KR101628438B1 - NITROGEN-CONTAINING HETEROCYCLIC COMPOUNDS AND ORGANIC ElECTRONIC DEVICE COMPRISING THE SAME - Google Patents

Abstract

The present invention provides a nitrogen-containing heterocyclic compound capable of significantly improving the lifetime, efficiency, electrochemical stability, and thermal stability of an organic electronic device, and an organic electronic device in which the organic compound layer is contained in the organic compound layer.

Description

TECHNICAL FIELD [0001] The present invention relates to a nitrogen-containing heterocyclic compound and an organic electronic device including the same. BACKGROUND ART < RTI ID = 0.0 >

The present specification relates to nitrogen-containing heterocyclic compounds and organic electronic devices containing the same.

This specification claims the benefit of Korean Patent Application No. 10-2012-0058692 filed on May 31, 2012, the entire contents of which are incorporated herein by reference.

An organic electronic device means an element requiring charge exchange between an electrode and an organic material using holes and / or electrons. The organic electronic device can be roughly classified into two types according to the operating principle as described below. First, an exciton is formed in an organic material layer by a photon introduced into an element from an external light source. The exciton is separated into an electron and a hole, and the electrons and holes are transferred to different electrodes to be used as a current source Type electric device. The second type is an electronic device that injects holes and / or electrons into an organic semiconductor that interfaces with an electrode by applying a voltage or current to two or more electrodes, and operates by injected electrons and holes.

Examples of the organic electronic device include an organic light emitting device, an organic solar cell, an organic photoconductor (OPC), an organic transistor, and the like. These devices may be used as a hole injecting or transporting material, an electron injecting or transporting material, need. Hereinafter, the organic light emitting device will be described in detail. However, in the organic electronic devices, hole injecting or transporting materials, electron injecting or transporting materials, or light emitting materials act on a similar principle.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layer structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out. Such an organic light emitting device is known to have characteristics such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

Materials used as an organic material layer in an organic light emitting device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. In addition, the luminescent material can be classified into blue, green and red luminescent materials and yellow and orange luminescent materials necessary for realizing a better natural color depending on the luminescent color. On the other hand, when only one material is used as the light emitting material, there arises a problem that the maximum light emitting wavelength shifts to a long wavelength due to intermolecular interaction, the color purity drops, or the efficiency of the device decreases due to the light emission attenuating effect. A host / dopant system may be used as a light emitting material in order to increase the efficiency of light emission through the light emitting layer.

In order for the organic luminescent device to sufficiently exhibit the above-described excellent characteristics, a material constituting the organic material layer in the device, such as a hole injecting material, a hole transporting material, a luminescent material, an electron transporting material and an electron injecting material is supported by a stable and efficient material However, development of a stable and efficient organic material layer material for an organic light emitting device has not yet been sufficiently developed. Therefore, development of new materials is continuously required, and the necessity of developing such materials is the same in other organic electronic devices described above.

Korean Patent Publication No. 2007-0078724

Accordingly, the present inventors aim to provide a nitrogen heterocyclic compound having a chemical structure capable of performing various functions required in an organic electronic device according to a substituent, and an organic electronic device containing the same.

The present invention provides a new nitrogen-containing heterocyclic compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

l and m are each an integer of 0 to 3,

n and o are integers from 1 to 4,

Ar is a substituted or unsubstituted arylene group; A substituted or unsubstituted alkenylene group; Or a substituted or unsubstituted heteroarylene group containing at least one of N, O, S and P atoms as a hetero atom,

R ₁ To R < ₈ > are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; Or a substituted or unsubstituted heterocyclic group containing at least one of N, O, S and P atoms,

R ₉ And R < ₁₀ > are the same or different and each independently represents a substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; Or a substituted or unsubstituted alkynyl group,

R ₁₁ And R < ₁₂ > are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; Or a substituted or unsubstituted heterocyclic group containing at least one of N, O, S and P atoms.

The present invention also relates to an organic electronic device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers is a nitrogen-containing heterocyclic compound And an organic electroluminescent device.

The novel nitrogen-containing heterocyclic compound according to the present invention can be used as a material for an organic material layer of an organic electronic device including an organic light emitting device, and an organic electronic device including the organic light emitting device using the same can improve efficiency, It is possible to improve the characteristics.

1 to 5 are cross-sectional views illustrating the structure of an organic electronic device according to the present invention.
6 is a diagram showing the mass spectrum of Compound 4 according to the present invention.
7 is a diagram showing the mass spectrum of compound 12 according to the present invention.

The present invention provides a nitrogen-containing heterocyclic compound represented by the above formula (1).

In another embodiment, Ar is a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group containing at least one of N, O, S and P atoms.

In one embodiment of the present specification, l and m are an integer of 0 to 3. In another embodiment, l + m? 1.

Ar of formula (1) may be selected from the following structures.

A group which is not a linking group in Ar is hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted alkynyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; Or a substituted or unsubstituted heterocyclic group containing at least one of N, O, S and P atoms.

Illustrative examples of such substituents are set forth below, but are not limited thereto.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and heptyl.

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 50. Specific examples thereof include, but are not limited to, an alkenyl group substituted with an aryl group such as a stilbenyl group or a styrenyl group.

In the present specification, the alkynyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 50. Specific examples include, but are not limited to, alkynyl groups such as ethynyl, propynyl, 2-methyl-2-propynyl, 2-butynyl and 2-pentynyl.

In the present specification, the alkoxy group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50.

The length of the alkyl group, alkenyl group, alkynyl group and alkoxy group contained in the compound does not affect the conjugate length of the compound, but the method of applying the compound to an organic electronic device, for example, a vacuum deposition method or a solution coating method And therefore the number of carbon atoms is not particularly limited.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and particularly preferably a cyclopentyl group and a cyclohexyl group.

In the present specification, the aryl group may be monocyclic or polycyclic, and the number of carbon atoms is not particularly limited, but is preferably 6 to 60. [ Specific examples of the aryl group include monocyclic aromatic and naphthyl groups such as phenyl group, biphenyl group, triphenyl group, terphenyl group and stilbene group, binaphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, But are not limited to, a cyclic aromatic group such as a cyclohexylene group, a cyclohexylene group, a chlorocenyl group, a fluorenyl group, an acenaphthacenyl group, a triphenylene group, and a fluoranthene group.

In the present specification, the heterocyclic group is a heterocyclic group and is a heterocyclic group containing at least one of N, O, S and P atoms. The number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrolyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a triazine group, , A quinolinyl group, an isoquinoline group, an indole group, a carbazole group, a benzoxazole group, a benzimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, But are not limited to these.

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

,

등이 있다. In the present specification, a fluorenyl group is a structure in which two ring organic compounds are connected via one atom,

,

.

및

등이 있다. In the present specification, a fluorenyl group includes a structure of an open fluorenyl group, wherein an open fluorenyl group is a structure in which one ring compound is disconnected in a structure in which two ring compounds are connected through one atom, For example,

And

.

In the present specification, the number of carbon atoms of the amine group is not particularly limited, but is preferably 1 to 50. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, a 9- , A diphenylamine group, a phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine group, a triphenylamine group, and the like, but are not limited thereto.

In the present specification, the number of carbon atoms of the arylamine group is not particularly limited, but is preferably 6 to 50. Examples of the arylamine group include a substituted or unsubstituted monocyclic diarylamine group, a substituted or unsubstituted polycyclic diarylamine group, or a substituted or unsubstituted monocyclic or polycyclic diarylamine group.

In the present specification, the aryloxy group, the arylthioxy group, the arylsulfoxy group, and the carbon number of the aralkylamine group are not particularly limited, but are preferably 6 to 50. The aryl group in the aryloxy group, arylthioxy group, arylsulfoxy group and aralkylamine group is the same as the aforementioned aryl group.

In the present specification, the alkyl group in the alkylthio group, alkylsulfoxy group, alkylamine group, and aralkylamine group is the same as the alkyl group described above.

In the present specification, the heteroaryl group in the heteroarylamine group can be selected from the examples of the above-mentioned heterocyclic group.

In the present specification, an arylene group, an alkenylene group, a fluorenylene group, and a heteroarylene group are each a divalent group of an aryl group, an alkenyl group, a fluorenyl group, and a heteroaryl group. The description of the above-mentioned aryl group, alkenyl group, fluorenyl group and heteroaryl group can be applied, except that these are two groups each.

In the present specification, the substituted arylene group means a group in which a phenyl group, biphenyl group, naphthyl group, fluorenyl group, pyrenyl group, phenanthrenyl group, perylene group, tetracenyl group, anthracenyl group, .

In the present specification, the substituted heteroarylene group includes 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 condensed heterocyclic groups, Such as a benzoquinoline group, a benzimidazole group, a benzoxazole group, a benzothiazole group, a benzocarbazole group, a dibenzothiophenyl group, etc., are substituted with other substituents.

The term "substituted or unsubstituted" A halogen group; An alkyl group; An alkenyl group; An alkoxy group; A cycloalkyl group; Silyl group; An arylalkenyl group; An aryl group; An aryloxy group; An alkyloxy group; An alkylsulfoxy group; Arylsulfoxy group; Boron group; An alkylamine group; An aralkylamine group; An arylamine group; A heteroaryl group; Carbazole group; An arylamine group; An aryl group; A fluorenyl group; A nitrile group; A nitro group; A hydroxy group; A cyano group, and a heterocyclic group containing at least one of N, O, S, or P atoms, or has no substituent group.

The present invention provides a nitrogen-containing heterocyclic compound represented by the above formula (1). Such a compound can be used as an organic material layer in an organic electronic device due to its structural specificity.

In one embodiment of the present specification, R ₉ and R ₁₀ are the same or different and are each independently a substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkenyl group; Or a substituted or unsubstituted alkynyl group.

In the embodiment of the present invention, R ₉ is a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted cycloalkyl group.

In another embodiment, R ₉ may be a substituted or unsubstituted methyl group.

In another embodiment, R ₉ may be a substituted or unsubstituted ethyl group.

In another embodiment, R ₉ may be a substituted or unsubstituted cyclopentyl group.

In another embodiment, R ₉ may be a substituted or unsubstituted cyclohexyl group.

In the present embodiment, R ₁₀ may be a substituted or unsubstituted alkyl group or a substituted or unsubstituted cycloalkyl group.

In another embodiment, R < ₁₀ > may be a substituted or unsubstituted methyl group.

In another embodiment, R < ₁₀ > may be a substituted or unsubstituted ethyl group.

In another embodiment, R < ₁₀ > may be a substituted or unsubstituted cyclopentyl group.

In another embodiment, R < ₁₀ > may be a substituted or unsubstituted cyclohexyl group.

In the practice of the present disclosure, R ₁ to R ₄ may be hydrogen.

In the embodiment of the present disclosure, R ₅ to R ₈ may be hydrogen.

In the embodiment of the present disclosure, Ar may be a substituted or unsubstituted aryl group.

In another embodiment, Ar may be a substituted or unsubstituted phenylene group.

In another embodiment, Ar may be a substituted or unsubstituted naphthylene group.

In another embodiment, Ar may be a substituted or unsubstituted fluorenylene group.

In another embodiment, Ar may be a fluorenylene group substituted with a methyl group.

일 수 있다. In another embodiment, Ar

Lt; / RTI >

일 수 있다.In another embodiment, Ar

Lt; / RTI >

일 수 있다.In another embodiment, Ar

Lt; / RTI >

일 수 있다.In another embodiment, Ar

Lt; / RTI >

In the embodiment of the present disclosure, l may be an integer from 0 to 3.

In another embodiment, l may be two.

In another embodiment, l may be one.

In the present embodiment, m may be an integer of 0 to 3.

In another embodiment, m may be 2.

In another embodiment, m may be 1.

The nitrogen-containing heterocyclic compound according to the present specification may be any one of the following compounds 1 to 18, but is not limited thereto.

Further, by introducing various substituents into the core structure having the above structure, it is possible to synthesize a compound having the intrinsic characteristics of the substituent introduced. For example, by introducing a substituent mainly used in a hole injecting layer material, a hole transporting material, a light emitting layer material, and an electron transporting layer material used in manufacturing an organic electronic device into the core structure, a material meeting the requirements of each organic layer is synthesized .

The nitrogen-containing heterocyclic compound of Formula 1 may be prepared on the basis of the following Production Examples.

The nitrogen-containing heterocyclic compound represented by Formula 1 may be prepared by reacting a benzoimidazole compound with a halogen-substituted Ar. A substituent of the benzimidazole compound and Ar may be optionally selected to prepare the compounds 1 to 18 and the compound represented by the formula 1.

The present invention also provides an organic electronic device using the nitrogen-containing heterocyclic compound of formula (1).

In one embodiment of the present invention, the organic electronic device may have a structure including a first electrode, a second electrode, and an organic layer disposed therebetween. The organic electronic device may be selected from the group consisting of an organic light emitting device, an organic solar cell, and an organic transistor.

In one embodiment of the present invention, the organic electronic device may be an organic light emitting device.

In one embodiment of the present disclosure, an organic light-emitting device includes a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers includes And a nitrogen-containing heterocyclic compound represented by the general formula (1).

The organic material layer of the organic light emitting device of 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, the organic light emitting device in this specification may have a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, etc. as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

Therefore, in another embodiment of the present disclosure, the organic material layer of the organic light emitting device may include at least one of a hole injecting layer, a hole transporting layer, and a layer simultaneously injecting holes and transporting holes, Or more of the nitrogen-containing heterocyclic compound represented by the above formula (1).

Specifically, the organic compound layer of the organic light emitting device may include a hole injection layer, and the hole injection layer may include a nitrogen heterocycle compound represented by Formula 1. [

In another embodiment, the organic material layer of the organic light emitting device may include a hole transporting layer, and the hole transporting layer may include a nitrogen-containing heterocyclic compound represented by Formula 1. [

In another embodiment, the organic material layer of the organic light emitting device may include a hole transporting layer and a hole injecting layer, and the hole transporting layer and the hole injecting layer may include a nitrogen-containing heterocyclic compound represented by Formula 1 have.

In addition, the organic layer may include a light emitting layer, and the light emitting layer may include a nitrogen-containing heterocyclic compound represented by the general formula (1).

In one embodiment, the nitrogen-containing heterocyclic compound represented by Formula 1 may be included as a host of the light-emitting layer.

In one embodiment, the organic compound layer comprising the nitrogen-containing heterocyclic compound represented by Formula 1 includes the nitrogen-containing heterocyclic compound represented by Formula 1 as a host, and other organic compound, metal, Can be included.

The organic material layer may include at least one of an electron transport layer, an electron injection layer, and a layer that simultaneously transports electrons and electrons, and at least one of the layers may contain a nitrogen-containing heterocyclic compound represented by Formula 1 . Specifically, the organic material layer of the organic light emitting device may include an electron injection layer, and the electron injection layer may include a nitrogen heterocycle compound represented by Formula 1. [

In another example, the organic layer of the organic light emitting device may include an electron transporting layer, and the electron transporting layer may include a nitrogen-containing heterocyclic compound represented by Formula 1. [

In another example, the organic material layer of the organic light emitting device may include an electron transport layer and an electron injection layer, and the electron transport layer and the electron injection layer may include the nitrogen-containing heterocyclic compound represented by Formula 1 .

In the organic compound layer having such a multilayer structure, the nitrogen-containing heterocyclic compound represented by the formula (1) may be used in combination with a light emitting layer, a layer that simultaneously transports holes and holes, a layer that simultaneously transports holes and emits light, Layer or the like.

In another embodiment, the organic compound layer of the organic light emitting device may contain, in addition to the organic compound layer containing the nitrogen-containing heterocyclic compound represented by Formula 1, a hole containing a compound containing an arylamino group, a carbazole group, or a benzocarbazole group An injection layer or a hole transport layer.

In one embodiment of the present invention, the organic electronic device may be an organic solar cell.

In one embodiment of the present disclosure, the organic electroluminescent device includes at least one organic layer including a first electrode, a second electrode, and a photoactive layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers Is a nitrogen-containing heterocyclic compound represented by the general formula (1).

In another embodiment, the photoactive layer may include a nitrogen-containing heterocyclic compound represented by Formula 1. [

In another embodiment, the organic solar cell may include a photoactive layer, an electron donor, and an electron acceptor. The photoactive layer and the electron donor or electron acceptor may be represented by Formula 1 Nitrogen-containing heterocyclic compounds.

In the embodiment of the present invention, when the organic solar cell receives photons from an external light source, electrons and holes are generated between the electron beams and the electron acceptors. The generated holes are transported to the anode through the electron donor layer.

In an embodiment of the present disclosure, the organic solar cell may further include an additional organic layer. The organic solar cell can reduce the number of organic layers by using organic materials having various functions at the same time.

In one embodiment of the present disclosure, the organic electronic device may be an organic transistor.

In one embodiment of the present disclosure, an organic transistor is provided that includes a source, a drain, a gate, and one or more organic layers.

In one embodiment of the present invention, the organic transistor may include a charge generation layer, and the charge generation layer may include a nitrogen-containing heterocyclic compound represented by the general formula (1).

In another embodiment, the organic transistor may comprise an insulating layer, and the insulating layer may be located on the substrate and the gate.

When the organic electronic device includes a plurality of organic layers, the organic layers may be formed of the same material or another material.

 The organic electronic device according to the present invention may have a structure as shown in Figs. 1 to 5, but the present invention is not limited thereto.

1 shows an organic electronic device in which a substrate 1, an anode 2, a hole injecting layer 3, a hole transporting layer 4, a light emitting layer 5, an electron transporting layer 6 and a cathode 7 are sequentially stacked Structure is illustrated.

2 illustrates the structure of an organic electronic device in which a substrate 1, 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.

3 illustrates the structure of an organic electronic device in which a substrate 1, 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.

4 shows a structure of an organic electronic device in which a substrate 1, an anode 2, a light emitting layer 5, an electron transport layer 6, and a cathode 7 are sequentially laminated.

5 illustrates a structure of an organic electronic device in which a substrate 1, an anode 2, a light emitting layer 5, and a cathode 7 are sequentially laminated.

The organic electronic device of the present invention is manufactured by materials and methods known in the art except that one or more of the organic layers include the nitrogenous heterocyclic compound of the present specification, i.e., the nitrogenous heterocyclic compound of the above formula .

For example, the organic electronic device of the present specification can be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as a sputtering method or an e-beam evaporation method, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate to form a positive electrode Forming an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer and an electron transporting layer thereon, and depositing a material usable as a cathode thereon. In addition to such a method, an organic light emitting device can be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate. (International Patent Application Publication No. 2003/012890)

In addition, the nitrogen-containing heterocyclic compound of Formula 1 may be formed into an organic material layer by a solution coating method as well as a vacuum evaporation method in the production of an organic electronic device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating and the like, but is not limited thereto.

The substrate may be a glass substrate or a plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness, but is not limited thereto and is not limited as long as it is a substrate commonly used in an organic electronic device.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SNO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

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

As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene- , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

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

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, and rubrene, but the present invention is not limited thereto.

As the electron transporting material, a material capable of transferring electrons from the cathode well into the light emitting layer, which is suitable for electrons, is suitable. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.

The organic electronic device according to the present invention may be a top emission type, a back emission type, or a both-sided emission type, depending on the material used.

The method for preparing the compound of Formula 1 and the production of the organic electronic device using the same will be described in detail in the following Examples. However, the following examples are intended to illustrate the present specification, and the scope of the present specification is not limited thereto.

Production Example 1 . Preparation of compound 4

[Compound A] [Compound 4]

Compound A (20 g, 75.2 mmol) and 2,7-dibromo-1-naphthalene (10.2 g, 35.8 mmol) were completely dissolved in 300 ml of tetrahydrofuran (THF) after addition of 2M aqueous potassium carbonate solution and 180ml, into a _{Pd (PPh 3) 4 (824mg} , 2mol%) it was refluxed for 24 h. The temperature was lowered to room temperature, the water layer was removed, and the organic layer was filtered. The solid was adsorbed onto silica gel and columned to obtain the compound of Formula 4 (9.1 g, 45%).

MS: [M + H] < ⁺ > = 568

Manufacturing example  2. Preparation of Compound 12

[Compound A] [Compound 12]

Compound A (20 g, 75.2 mmol) and 1,5-dibromo-1-naphthalene (0.2 g, 35.8 mmol) were completely dissolved in 300 ml of tetrahydrofuran (THF) 180 ml of a 2M potassium carbonate aqueous solution was added, Pd (PPh3) 4 (824 mg, 2 mol%) was added, and the mixture was refluxed for 24 hours. The temperature was lowered to room temperature, the water layer was removed, and the organic layer was filtered. The solid was adsorbed on silica gel and columned to give 12 (13.0 g, 64%).

MS: [M + H] < ⁺ > = 569

Experimental Example  One

A glass substrate (corning 7059 glass) coated with ITO (indium tin oxide) having a thickness of 1000 Å was immersed in distilled water in which a dispersant was dissolved and ultrasonically washed. The detergent was a product of Fisher Co., distilled water was purchased from Millipore Co. Distilled water, which was secondly filtered with a filter of the product, was used. After the ITO was washed for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After the distilled water was washed, ultrasonic washing was performed in the order of isopropyl alcohol, acetone, and methanol solvent, followed by drying.

(500 Å), 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB) (400 Å), Alq ₃ (300 Å) And Compound 4 (200 Å) prepared in Preparation Example 1 were sequentially subjected to thermal vacuum deposition to form a hole injecting layer, a hole transporting layer, a light emitting layer, and an electron transporting layer in this order.

Lithium fluoride (LiF) having a thickness of 12 Å and aluminum having a thickness of 2000 Å were sequentially deposited on the electron transporting layer to form a cathode, thereby preparing an organic electronic device.

Was maintained at the deposition rate was 0.4 ~ 0.7Å / sec for organic material in the above process, the lithium fluoride of the cathode was deposited at a rate of 0.3Å / sec, aluminum 2Å / sec, the degree of vacuum upon deposition was 2 x 10 ^{- 7} to 5 x 10 < ^-8 > torr.

When a forward electric field of 6 V was applied to the device fabricated as described above, green emission corresponding to 3200 nit was observed.

Experimental Example  2

An organic light emitting device was fabricated in the same manner as in Experimental Example 1, except that Compound 12 prepared in Preparation Example 2 was used instead of Compound 4 in Experimental Example 1.

Comparative Example  One

A glass substrate (corning 7059 glass) coated with ITO (indium tin oxide) having a thickness of 1000 Å was immersed in distilled water in which a dispersant was dissolved and ultrasonically washed. The detergent was a product of Fisher Co., distilled water was purchased from Millipore Co. Distilled water, which was secondly filtered with a filter of the product, was used. After the ITO was washed for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After the distilled water was washed, ultrasonic washing was performed in the order of isopropyl alcohol, acetone, and methanol solvent, followed by drying.

(500 Å), 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB) (400 Å), Alq ₃ (300 Å) And the compound of Formula B (200 Å) prepared in Preparation Example 1 were sequentially subjected to thermal vacuum deposition to form a hole injecting layer, a hole transporting layer, a light emitting layer, and an electron transporting layer in this order.

[Chemical Formula B]

Lithium fluoride (LiF) having a thickness of 12 Å and aluminum having a thickness of 2000 Å were sequentially deposited on the electron transporting layer to form a cathode, thereby preparing an organic electronic device.

Was maintained at the deposition rate was 0.4 ~ 0.7Å / sec for organic material in the above process, the lithium fluoride of the cathode was deposited at a rate of 0.3Å / sec, aluminum 2Å / sec, During the deposition, a vacuum 2 x 10 ^{- 7} to 5 x 10 < ^-8 > torr.

When a forward electric field of 6 V was applied to the device fabricated as described above, green emission corresponding to 3200 nit was observed.

Table 1 below shows the results of measuring and comparing the voltage and efficiency of Experimental Example 1, Experimental Example 2 and Comparative Example 1.

compound Voltage (V) Efficiency (cd / A) Experimental Example 1 Compound 4 4.35 7.05 Experimental Example 2 Compound 12 4.80 7.10 Comparative Example 1 Formula B 5.12 4.30

As shown in Table 1, when R ₉ and R ₁₀ are alkyl groups, R ₉ and R ₁₀ have a lower driving voltage and / or higher efficiency than the allyl group.

1: substrate
2: anode
3: Hole injection layer
4: hole transport layer
5: light emitting layer
6: electron transport layer
7: cathode

Claims (18)

A nitrogen-containing heterocyclic compound represented by the following formula (1)
[Chemical Formula 1]

In Formula 1,
l and m are each an integer of 0 to 3,
n and o are integers from 1 to 4,
Ar represents a phenylene group; A terphenylene group; Naphthylene group; Or a fluorenylene group,
R ₁ to R ₈ are the same or different from each other, and each independently hydrogen; Or deuterium,
R ₉ and R ₁₀ are the same as or different from each other, and each independently represents an alkyl group; Or a cycloalkyl group,
R ₁₁ and R ₁₂ are the same or different from each other, and each independently hydrogen; Or deuterium. delete delete delete The nitrogen-containing heterocyclic compound according to claim 1, wherein the nitrogen-containing heterocyclic compound of formula (1) is any one of the following compounds 1 to 18:

. 1. An organic electronic device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers is provided in any one of claims 1 to 5 And a nitrogen-containing heterocyclic compound. The organic electronic device according to claim 6, wherein the organic electronic device is selected from the group consisting of an organic light emitting device, an organic solar cell, and an organic transistor. 7. The organic electroluminescent device according to claim 6, wherein the organic electronic device is an organic light emitting device comprising a first electrode, a second electrode, and one or more organic layers disposed between the first electrode and the second electrode, And the nitrogen-containing heterocyclic compound. The organic electronic device according to claim 8, wherein the organic material layer includes a hole injection layer or a hole transport layer containing the nitrogen-containing heterocyclic compound. 9. The organic electronic device according to claim 8, wherein the organic layer includes a light emitting layer containing the nitrogen-containing heterocyclic compound. 9. The organic electronic device according to claim 8, wherein the organic material layer comprises an electron transport layer containing the nitrogen-containing heterocyclic compound. [Claim 8] The organic electroluminescent device according to claim 8, wherein the organic material layer includes a hole injection layer or a hole transport layer containing a compound including an arylamino group, a carbazole group, or a benzazole group in addition to the organic material layer containing the nitrogen- device. [Claim 9] The organic electronic device according to claim 8, wherein the organic compound layer containing the nitrogen-containing heterocyclic compound includes the nitrogen-containing heterocyclic compound as a host and includes another organic compound, metal or metal compound as a dopant. The organic electroluminescent device according to claim 6, wherein the organic electronic device is an organic solar cell including at least one organic layer including a first electrode, a second electrode, and a photoactive layer disposed between the first electrode and the second electrode, And at least one layer comprises the nitrogen-containing heterocyclic compound. 15. The organic electronic device according to claim 14, wherein the organic material layer comprises a photoactive layer containing the nitrogen-containing heterocyclic compound. 14. The organic electronic device according to claim 14, wherein the organic layer includes an electron donor and an electron acceptor, and the electron donor or electron acceptor comprises the nitrogen hetero heterocyclic compound. 7. The organic electronic device according to claim 6, wherein the organic electronic device is an organic transistor including a source, a drain, a gate, and one or more organic layers, wherein at least one of the organic layers includes the nitrogen-containing heterocyclic compound. 18. The organic electronic device according to claim 17, wherein the organic layer includes a charge generation layer containing the nitrogen-containing heterocyclic compound.

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