56 g, 0.163 mol, sigma aldrich), put in 250 mL of acetic acid and stirred at 110 ℃ for 12 hours And reacted. After the reaction was completed, ice H ₂ O was added for extraction, followed by column purification to obtain 6 g (yield 49.7%) of <Intermediate 20-3>.

(4) Preparation Example 4: Synthesis of Intermediate 20-4

Intermediate 20-3 (10 g, 0.0225 mol) and 300 mL of THF were added, cooled to 0° C., and N- bromosuccinimide (16.02 g, 0.090 mol, sigma aldrich) was slowly added, followed by stirring at room temperature for 5 hours to react. After completion of the reaction, extraction and purification were performed to give 13.3 g (77.7% yield) of <Intermediate 20-4>.

(5) Preparation Example 5: Synthesis of Intermediate 20-5

Intermediate 20-4 (10 g, 0.013 mol), CuCN (11.78 g, 0.132 mol, sigma aldrich), 250 mL of DMF were added, stirred under reflux and stirred for 8 hours to react. After completion of the reaction, extraction and purification were performed to give 3.5 g (yield 48.8%) of <Intermediate 20-5>.

(6) Preparation Example 6: Synthesis of Intermediate 20-6

Intermediate 20-5 (10 g, 0.018 mol), potassium hydroxide (10.31 g, 0.184 mol) H ₂ O 20 mL, 1,4-dioxane 400 mL added to K ₃ Fe(CN) ₆ (42.33 g, 0.129 mol) After adding a solution (420 mL of H ₂ O) dropwise, the mixture was stirred at 100° C. for 12 hours to react. After the reaction was completed, extraction was performed and column purification was performed to obtain 3.8 g (38.1% yield) of compound 20.

H-NMR (200MHz, CDCl3): δppm, 2H(7.41/m) 4H(8.05/d, 7.51/m)

LC/MS: m/z=542[(M+1) ⁺ ]

Synthesis Example 3: Synthesis of Compound 58

(1) Preparation Example 1: Synthesis of Intermediate 58-1

1,4-difluoro-2,5-dimethoxybenzene (10 g, 0.057 mol, sigma aldrich), 300 mL of dimethyl chloride were added, cooled to 0° C., bromine was slowly added dropwise, and stirred at room temperature for 5 hours to react. After completion of the reaction, extraction and purification were performed to give 14 g (yield 73.4%) of <Intermediate 58-1>.

(2) Preparation Example 2: Synthesis of Intermediate 58-2

Intermediate 58-1 (10 g, 0.030 mol), 2-hydroxyphenylboronic acid (9.14 g, 0.066 mol, sigma aldrich), potassium carbonate (20.82 g, 0.151 mol, sigma aldrich), Pd(PPh ₃ ) ₄ (1.74 g, 0.0015 mol, sigma aldrich), 250 mL of Tol, 50 mL of EtOH, 30 mL of H ₂ O were added and stirred under reflux for 12 hours to react. After completion of the reaction, extraction was performed and column purification was performed to obtain 8 g (74.1% yield) of <Intermediate 58-2>.

(3) Preparation Example 3: Synthesis of Intermediate 58-3

Intermediate 58-2 (10 g, 0.046 mol), potassium carbonate (11.57 g, 0.084 mol, sigma aldrich), DMAP (0.34 g, 0.0028 mol, sigma aldrich), 300 mL of DMF, and stirred under reflux at 160° C. for 3 hours Reacted. After completion of the reaction, extraction was performed and column purification was performed to give 7.3 g (yield 82.1%) of <Intermediate 58-3>.

(4) Preparation Example 4: Synthesis of Intermediate 58-4

200 mL of dichloromethane was added to Intermediate 4-5 (10 g, 0.031 mol), borontribromide, and stirred for 6 hours to react. After the reaction was completed, extraction was performed and column purification was performed to give 5 g (54% yield) of <Intermediate 58-4>.

(5) Preparation Example 5: Synthesis of Intermediate 58-5

Gallium trichloride (0.61 g, 0.0029 mol, sigma aldrich) was added to 150 mL of 1,2-dichloroethane, intermediate 4-6 (10 g, 0.035 mol), cyanic bromide (8.03 g, 0.076 mol, sigma aldrich) was added and then 120 The reaction was carried out by stirring at °C for 5 hours. After completion of the reaction, extraction was performed and column purification was performed to obtain 6 g (yield 56.4%) of <Intermediate 58-5>.

(6) Preparation Example 6: Synthesis of Intermediate 58-6

Intermediate 20-1 (10 g, 0.032 mol) was added to 150 mL of dichloromethane, cooled to -78 °C, DIBAL (1.0 M in THF) was slowly added dropwise, stirred for 1 hour, and then stirred at room temperature for 1 hour. After cooling to 0° C., acetic acid and H ₂ O were added for extraction, followed by column purification to obtain 7.6 g (yield 74.5%) of <Intermediate 58-6>.

(7) Preparation Example 7: Synthesis of Intermediate 58-7

Intermediate 58-6 (10 g, 0.032 mol), 1,1,1,4,4,4-hexafluorobutane-2,3-dione (15.43 g, 0.080 mol, Mascot.), ammonium acetate (14.72 g, 0.191 mol) , sigma aldrich), acetic acid (250 mL) and stirred at 110° C. for 12 hours to react. After the reaction was completed, ice H ₂ O was added for extraction, followed by column purification to give 11.6 g (yield 55%) of <Intermediate 58-7>.

(8) Preparation Example 8: Synthesis of Compound 58

Intermediate 58-7 (10 g, 0.015 mol), potassium hydroxide (8.47 g, 0.151 mol) H ₂ O 25 mL, 1,4-dioxane 500 mL were added and K ₃ Fe(CN) ₆ (34.79 g, 0.106 mol) After adding a solution (350 mL of H ₂ O) dropwise, the mixture was stirred at 100° C. for 12 hours to react. After completion of the reaction, extraction was performed and column purification was performed to obtain 4 g (40% yield) of compound 58.

H-NMR (200MHz, CDCl3): δppm, 2H (7.89/d, 7.66/d, 7.38/m, 7.32/m)

LC/MS: m/z=660[(M+1) ⁺ ]

Synthesis Example 4: Synthesis of Compound 98

(1) Preparation Example 1: Synthesis of Intermediate 98-1

Bromobenzene (10 g, 0.064 mol, sigma aldrich), 2-naphthylamine (10.94 g, 0.076 mol, sigma aldrich), sodium tert-butoxide (12.24 g, 0.13 mol, sigma aldrich), catalyst Pd(dba) ₂ (1.83 g , 0.0032 mol, sigma aldrich), tri-tert-Bu-phosphine (1.24 g, 0.0064 mol, sigma aldrich) was added to 300 mL of Toluene and stirred at 100° C. for 4 hours to react. After the reaction was completed, extraction was performed and column purification was performed to obtain 18 g (71.6% yield) of <Intermediate 98-1>.

(2) Preparation Example 2: Synthesis of Intermediate 98-2

Bromobenzene (10 g, 0.064 mol, sigma aldrich), 2-aminobiphenyl (12.93 g, 0.076 mol, sigma aldrich), sodium tert-butoxide (12.24 g, 0.13 mol, sigma aldrich), catalyst Pd(dba) ₂ (1.83 g , 0.0032 mol, sigma aldrich), tri-tert-Bu-phosphine (1.24 g, 0.0064 mol, sigma aldrich) was added to 300 mL of Toluene and stirred at 100° C. for 4 hours to react. After completion of the reaction, extraction was performed and column purification was performed to obtain 11.7 g (74.8% yield) of <Intermediate 98-2>.

(3) Preparation Example 3: Synthesis of Intermediate 98-3

Intermediate 98-1 (10 g, 0.046 mol), Intermediate 4-4 (12.93 g, 0.058 mol), sodium tert-butoxide (8.77 g, 0.055 mol, sigma aldrich), catalyst Pd(dba) ₂ (1.31 g, 0.091) mol, sigma aldrich), tri-tert-Bu-phosphine (1.31 g, 0.0046 mol, sigma aldrich) was added to 300 mL of Toluene and stirred at 100° C. for 4 hours to react. After the reaction was completed, extraction was performed and column purification was performed to obtain 7.2 g (yield 52.7%) of <Intermediate 98-3>.

(4) Preparation Example 4: Synthesis of Intermediate 98-4

Intermediate 98-3 (10 g, 0.019 mol), Intermediate 98-2 (5.70 g, 0.023 mol), sodium tert-butoxide (8.77 g, 0.055 mol, sigma aldrich), catalyst Pd(dba) ₂ (0.56 g, 0.001) mol, sigma aldrich), tri-tert-Bu-phosphine (0.39 g, 0.0019 mol, sigma aldrich) was added to 300 mL of Toluene and stirred at 100° C. for 6 hours to react. After the reaction was completed, extraction was performed and column purification was performed to obtain 10 g (75.8% yield) of <Intermediate 98-4>.

(5) Preparation Example 5: Synthesis of Intermediate 98-5

200 mL of dichloromethane was added to Intermediate 98-4 (10 g, 0.015 mol), borontribromide, and stirred for 6 hours to react. After completion of the reaction, extraction was performed and column purification was performed to give 4.8 g (yield 50%) of <Intermediate 98-5>.

(6) Preparation Example 6: Synthesis of Intermediate 98-6

Intermediate 98-5 (10 g, 0.015 mol), an excess of MnO ₂ , 150 mL of methylene chloride were added, stirred under reflux, and stirred for 24 hours to react. After completion of the reaction, extraction was performed and column purification was performed to give 8.7 g (yield 87.28%) of <Intermediate 98-6>.

(7) Preparation Example 7: Synthesis of Intermediate 98-7

Intermediate 4-7 (10 g, 0.015 mol), malononitrile (3.05 g, 0.046 mol, sigma aldrich), methylene chloride 300 mL, cooled in an ice-bath, and TiCl ₄ (8.75 g, 0.046 mol, sigma aldrich) was slowly dropped and pyridine (4.86 g, 0.062 mol) was added dropwise very slowly. After 1 hour, the ice bath was removed and stirred for 24 hours to react. After completion of the reaction, extraction was performed with an aqueous hydrochloric acid solution, followed by column purification to give 6.1 g (yield 61.4%) of <Intermediate 98-7>.

(8) Preparation Example 8: Synthesis of Compound 98

Intermediate 98-7 (10 g, 0.014 mol), bis(3-fluorophenyl)methane (8.77 g, 0.043 mol), methylene chloride 300 mL, cooled in an ice-bath, and TiCl ₄ (8.14 g, 0.043 mol, sigma) aldrich) was slowly dropped, and pyridine (4.53 g, 0.057 mol) was added dropwise very slowly. After 1 hour, the ice bath was removed and stirred for 24 hours to react. After the reaction was completed, extraction was performed with an aqueous hydrochloric acid solution, followed by column purification to obtain 7.7 g (60.8% yield) of compound 98.

H-NMR (200MHz, CDCl3): δppm, 1H (7.88/d, 7.84/d, 7.77/d, 7.74/s, 7.50/m, 7.49/d, 7.41/m, 7.36/m) 2H (7.54/d , 7.52/d, 7.51/m, 7.26/m, 7.15/d, 7.12/d, 6.96/d, 6.81/m, 6.69/s) 4H (7.20/m, 6.63/d)

LC/MS: m/z=884[(M+1) ⁺ ]

Device Example

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 10

By using the multifunctional HTL (Multi functional HTL) compound according to the present invention as a material employed in the multifunctional HTL hole layer according to the present invention, a blue light-emitting organic electroluminescent device having the following device structure is manufactured, and light emission including luminous efficiency The properties were measured.

ITO / multifunctional HTL hole layer (100 nm) / electron blocking layer (10 nm) / light emitting layer (20 nm) / electron transport layer (201:Liq 30 nm) / LiF (1 nm) / Al (100 nm)

A hole layer was formed on an ITO transparent electrode using multifunctional HTL compounds 61, 65, 72, 75, 83, 89, 91 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) An organic light-emitting device was manufactured by depositing 30 nm, 1 nm of LiF, and 100 nm of aluminum by a vapor deposition method.

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 the hole layer was doped with 5% F4TCNQ in α-NPB in place of the compound according to the present invention.

Element Comparative Example 2

The organic electroluminescent device for Device Comparative Example 2 was fabricated in the same manner as in the device structure of Example 1, except that α-NPB was used for the hole layer in place of the compound according to the present invention.

Experimental Example 1: Light emission characteristics of device Examples 1 to 10

The organic electroluminescent device manufactured according to the above embodiment measured voltage, current, and luminous efficiency using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research), and a voltage having a luminance of 1000 nit. Was defined as "driving voltage" and compared. The results are shown in Table 1 below.

Example Multifunctional HTL V cd/A CIEx CIEy One Compound 61 4.8 8.29 0.145 0.142 2 Compound 65 4.8 8.12 0.144 0.142 3 Compound 72 4.8 8.20 0.145 0.143 4 Compound 75 4.9 7.92 0.145 0.148 5 Compound 83 4.9 8.06 0.144 0.151 6 Compound 89 5.0 8.13 0.145 0.146 7 Compound 91 4.9 7.86 0.145 0.152 8 Compound 93 4.9 7.97 0.145 0.153 9 Compound 97 4.9 8.41 0.145 0.152 10 Compound 98 5.0 8.25 0.144 0.150 Comparative Example 1 α-NPB: F4TCNQ 5.7 6.84 0.145 0.146 Comparative Example 2 α-NPB 6.2 6.20 0.148 0.155

Looking at the results shown in [Table 1], when the compound according to the present invention is applied to the multi-functional HTL layer of the device alone, even though doping was not separately compared to the conventional device (comparative example) And it can be confirmed that the luminous properties such as luminous efficiency and quantum efficiency are remarkably excellent.

[α-NPB] [EBL1] [BH1] [BD1] [201] [F4TCNQ]

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 11 to 16

Using the compound 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 injection layer (5 nm) / hole transport layer (100 nm) / electron blocking layer (10 nm) / emitting layer (20 nm) / electron transport layer (201:Liq 30 nm) / LiF (1 nm) / Al (100 nm)

Compounds 4, 20, 46, 58, 60, and 95 according to the present invention were formed in a thickness of 5 nm on the hole injection layer on the ITO transparent electrode, and the hole transport layer was formed at 100 nm using α-NPB. At this time, 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) An organic light-emitting device was manufactured by depositing 30 nm, 1 nm of LiF, and 100 nm of aluminum by a vapor deposition method.

Element Comparative Example 3

The organic light emitting device for Device Comparative Example 3 was fabricated in the same manner as in Example 11 except that HAT-CN was used as a material for the hole injection layer in the device structure.

Experimental Example 2: Light emission characteristics of device Examples 11 to 16

The organic light-emitting 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 voltage having a luminance of 1000 nit was measured. It was defined and compared as "driving voltage". The results are shown in Table 2 below.

Example P-doped substance V cd/A QE(%) CIEx CIEy 11 Compound 4 4.70 8.24 7.65 0.145 0.153 12 Compound 20 4.75 8.27 7.69 0.145 0.153 13 Compound 46 4.80 8.33 7.73 0.145 0.152 14 Compound 58 4.85 8.25 7.67 0.145 0.152 15 Compound 60 4.90 8.29 7.71 0.145 0.152 16 Compound 95 4.95 8.30 7.72 0.146 0.153 Comparative Example 3 HAT-CN 5.40 7.5 6.1 0.147 0.156

Looking at the results shown in [Table 2], when the compound according to the present invention is applied to a device as a material for a hole injection layer, luminous properties such as luminous efficiency and quantum efficiency are more than when using HAT-CN compared to the conventional device (Comparative Example). This remarkably excellent can be confirmed.

[α-NPB]

[HAT-CN] [EBL1] [BH1] [BD1] [201]

Claims (11)

Organic light-emitting compounds represented by the following [Chemical Formula I] to [Chemical Formula II]:
[Formula Ⅰ] [Formula Ⅱ]

In the above [Formula I] or [Formula II],
X ₁ is any one selected from O, S, R ₁₃ -CR ₁₄ , R ₁₅ -Si-R ₁₆ and NR ₁₇ ,
X ₂ is CR ₁₉ or N,
X ₃ and X ₄ are each independently any one selected from O, S, R ₂₀ -CR ₂₁ , R ₂₂ -Si-R ₂₃ and NR ₂₄ ,
A and B are the same as or different from each other, and each independently is any one selected from the following [Structural Formula 1],
[Structural Formula 1]

In [Structural Formula 1],
R ₁ to R ₄ are each independently a halogen group, cyano group, nitro group, sulfonyl group (SO ₂ R'), sulfoxide group (SO ₃ ), carbonyl group (COR'), carboxyl group (CO ₂ R'), substituted Or an unsubstituted silyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted halogenated alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted Is any one selected from a heteroaryl group having 2 to 30 carbon atoms,
R'is hydrogen, deuterium, cyano group, halogen group, amino group, thiol group, hydroxy group, nitro group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl group having 1 to 24 carbon atoms, alkenyl group having 2 to 24 carbon atoms, 6 carbon atoms It is selected from an aryl group of to 24, a heteroaryl group of 2 to 24 carbon atoms, an alkoxy group of 1 to 24 carbon atoms, an alkylsilyl group of 1 to 24 carbon atoms, and an arylsilyl group of 1 to 24 carbon atoms,
R is hydrogen, deuterium, cyano group, halogen group, substituted or unsubstituted silyl group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted It is selected from a C3-C30 heteroaryl group, a substituted or unsubstituted C6-C50 arylamine group, and a substituted or unsubstituted C3-C50 heteroarylamine group,
R ₅ to R ₂₄ are each independently hydrogen, deuterium, halogen group, cyano group, substituted or unsubstituted silyl group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms It is selected from a group, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 6 to 50 carbon atoms, and a substituted or unsubstituted heteroarylamine group having 3 to 50 carbon atoms. The method of claim 1,
In the [Chemical Formula I], two Rs are the same as or different from each other, and an organic light-emitting compound, characterized in that they are selected from the following [Structural Formula 2] and [Structural Formula 3]:
[Structural Formula 2]

[Structural Formula 3]

In the [Structural Formula 2] and [Structural Formula 3],
L ₁ and L ₂ are each a single bond, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, n and m are each 0 to 4 Is an integer, when n and m are each 2 or more, a plurality of L ₁ and L ₂ are each the same or different from each other,
Ar ₁ to Ar ₃ are the same as or different from each other, and each independently selected from a substituted or unsubstituted aryl group having 5 to 50 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms,
The Ar ₁ and Ar ₂ may be bonded to each other or linked with an adjacent substituent to form an alicyclic, aromatic monocyclic or polycyclic ring, and carbon atoms of the formed alicyclic, aromatic monocyclic or polycyclic ring are N, S and O may be substituted with any one or more heteroatoms selected from,
o, p, and q are each an integer of 1 to 3, and when o, p, and q are each 2 or more, a plurality of Ar ₁ to Ar ₃ are the same or different from each other. The method of claim 2,
In the [Chemical Formula I], two Rs are the same as or different from each other, and are each represented by the [Structural Formula 2]. The method of claim 1,
At least one of R ₅ to R ₈ in the [Chemical Formula II] and at least one of R ₉ to R ₁₂ are the same as or different from each other, and are each selected from [Structural Formula 2] and [Structural Formula 3] Organoluminescent compounds made of:
[Structural Formula 2]

[Structural Formula 3]

In the [Structural Formula 2] and [Structural Formula 3],
L ₁ and L ₂ are each a single bond, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, n and m are each 0 to 4 Is an integer, when n and m are each 2 or more, a plurality of L ₁ and L ₂ are each the same or different from each other,
Ar ₁ to Ar ₃ are the same as or different from each other, and each independently selected from a substituted or unsubstituted aryl group having 5 to 50 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms,
The Ar ₁ and Ar ₂ may be bonded to each other or linked with an adjacent substituent to form an alicyclic, aromatic monocyclic or polycyclic ring, and carbon atoms of the formed alicyclic, aromatic monocyclic or polycyclic ring are N, S and O may be substituted with any one or more heteroatoms selected from,
o, p, and q are each an integer of 1 to 3, and when o, p, and q are each 2 or more, a plurality of Ar ₁ to Ar ₃ are the same or different from each other. The method of claim 4,
At least one of R ₅ to R ₈ in the [Chemical Formula II] and at least one of R ₉ to R ₁₂ are the same as or different from each other, and are each represented by the following [Structural Formula 2]. . The method of claim 1,
The compound represented by [Chemical Formula I] or [Chemical Formula II] is an organic light-emitting compound, characterized in that it is selected from compounds represented by the following compounds 1 to 100:

An organic light emitting device comprising a first electrode, a second electrode, and one or more organic material layers disposed between the first electrode and the second electrode,
An organic light-emitting device, wherein at least one of the organic material layers includes any one compound selected from compounds represented by [Chemical Formula I] or [Chemical Formula II] according to claim 1. The method of claim 7,
The organic material layer includes at least one of a hole injection layer, a hole transport layer, a multifunctional HTL layer, an electron transport layer, an electron injection layer, a layer for simultaneous electron transport and electron injection, and a light emitting layer,
An organic light-emitting device, wherein at least one of the layers includes any one compound selected from compounds represented by [Chemical Formula I] or [Chemical Formula II]. The method of claim 8,
The hole injection layer or the hole transport layer contains any one compound selected from the compounds represented by [Chemical Formula I] or [Chemical Formula II],
The organic light emitting device, characterized in that the compound is a p-type doping material. The method of claim 9,
The multifunctional HTL layer (Multi functional Hole Transportation Layer) contains any one compound selected from the compounds represented by the [Chemical Formula I] or [Chemical Formula II],
The compound is an organic light-emitting device, characterized in that the hole transport moiety (Hole Transportation Unit) and a p-doped moiety (p-Dopant Unit), including a compound that combines hole injection and hole transport functions. The method of claim 8,
The multifunctional HTL layer (Multi functional Hole Transportation Layer) is characterized in that it is composed of a single layer, is formed without a p-dopant doping process, and is made of an organic light emitting compound represented by the above [Chemical Formula I] or [Chemical Formula II] Organic light-emitting device characterized by.

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