WO2018155904A1

WO2018155904A1 - Novel heterocyclic compound and organic light emitting element using same

Info

Publication number: WO2018155904A1
Application number: PCT/KR2018/002134
Authority: WO
Inventors: 정민우; 이동훈; 조성미; 허동욱; 한미연; 이정하
Original assignee: 주식회사 엘지화학
Priority date: 2017-02-21
Filing date: 2018-02-21
Publication date: 2018-08-30

Abstract

The present invention provides a novel heterocyclic compound and an organic light emitting element using the same.

Description

[Name of invention]

Novel heterocyclic compounds and organic light emitting devices using the same

Technical Field

Cross Citation with Related Application (s)

This application is filed with the Korean Patent Application as of February 21, 2017. ^■ 10—2017-

All contents disclosed in the literature of the Korean patent applications claiming the benefit of priority based on 0022903 and Korean Patent Application No. 10-2018—0020039 dated February 20, 2018 are included as part of this specification. The present invention relates to a novel heterocyclic compound and an organic light emitting device comprising the same.

[Technique to become background of invention]

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time. Many studies have been conducted because of excellent luminance, driving voltage and response speed. The organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode. The organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, for example, a hole injection layer, a hole transport insect. The light emitting layer may be formed of an electron transport layer, an electron injection layer, and the like. When the voltage is applied between the two electrodes in the structure of the organic light emitting diode, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer, and excitons are formed when the injected holes and the electrons meet each other. It will glow when the excitons fall back to the ground. There is a continuous demand for the development of new materials for organic materials used in such organic light emitting devices. Prior Art Documents

[Patent literature]

(Patent Document 0001) Korean Patent Publication No. 10-2013-073537

[Content of invention]

Problem to be solved

The present invention relates to a novel heterocyclic compound compound and an organic light emitting device comprising o.

[Measures to solve the problem].

The present invention provides a compound represented by Formula 1:

In Chemical Formula 1,

Xi, X ₂ and X ₃ are each independently CH or N, provided that one of ¾ and ¾ is N;

Li is a substituted or unsubstituted C ₆ - ₆₀ and by interrogating arylene, - ₆₀ arylene, or substituted or unsubstituted N, C ₅ comprising one or more hetero atoms selected from the group consisting of 0 and S

Is a single bond. A substituted or unsubstituted C ₆ - ₆₀ arylene. Substituted or unsubstituted N. C ₅ _-60 heteroarylene comprising at least one hetero atom selected from the group consisting of 0 and S, An, Ar ₂ and Ar ₃ are each independently a substituted or unsubstituted C ₆ - ₆₀ aryl, or a substituted or unsubstituted N. C ₅ _-60 heteroaryl comprising at least one hetero atom selected from the group consisting of 0 and ^' S. The aryl or heteroaryl may be further substituted with a cyano group

Of the above phenanthryl

Ar ₃

Are different from each other. In addition, the present invention is a first electrode; A second electrode provided to face the first electrode; And at least one organic material charge disposed between the first electrode and the second electrode. One or more layers of the organic material layer provide an organic light emitting device including the compound of the present invention described above.

[Brief Description of Drawings]

FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.

2 shows an example of an organic light emitting element consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8 and a cathode 4. It is. 【Effects of the Invention】

The compound represented by Chemical Formula 1 may be used as a material of the organic material layer of the organic light emitting diode, and may improve efficiency, low driving voltage, and / or lifespan characteristics in the organic light emitting diode. In particular, the compound represented by Chemical Formula 1 described above includes hole injection, hole transport, hole injection and transport, and luminescence. It can be used as an electron transporting or electron injection material. [Specific contents to carry out invention]

The present invention provides a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

Xi, X ₂ and ¾ are each independently CH or N, provided that at least one of, ¾ and ¾ is N,

Silver substituted or unsubstituted C ₆ _-60 arylene. Or substituted or unsubstituted C ₅ _-60 heteroarylene comprising one or more hetero atoms selected from the group consisting of N, 0 and S.

Is a single bond. A substituted or unsubstituted C ₆ - ₆₀ arylene, a substituted or unsubstituted N, C comprising one or more hetero atoms selected from the group consisting of 0 and S ₅ - ₆₀ heteroarylene and.

An, Ar ₂ and Ar ₃ are each independently C _{5 60} containing one or more hetero atoms selected from the group consisting of substituted or unsubstituted C ₆ _-60 aryl, or substituted or unsubstituted N, 0 and S Heteroaryl, and the aryl or heteroaryl may be further substituted with a cyano group.

only. Two substituents of the phenanthryl

'Ar ₃

--L

Are different from each other. In this specification,

It means the bond connected to another substituent. As used herein, the term "substituted or unsubstituted" is deuterium halogen group; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group imide group; Amino group; Phosphine oxide groups; An alkoxy group; Aryloxy group alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Aryl sulfoxy group; Silyl group boron group; An alkyl group; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group aralkenyl group; Alkylaryl group; Alkylamine group; Aralkyl amine groups; Heteroaryl amine group Aryl amine group; Aryl phosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups including one or more of N, 0, and S atoms, or two or more substituents in the above-described substituents connected or unsubstituted. . For example, "the substituent to which two or more substituents are linked"'may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are linked. In the present specification, the carbon number of the carbonyl group is particularly limited. It is preferably 1 to 40. Specifically, the compound may have the following structure, but is not limited thereto.

In the present specification, the oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the carbon number of the imide group is not particularly limited.

It is preferable that it is C1-C25. Specifically, the compound may be as follows, but is not limited thereto.

In the present specification, the silyl group specifically includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like. It is not limited to this. In the present specification, the boron group specifically includes, but is not limited to, trimethylboron group, triethylboron group, t-butyldimethylboron group, triphenylboron group, phenylboron group, and the like. In the present specification, examples of the halogen group include fluorine, chlorine,

There is iodine In the present specification, the alkyl group may be linear or branched, carbon number is not particularly limited, but 1 to _. 40 people _. It is preferable. Work According to the exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. In accordance with one embodiment of _i, the number of carbon atoms of the alkyl group is from 1 to 10 eu is, according to still one embodiment, the number of carbon atoms of the alkyl group is 1 to 6. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, ter t-butyl, sec ᅳ butyl, 1-methyl-butyl ᅳ 1-ethyl-butyl, pentyl, n—pentyl, isopentyl, neopentyl, tert-pentyl, nuclear chamber. n-nuclear, 1-methylpentyl ᅳ 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2—ethylbutyl, heptyl, n-haptyl, 1-methylnuclear, cyclopentylmethyl, cyclo Hectylmethyl ᅳ octyl, n-octyl, ter t-octyl, 1-methylheptyl, 2-ethylnuclear 2-propylpentyl. n-nonyl. 2,2 'dimethylheptyl, 1-ethyl-propyl, 1, 1-dimethyl-propyl, isonuclear chamber, 2-methylpentyl, 4-methylnuclear chamber, 5-methylnuclear chamber, and the like, but is not limited thereto. In the present specification, the alkenyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1—propenyl and isopropenyl. 1-butenyl. 2-butenyl. 3-butenyl, 1-pentenyl, 2—pentenyl, 3-pentenyl, 3-methyl— 1-butenyl. 1, 3-butadienyl, allyl. 1-phenylvinyl— 1-yl, 2-phenylvinyl-1-yl, 2, 2-diphenylvinyl-1-yl, 2-phenyl-2- (naphthyl-1-yl) vinyl-1 days, 2 2, bisbis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group and the like, but are not limited to these. In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. According to one embodiment. Carbon number of the said cycloalkyl group is 3-30. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically cyclopropyl, cyclobutyl, cyclopentyl, 3—methylcyclopentyl. 2, 3-dimethylcyclopentyl, cyclonuclear chamber, 3 ᅳ methylcyclonuclear chamber, ^' 4- Methylcyclonuclear chamber, 2, 3-dimethylcyclonuclear chamber, 3, 4, 5-trimethylcyclonuclear chamber, 4-tert-butylcyclonuclear chamber, cycloheptyl, cyclooctyl, and the like, but are not limited thereto. In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. As said aryl group, a monocyclic aryl group is a phenyl group and a biphenyl group. It may be a terphenyl group and the like, but is not limited thereto. The polycyclic aryl group may be naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, peryleneyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto. In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. The fluorenyl group

' Occation,

And so on. However, the present invention is not limited thereto. In the present specification, the heterocyclic group is a heterogeneous element of 0, N, Si and S

As a heterocyclic group containing one or more, although carbon number is not specifically limited, It is preferable that it is C2-C60. Examples of heterocyclic groups are thiophene groups. Furan group, pyrrole group. Imidazole. Thiazole group, oxazole group, oxadiazole group. Triazole group, pyridyl group, bipyridyl group, pyrimidyl group. Triazine group, triazole group, acridil group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group. Quinoxalinyl group. A phthalazinyl group, a pyrido pyrimidinyl group. Pyridopyrazinyl groups. Pyrazino pyrazinyl groups, isoquinoline groups, indole groups. Carbazole. Benzoxazole group ， Benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthrol group (phenanthrol ine), thiazolyl group isoxazolyl group ,. There may be an oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, but is not limited thereto. In the present specification, an aralkyl group. . Aralkenyl group. The aryl group in an alkylaryl group and an arylamine group is the same as the example of the aryl group mentioned above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the example of the alkyl group described above. In the present specification, the heteroaryl of the heteroarylamine may be applied to the description of the aforementioned heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the example of the alkenyl group described above. In the present specification, the description of the aforementioned aryl group may be applied except that the arylene is bivalent. In the present specification, the description of the aforementioned heterocyclic group may be applied except that the heteroarylene is bivalent. In the present specification, the hydrocarbon ring is not monovalent, and the description of the aforementioned aryl group or cycloalkyl group may be applied except that two substituents are formed by bonding. In the present specification, the heterocyclic ring is not 1 group, and the description of the aforementioned heterocyclic group may be applied except that two substituents are formed by bonding. Preferably, the compound represented by Formula 1 may be a compound represented by any one of the following Formulas 1-1 to 1-4.

[Formula 1-1]

10 In Chemical Formulas 1-1 to 1-4,

Li, L ₂ . An, Ar ₂ and Ar ₃ are as defined above.

Preferably any one selected from the group consisting of

It can be one.

Preferably, L ₂ is a single bond or a group consisting of

More preferably, L ₂ is a single

It may be any one selected from the group consisting of. Preferably, An, Ar ₂ and Ar ₃ may each independently be any one consisting of

Preferably, the compound represented by Formula 1 may be any one selected from the group consisting of: .

-CIlOO / 8TOZaM / X3d 1-06SST / 810Z OW

6SSI / 8I0Z OAV

^ εΐΖΟΟ / 8ΐΟΖΗΜ / Χ3 <Ι) 6SSI / 8I0Z OAV

The compound represented by Formula 1 has a basic structure of phenanthryl including a triazine (pyridine. Pyrimidine) substituent, and since both substituents of phenanthryl have an asymmetric structure at the same time, it is excellent in heat resistance when driving in a device. In addition, crystallization can be suppressed. Therefore, the organic light emitting device using the same may have high efficiency, low driving voltage, high brightness, long life, and the like. In addition, the compound represented by Formula 1 may be prepared by the same method as in Schemes 1A to 1C. The manufacturing method may be more specific in the production examples to be described later.

Scheme 1A

compound A

[Bungungsik 1B]

compound A compound B Scheme ic

compound B compound I In the above reaction formulas 1A to 1C,,, ¾, Li, L ₂ , An and Ar ₂ are as defined above.

The compound represented by Chemical Formula 1 may be prepared by appropriately replacing the starting material, the type of semi-unggi and the type of catalyst according to the structure of the compound to be prepared by referring to the contents of Schemes 1A to 1C. In addition, the present invention provides an organic light emitting device comprising the compound represented by the formula (1). In one embodiment, the present invention is a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include a compound represented by Chemical Formula 1. do. 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 emission of the present invention. The device 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 as an organic layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers. In addition, the organic layer is a hole injection layer, a hole transport layer. Or a layer for simultaneously injecting and transporting holes and injecting the hole. Hole transport layer Alternatively, the layer for simultaneously injecting and transporting a hole may include the compound represented by Chemical Formula 1. In addition, the organic layer can ^'may include an emission layer, the balgwangchung comprises a compound represented by the formula (1). In addition, the organic layer may include an electron transport layer, or an electron injection layer, the electron transport layer, or the electron injection layer comprises a compound represented by the formula (1) In addition, the electron transport layer, electron injection layer, Alternatively, the layer for simultaneously injecting and transporting electrons may include the compound represented by Chemical Formula 1. Especially . The compound represented by Formula 1 according to the present invention has excellent thermal stability, has a deep HOMO level of 6.0 eV or higher, high triplet energy (ET), and hole stability. Also. Simultaneously injecting and transporting electrons to the compound represented by the formula (1). When used in the organic material filling can be used a mixture of n-type dopants used in the art. In addition, the organic layer may include a light emitting layer and an electron transport layer, the electron transport layer may include a compound represented by the formula (1). Also in the present invention. The organic light emitting device may be an organic light emitting device having a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting device according to the present invention may be an organic light emitting device of an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2. 1 is a substrate (1). The example of the organic light emitting element which consists of the anode 2, the light emitting layer 3, and the cathode 4 is shown. In such a structure, the compound represented by Formula 1 may be included in the light emitting layer. FIG. 2 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8 and a cathode 4 It is. In such a structure, the compound represented by Formula 1 may be included in at least one of the hole injection layer, the hole transport layer, the light emitting layer and the electron transport layer ᅳ the organic light emitting device according to the present invention. One or more layers of the organic material layer may be prepared by materials and methods known in the art, except that the compound represented by Chemical Formula 1 is included. In addition, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials. For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time. Metal oxides or conductive metal oxides on the substrate, or by using a physical vapor deposition deposition (PVD) method such as sput tering or e-beam evaporation After depositing an alloy of the anode to form an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to this method, the organic material layer from the negative electrode material on the substrate. An anode material may be sequentially deposited to make an organic light emitting device.

. In addition, the compound represented by Formula 1 may be formed as an organic layer by a solution coating method as well as a vacuum deposition method in the manufacture of the organic light emitting device. here. Solution coating methods are spin coating, dip coating and doctor blading. Inkjet printing, screen printing, spray method, coating, etc., but is not limited to these. In addition to methods like this. An organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material on a substrate from a cathode material (W0 2003/012890). However, the manufacturing method is not limited thereto. In one example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode, the second electrode is an anode. As the anode material, a material having a large work function is generally preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (IT0), indium zinc oxide (IZ0); Ζη0: A1 or SN0 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 KPED0T), polypyri and polyaniline, and the like, 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 magnesium, calcium, sodium, potassium, titanium, indium, yttrium, and lithium. Metals such as gadolinium, aluminum, silver, tin and lead or alloys thereof; Multilayer structure materials such as LiF / Al or Li0 ₂ / Al, and the like, but are not limited thereto. The hole injection layer is a layer for injecting holes from the electrode, and the hole injection material has the ability of transporting holes. The hole injection layer has a hole injection effect at the anode, and has an excellent hole injection effect for the light emitting layer or the light emitting material. Prevents the movement of the generated excitons into the electron injection layer or electron injection material, and also Compounds that are excellent in their ability to form are preferred. The HOMO highest occupied molecular orbi ta) of the hole injection material is preferably between the work function of the positive electrode material and the HOMO of the surrounding organics' layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic matter, nucleonitrile-nuclear azatriphenylene-based organic material quinacridone-based organic material, and perylene Organic, anthraquinone and polyaniline and polythiophene-based conductive polymers, but are not limited thereto. The hole transport insect is a layer for receiving holes from the hole injection layer to transport holes to the light emitting layer. As a material for transporting holes from the anode or the hole injection layer to the light emitting layer as a hole transporting material, a material having high mobility to holes is suitable. Specific examples thereof include an arylamine-based organic material and a conductive polymer. And block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto. As the light emitting material are a material capable of visible light by combining each of the received transport holes and electrons from the hole transport layer and the electron transport layer, a high quantum efficiency for fluorescence and phosphorescence _i materials are preferred. Specific examples include 8—hydroxyquinoline aluminum complex (Alq ₃ ); Carbazole series compounds; Dimer i zed styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Poly (P-phenylenevinylene KPPV) series polymer; Spi ro compounds; Polyfluorene. Rubren, etc. It is not limited only to these. The light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a heterocyclic containing compound. Specifically, as the condensed aromatic ring derivatives, anthracene derivatives, pyrene derivatives, naphthalene derivatives. Pentacene derivatives. Phenanthrene compound. Fluoranthene Compound There is a back. Heterocyclic compounds include, but are not limited to, carbazole derivatives, dibenzofuran derivatives, ladder type furan compounds, pyrimidine derivatives, and the like. Dopant materials include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, as the aromatic amine derivative, a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group includes pyrene, anthracene, chrysene, periplanthene having an arylamino group, and a styrylamine compound is substituted or unsubstituted. At least one arylvinyl group is substituted with the above-mentioned arylamine, and one or two or more substituents selected from the group consisting of aryl, silyl, alkyl, cycloalkyl and arylamino groups are substituted or unsubstituted. Specifically styrylamine styryldiamine, styryltriamine. Styryltetraamine and the like, but is not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto. The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As an electron transporting material, a material capable of injecting electrons well from the cathode and transferring the electrons to the light emitting layer is suitable. Do. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function followed by an aluminum or silver layer. Specifically cesium, barium. Calcium, ytterbium and samarium, each followed by an aluminum or silver layer. The electron injection layer is a layer for injecting electrons from the electrode. Has the ability to transport electrons, the effect of electron injection from the cathode. It has an excellent electron injection effect on the light emitting layer or the light emitting material, prevents the excitons generated in the light emitting layer from moving to the hole injection layer, and has excellent thin film formation ability Compound is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane. Anthrone and the like, derivatives thereof, metal complex compounds and nitrogen-containing five-membered ring derivatives, and the like, but are not limited thereto. As said metal complex compound, 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper bis (8-hydroxyquinolinato) manganese, Tris (8-hydroxyquinolinato) aluminum, Tris (2-methyl-8-hydroxyquinolinato) aluminum, Tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] Quinolinato) beryllium, bis (10—hydroxybenzo [h] quinolinato) zinc. Bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (0—cresolato) gallium, bis (2-methyl-8-quinolinato) (1- Naphlato) aluminum, bis (2-methyl-8-quinolinato) (2-naphlato) gallium and the like, but are not limited thereto. The organic light emitting device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used. In addition, the compound represented by Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device. Preparation of the compound represented by Chemical Formula 1 and an organic light emitting device including the same will be described in detail in the following Examples. However, the following examples are only for illustrating the present invention and the scope of the present invention is not limited thereto.

[Production example]

Preparation Example 1 Preparation of Compound 1

[Bungungsik 1-1]

A1

9-bromophenanthrene (50 g, 195 睡 ol), (4-chlorophenyl) boronic acid (33.5 g, 215 隱 ol) was dissolved in tetrahydrofuran (500 mL). Sodium carbonate 2 M solution (162 mL) and tetrakis (triphenylphosphine) palm (0) [Pd (PPh ₃ ) ₄ ] (6.8 g '5.9 Pa ol) were added and refluxed for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and the resulting mixture was extracted three times with water and toluene. The toluene was separated, dried over magnesium sulfate, and the filtrate was filtered and distilled under reduced pressure. The mixture was recrystallized three times with chloroform and ethane to give Compound AK28.1 g. Yield 50%; MS: [M + H] ⁺ = 289).

A1 A2

Compound AK28.1 g, 98 mmol) was dissolved in dimethylformamide (140 mU and then angled to 0 ^° C. Thereafter, N-bromosucciamide (17.4 g, 98 μl) was dissolved in DMF 3½1 and slowly After the reaction was slowly added, the mixture was stirred for 1 hour at room temperature, and after the reaction was completed, the mixture was washed once with sodium thiosulfate solution and once with water, dried over magnesium sulfate, and the filtrate was filtered under reduced pressure and column chromatographed. Purification by Torque Rape gave Compound A2 (25 g. Yield 首, MS: [M + H] ⁺ = 367).

Scheme 1-3

A2 A3

Compound A2 (20.0 g, 55 μl ol) and (4-thianophenyl) boronic acid (8.8 g, 60 μl ol) were dispersed in tetrahydrofuran (200 mL). 2M aqueous potassium carbonate solution (82 mL, 164 mmol) was added, followed by tetrakistriphenylphosphinopalladium [P (KPPh ₃ ) ₄ ] (1.9 g, 3 mol «

Stir and reflux for 4 hours. The temperature was lowered to room temperature and the resulting solid was filtered. The filtered solid was recrystallized with tetrahydrofuran and ethyl acetate, filtered and dried to give compound A3 (16.4 g, yield 77%; MS: [M + H] ⁺ = 390).

A3 A4

Compound A3 (15 g, 39 mmol) bis (pinacolato) diboron (10.8 g, 42 μl ol). Potassium acetate (11.4 g, 115 mmol). Bi (tritrinucleusphosphino) palladium biacetate (0) [Pd (OAc) ₂ (PCy ₃ ) ₂ ] (0.9 g. 3 inol%) was converted to dioxane ( 200 niL) and refluxed for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and then distilled under reduced pressure to remove the solvent. This was dissolved in chloroform, washed three times with water, the organic layer was separated and dried over magnesium sulfate. Distillation under reduced pressure gave Compound A4 (16.3 g, yield 88%; MS: [M + H] + = 482).

Compound 1

A4

Compound A4 (16.2 g, 34 mmol) and .2-chloro-4, 6-diphenyl-1,3,5-triazine (9 g, 34 μl) were dispersed in tetrahydrofuran (200 mL) 2M aqueous potassium carbonate solution (aq. K ₂ C0 ₃ ) (50 mL. 101 隱 ol) was added and tetrakistriphenylphosphinopalladium [Pd (PPh ₃ ) ₄ ] (1.2 g, 3 inol%) was added. Stir and reflux for 5 hours. The temperature was lowered with phase silver and the resulting solid was filtered off. The filtered solid was recrystallized from chloroform and ethyl acetate and filtered. Drying afforded compound 1 (9.5 g, yield 48%; MS: [M + H] ⁺ = 587). Preparation Example 2 Preparation of Compound 2

Compound BK19.0 g, in the same manner as in the preparation of Compound A3, except that [1,1'—biphenyl] —4-yl boronic acid (11.9 g, 60 mmol) was used instead of (4-thianophenyl) boronic acid, Yield 79%: MS: [M + H] ⁺ = 441) was prepared.

[Bungungsik 2-2]

B1 B2

Compound Bl (15 g, 34 mmol) instead of compound A4

Compound B2 (19.0 in the same manner as in the preparation of compound A4

MS: [M + H] ⁺ = 532).

Compound 2

B2

Compound 2 (12.9 g, yield 60%; MS: [M + H] ⁺ = 638) was prepared in the same manner as the preparation of Compound A4, except that Compound B2U7.9 g, 34 mmol) was used instead of Compound A3. Preparation Example 3 Preparation of Compound 3

Compound CK19.0 g, yield in the same manner as in the preparation of Compound A3, except that (4- (pyridin-2-yl) phenyl) boronic acid (11.9 _g , 60 minol) was used instead of (4-thianophenyl) boronic acid. 81%; MS: [M + H] ⁺ = 442).

C1 C2

Compound C2 (18. ^' lg, yield 88%: MS: [M + H] ⁺ = 533) was prepared in the same manner as the preparation of Compound A4, except that Compound Cl (15 g, 34 mmol) was used instead. It was.

C2 Compound 3 Compound 3 (9.7 g, yield 45%; MS: [M + H] ⁺ = 639) was prepared in the same manner as the preparation of Compound A4, except that Compound C2U7.9 g, 34 mmol) was used instead of Compound A3. It was. Preparation Example 4 Preparation of Compound 4

[Bungungsik 4-1]

(4-Im-cyano-phenyl) boronic acid ₍₄ (9H- _carbazol-9 euil) phenylboronic acid (17.3 g, compound in the same manner to the preparation of compound A3 except that the 60 mmol) DK22.0 g, yield: 76 %; MS: [M + H] + = 530).

D1 D2

Compound D2 (21.3 g, yield 89%; MS: [M + H] + = 622) was prepared in the same manner as the preparation of Compound A4, except that Compound D1 (15 g, 34 mmol) was used instead of Compound A4.

Compound 4

D2 Compound 4 (15.4 g, yield 63%; MS: [M + H] ⁺ = 727) was prepared in the same manner as the preparation of Compound A4, except that Compound D2 (20.9 g, 34 mmol) was used instead of Compound A3. Preparation Example 5 Preparation of Compound 5

A4 E1

Compound EK21.3 g, yield in the same manner as in the preparation of Compound A3, except that (4-thianophenyl) boronic acid dibenzo [b, d] furan-4-ylboronic acid (12.7 g, 60 画 ol) was used 89%; MS: [M + H] + = 455).

E1 E2

Compound E2 (21.1 g, yield 93%; MS: [M + H] ⁺ = 547) was prepared in the same manner as the preparation of Compound A4, except that Compound El (15 g. 33 mmol) was used instead of Compound A4.

Scheme 5-3

Compound 5 (11 g, yield 50%; MS: [M + H] ⁺ = 652) was prepared in the same manner as the preparation of Compound A4, except that Compound E2 (18.4 g, 34 mmol) was used instead of Compound A3.

Experimental Example

Experimental Example 1-1

A glass substrate coated with a thin film having an indium tin oxkle (IT0) of 1,300 A was placed in distilled water in which detergent was dissolved and ultrasonically cleaned. At this time, the detergent was used the Fisher Company _(Fischer. Co.) products, distilled water was Millipore (MiUipore Co.) was used as the second filtered distilled water to drive a filter (Filter) of the product. _. After washing IT0 for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After the distilled water wash, ultrasonic cleaning with a solvent of isopropyl alcohol, acetone, methanol, dried and transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator. A hole injection layer was formed by thermally vacuum depositing the following HI-1 compound to a thickness of 50 A on the IT0 transparent electrode prepared as described above. A hole transport layer was formed by thermal vacuum deposition of the following HT-1 compound at a thickness of 250 A on the hole injection layer, and an electron blocking layer was formed by vacuum deposition of the following HT-2 compound at a thickness of 50 A on the HT-1 deposition film. Compound 1 prepared in Example 1 and the following YGD-1 compound, which is a phosphorescent dopant, were co-deposited at a weight ratio of 88:12 on the HT-2 deposited film to form a light emitting insect having a thickness of 400A. Vacuum depositing the following ET-1 compound to a thickness of 250 A on the emission layer; The following ET-2 compounds were co-deposited with Li in a 2% weight ratio to a thickness of 100 A to form an electron transport layer and an electron injection bug. Alumina with a thickness of 1000A on the electron injection layer

YGD-1 ET-1 ET-2

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7 A / sec, the aluminum was maintained at the deposition rate of 2 A / sec, and the vacuum degree during deposition was maintained at 1 X 10— ⁷ ~ 5 X 10 ^"8 torr. Experimental Examples 1-2 to 1-5

An organic light emitting diode was manufactured according to the same method as Experimental Example 1-1 except for using the compound described in Table 1 below instead of compound 1 of Example 1 in Experimental Example 1-1. Comparative Experimental Examples 1-1 to 1-3

Except for using the compound shown in Table 1 instead of compound 1 of Example 1 in Experimental Example 1 in the same manner as in Experimental Example 1-1 A light emitting device was manufactured. To the compounds of CE1 to CE3 in Table 1

CE1 CE2 CE3

In the above Experimental Examples and Examples, the driving voltage and the luminous efficiency of the organic light emitting diode were measured at a current density of 10 mA / cm ² , and the time (LT95) of initial luminance vs. 95% at a current density of 50 mA / cm ² was measured. It was. The results are shown in Table 1 below.

Table 1

1-2 0.55 Comparative Experimental Example 0.44,

CE 3 3.5 62 5 1-3 0.55 As shown in Table 1, when the compound of the present invention is used as a light emitting layer material. As compared with the comparative experimental example, it was confirmed that the characteristics showed excellent efficiency and lifespan. Experimental Example 2-1

A glass substrate (corning 7059 gl ass) coated with a thin film of I0 (indium t in oxide) Ι, ΟΟΟΑ thickness was placed in distilled water in which a dispersant was dissolved and washed ultrasonically. The detergent used was Fischer Co.'s product. Distilled water was used in Mi ll ipore Co. Secondarily filtered distilled water was used as a product filter. After washing IT0 for 30 minutes, the ultrasonic washing was repeated 10 times with distilled water twice. After washing with distilled water, ultrasonic washing was performed in the order of isopropyl alcohol, acetone, and methanol solvent and dried. The following HI-1 compound was vacuum-deposited to a thickness of 500 A on the prepared IT0 transparent electrode to form a hole injection layer. The following HT-1 compound was vacuum deposited to a thickness of 400 A on the hole injection layer to form a hole transport layer, and the host HI and the dopant D1 compound were vacuum deposited to a thickness of 300 A at a weight ratio of 97.5: 2.5 as the light emitting layer. The following compound ET-A was vacuum deposited to a thickness of 50 A on the emission layer to form an electron transport layer. Compound 1 and LiQ (Li thium Quinolate) prepared in Example 1 were vacuum deposited on the electron transport layer at a weight ratio of 1: 1 to form an electron injection and transport layer at a thickness of 350A. Lithium fluoride (LiF) and aluminum at a thickness of 2,000 A were sequentially deposited on the electron injection and transport layer to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7A / sec and the lithium fluoride of the cathode was 0.3A / sec. Aluminum maintained the deposition rate of 2A / sec, the vacuum degree during deposition was maintained at 2 Χ ΓΓ ⁷ ~ 5 X 10 ^"6 torr, to fabricate an organic light emitting device. Experimental Example 2-2 to 2-5

An organic light emitting device was manufactured according to the same method as Experimental Example 2-1, except for using the compound shown in Table 2 below instead of compound 1 of Example 1 in Experimental Example 2-1. Comparative Experimental Examples 2-1 to 2-3

An organic light emitting device was manufactured according to the same method as Experimental Example 2-1, except for using the compound shown in Table 2 below instead of compound 1 of Example 1 in Experimental Example 2-1. The compounds of CE4, CE2 and CE3 in Table 2 are as follows.

CE4 CE2 CE3 In the above experimental and comparative examples, the driving voltage and the luminous efficiency were measured at a current density of 10 mA / cm ² , and the time became 95% of the initial luminance at a current density of 50 mA / cm ² . (LT95) was measured. The results are shown in Table 1 below.

Table 2

1-3 0.132 As shown in Table 2 above. When the compound of the present invention is used as the electron transport layer material, it was confirmed that exhibits excellent efficiency and lifespan as compared to the comparative experimental example.

[Explanation of code]

Substrate 2: Anode

Light emitting layer 4: cathode

Hole injection layer 6: Hole transport layer

Light Emitting Layer 8: Electron Transport Layer

Claims

[Patent Claims]

[Claim 11

The compound represented by following formula (1):

In Formula 1,

. , ¾ and ¾ are each independently CH or N, provided that at least one of, ¾ and ¾ is N,

Is a substituted or unsubstituted C ₆ - ₆₀ and heteroarylene, - ₆₀ arylene, or C ₅ containing one or more heteroatoms selected from the group consisting of a substituted or unsubstituted N, 0 and S

Is a single bond, a substituted or unsubstituted C ₆ - C ₅ comprising one or more heteroatoms selected from the group consisting of ₆₀ arylene, a substituted or unsubstituted N, 0 and S - ₆₀ heteroarylene and eu

An, Ar ₂ and Ar ₃ ^ each independently represent a substituted or unsubstituted (C: _{6 60} aryl, or a substituted or unsubstituted N, 0 and S C ₅ -containing at least one hetero atom selected from the group consisting of ₆₀ heteroaryl, wherein the aryl or heteroaryl may be further substituted with a cyano group,

only. Two substituents of the phenanthryl

/ Ar ₃

ζ ² is different from each other. [Claim 2]

The method of claim 1,

Compound represented by Formula 1 is any one selected from compounds represented by Formula 1-1 to 1-4, Compound:

[Formula 1-4]

In Chemical Formulas 1-1 to 1-4,

L _1; L _{2 (} An, Ar ₂ and Ar ₃ are as defined in Claim 1. [Claim 3]

The method of claim 1,

[Claim 5]

The method of claim 1,

[Claim 6]

One, the compound.

[Claim 7]

The method of claim 1.

An, Ar ₂ and Ar ₃ are each independently any one selected from the group consisting of:

[Claim 8]

The method of claim 1,

The compound represented by Formula 1 is any one selected from the group consisting of: Compound:

-niOO / 8TOZaM / X3d 1-06SST / 810Z OAV

6SSI / 8I0Z OAV

^ εΐΖΟΟ / 8ΐΟΖΗΜ / Χ3 <Ι) 6SSI / 8I0Z OAV

[Claim 9]

A first electrode; A second electrode provided to face the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes a compound according to any one of claims 1 to 8. That is, an organic light emitting device.

[Claim 10]

The method of claim 9,

The organic material layer containing the compound is an electron injection layer; Electron transport layer; Or an electron injection and electron transport layer at the same time.