KR102523030B1 - Novel hetero-cyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

Novel heterocyclic compound and organic light emitting device using the same

The present invention relates to a novel heterocyclic compound and an organic light emitting device including the same.

In general, the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon has a wide viewing angle, excellent contrast, and a fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.

An organic light emitting device generally has a structure including an anode, a cathode, and an organic material layer between the anode and the cathode. In order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often composed of a multi-layered structure composed of different materials, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. In the structure of this organic light emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and when the injected holes and electrons meet, excitons are formed. When it falls back to the ground state, it glows.

The development of new materials for organic materials used in the organic light emitting device as described above is continuously required.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to a novel heterocyclic compound and an organic light emitting device including the same.

The present invention provides a compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

X ₁ to X ₃ are each independently N or CR', but at least one is N;

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted aryl having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms including at least one of O, N, Si and S, wherein at least one of Ar ₁ and Ar ₂ is represented by Formula 2 or Formula 3 below,

R ₁ , R ₂ and R' are each independently hydrogen; heavy hydrogen; halogen; hydroxy; nitrile; nitro; amino; substituted or unsubstituted alkyl having 2 to 60 carbon atoms; 2 to 60 substituted or unsubstituted alkoxy; Substituted or unsubstituted 2 to 60 alkenyl; 6 to 60 substituted or unsubstituted aryl; Or a substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms including one or more of O, N, Si and S,

a is an integer from 1 to 7;

b is an integer from 1 to 10;

[Formula 2]

[Formula 3]

In Formulas 2 and 3,

R ₃ is hydrogen; heavy hydrogen; halogen; hydroxy; nitrile; nitro; amino; substituted or unsubstituted alkyl having 2 to 60 carbon atoms; 2 to 60 substituted or unsubstituted alkoxy; Substituted or unsubstituted 2 to 60 alkenyl; 6 to 60 substituted or unsubstituted aryl; Or a substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms including one or more of O, N, Si and S,

c is an integer from 1 to 7;

In addition, 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 at least one of the organic material layers includes the compound represented by Chemical Formula 1. do.

The compound represented by Chemical Formula 1 may be used as a material for an organic layer of an organic light emitting diode, and may improve efficiency, low driving voltage, and/or lifespan characteristics of an organic light emitting diode. In particular, the compound represented by Chemical Formula 1 may be used as a material for hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection.

1 shows an example of an organic light emitting device composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
2 shows a substrate (1), an anode (2), a hole transport layer (5), an electron blocking layer (6), a light emitting layer (3), a hole blocking layer (7), an electron transport and injection layer (8), and a cathode (4). ) It shows an example of an organic light emitting device made of.

Hereinafter, in order to aid understanding of the present invention, it will be described in more detail.

The present invention provides a compound represented by Formula 1 above.

및

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

and

means a bond connected to another substituent.

In this specification, the term "substituted or unsubstituted" means deuterium; halogen group; nitrile group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; Alkyl thioxy group; Arylthioxy group; an alkyl sulfoxy group; aryl sulfoxy groups; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; Aralkenyl group; Alkyl aryl group; Alkylamine group; Aralkylamine group; heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing at least one of N, O, and S atoms, or substituted or unsubstituted with two or more substituents linked to each other among the substituents exemplified above. . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

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

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the silyl group is specifically a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. but not limited to

In the present specification, the boron group specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, a phenyl boron group, but is not limited thereto.

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

In the present specification, the alkyl group may be straight-chain or branched-chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the number of carbon atoms of the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited thereto.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one 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, 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-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, etc., but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 6. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, 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 one embodiment, the number of carbon atoms of the aryl group is 6 to 30. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 20. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc. as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

etc. However, it is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group containing at least one of O, N, Si, and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but preferably has 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, and an acridyl group. , pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinoline group, indole group , carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia A zolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, an aralkyl group, an aralkenyl group, an alkylaryl group, and an aryl group among arylamine groups are the same as the examples of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the examples of the above-mentioned alkyl group. In the present specification, the description of the heterocyclic group described above may be applied to the heteroaryl of the heteroarylamine. In the present specification, the alkenyl group among the aralkenyl groups is the same as the examples of the alkenyl group described above. In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group. In the present specification, the description of the heterocyclic group described above may be applied except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aryl group or cycloalkyl group described above may be applied, except that the hydrocarbon ring is formed by combining two substituents. In the present specification, the heterocyclic group is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that it is formed by combining two substituents.

Preferably, Chemical Formula 1 may be any one selected from compounds represented by Chemical Formulas 1-1 to 1-8.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

In Formulas 1-1 to 1-8,

Descriptions of X ₁ , X ₂ , X ₃ , Ar ₁ , Ar ₂ , R ₁ to R ₃ , a, b and c are as defined above.

Preferably, all of X ₁ to X ₃ are N.

Preferably, Ar ₁ and Ar ₂ may each independently be any one selected from the group consisting of the following.

.

.

Preferably, R ₁ to R ₃ may each independently represent hydrogen or deuterium.

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

.

.

The compound represented by Chemical Formula 1 can be prepared by a preparation method as shown in Reaction Scheme 1 below. The manufacturing method may be more specific in the manufacturing examples described below.

[Scheme 1]

In Reaction Scheme 1, the definitions except for X are as defined above, and X is halogen, and more preferably bromo or chloro. The above reaction is a Suzuki coupling reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and a reactor for the Suzuki coupling reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

In addition, the present invention provides an organic light emitting device including the compound represented by Formula 1 above. In one example, the present invention provides 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 at least one of the organic material layers includes the 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, or may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention 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 as organic layers. However, the structure of the organic light emitting device is not limited thereto and may include fewer organic layers.

In addition, the organic material layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes, and the hole injection layer, the hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 above. Contains the indicated compounds.

Also, the organic layer may include a light emitting layer, and the light emitting layer includes the compound represented by Chemical Formula 1. For example, the compound represented by Chemical Formula 1 may be included as a host material of the light emitting layer.

The light emitting layer may include a compound represented by Chemical Formula 4 below. For example, a compound represented by Chemical Formula 4 may be further included as a host material of the light emitting layer.

[Formula 4]

In Formula 4,

Ar ₃ and Ar ₄ are each independently substituted or unsubstituted aryl having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms including one or more of O, N, Si and S,

R ₄ and R ₅ are each independently hydrogen; heavy hydrogen; halogen; cyano; nitro; amino; substituted or unsubstituted alkyl having 1 to 60 carbon atoms; Substituted or unsubstituted 3 to 60 cycloalkyl; Substituted or unsubstituted 2 to 60 alkenyl; 6 to 60 substituted or unsubstituted aryl; Or a substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms including one or more of O, N, Si and S,

p and q are each independently an integer of 0 to 7;

In Formula 4, Ar ₃ and Ar ₄ may each independently be phenyl, biphenylyl, terphenylyl, naphthyl, dibenzofuranyl, dibenzothiophenyl or dimethylfluorenyl.

In addition, the compound represented by Chemical Formula 4 may be any one selected from the group consisting of the following.

.

.

In addition, the organic material layer may include an electron transport layer or an electron injection layer, and the electron transport layer or electron injection layer includes the compound represented by Chemical Formula 1.

In addition, the electron transport layer, the electron injection layer, or the layer simultaneously transporting and injecting electrons includes the compound represented by Formula 1.

In addition, the organic material layer may include a light emitting layer and an electron transport layer, and the electron transport layer may include the compound represented by Chemical Formula 1.

Also, the organic light emitting device according to the present invention may be a normal type organic light emitting device 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 shows an example of an organic light emitting device composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. In this structure, the compound represented by Chemical Formula 1 may be included in the light emitting layer.

2 shows a substrate (1), an anode (2), a hole transport layer (5), an electron blocking layer (6), a light emitting layer (3), a hole blocking layer (7), an electron transport and injection layer (8), and a cathode (4). ) It shows an example of an organic light emitting device made of. In this structure, the compound represented by Chemical Formula 1 may be included in at least one layer of the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, and the electron transport and injection layer.

The organic light emitting device according to the present invention may be manufactured using materials and methods known in the art, except that at least one of the organic layers includes the compound represented by Chemical Formula 1. Also, 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, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, depositing a metal or a metal oxide having conductivity or an alloy thereof on the substrate to form an anode After forming an organic material layer including a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, and an electron transport and injection layer thereon, depositing a material that can be used as a cathode thereon can be prepared. 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.

In addition, the compound represented by Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

In addition to this method, 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 (WO 2003/012890). However, the manufacturing method is not limited thereto.

In one example, the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.

As the anode material, a material having a high work function is generally preferred so that holes can be smoothly injected into the organic layer. Specific examples of the cathode 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 (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

The cathode material is preferably a material having a small work function so as to easily inject electrons into the organic material layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

The hole injection material is a layer for injecting holes from the electrode, and the hole injection material has the ability to transport holes and has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and is formed in the light emitting layer. A compound that prevents migration of excitons to an electron injecting layer or electron injecting material and has an excellent ability to form a thin film is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include metal porphyrins, oligothiophenes, arylamine-based organic materials, hexanitrilehexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene-based organic materials. of organic matter, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer. As a hole transport material, a material capable of receiving holes from the anode or the hole injection layer and transferring them to the light emitting layer is a material having high hole mobility. this is suitable Specific examples include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated parts.

The light emitting material is a material capable of emitting light in the visible ray region by receiving 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; compounds of the benzoxazole, benzthiazole and benzimidazole series; poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; Polyfluorene, rubrene, etc., but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material includes a condensed aromatic ring derivative or a compound containing a hetero ring. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type furan compounds, pyrimidine derivatives, etc., but are not limited thereto.

Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, aromatic amine derivatives are condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, periplanthene, etc. having an arylamino group, and styrylamine compounds include substituted or unsubstituted arylamine is substituted with at least one arylvinyl group, wherein one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc., but is not limited thereto. In addition, metal complexes include, but are not limited to, iridium complexes and platinum complexes.

The electron transport material is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. The electron transport material is a material that can receive electrons from the cathode and transfer them to the light emitting layer, and has high electron mobility. this is suitable Specific examples include Al complexes of 8-hydroxyquinoline; Complexes containing 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 according to the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by a layer of aluminum or silver.

The electron injection layer is a layer for injecting electrons from an electrode, has the ability to transport electrons, has an excellent electron injection effect from a cathode, an excellent electron injection effect for a light emitting layer or a light emitting material, and injects holes of excitons generated in the light emitting layer. A compound that prevents migration to a layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preonylidene methane, anthrone, etc. and their derivatives, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include 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)( There are o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium. Not limited to this.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type, or a double side emission type depending on the material used.

In addition, the compound represented by Chemical Formula 1 may be included in an organic solar cell or an organic transistor in addition to an organic light emitting device.

Hereinafter, preferred embodiments are presented to aid understanding of the invention. However, the following examples are only for exemplifying the present invention, and do not limit the present invention only to these.

<Example>

Example 1: Preparation of Compound 1

Step 1) Preparation of compound 1-a

11,12-dihydroindolo[2,3-a]carbazole (15.0 g, 58.5 mmol) and intermediate a (10.1 g, 64.4 mmol) in a nitrogen atmosphere ) was added to toluene (300 ml), stirred and refluxed. Then, sodium tert-butoxide (8.4 g, 87.8 mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.9 g, 1.8 mmol) were added. After reacting for 7 hours, the mixture was cooled at room temperature, and the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare compound 1-a. (14.2 g, yield 73%, MS: [M+H] ⁺ = 333)

Step 2) Preparation of Compound 1

Compound 1-a (15.0 g, 45.1 mmol) and Intermediate A (23.0 g, 49.6 mmol) were added to toluene (300 ml) under a nitrogen atmosphere, followed by stirring and reflux. Then, sodium tert-butoxide (6.5 g, 67.7 mmol) and bis(tri-tert-butylphosphine)palladium(0) (0.7 g, 1.4 mmol) were added. After reacting for 9 hours, the mixture was cooled at room temperature, and the organic layer was separated using chloroform and water, and then the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, Compound 1 was prepared by sublimation purification. (11.7 g, yield 34%, MS: [M+H] ⁺ = 761)

Example 2: Preparation of Compound 2

Compound 2 was prepared in the same manner as in Example 1, except that intermediate b was used instead of intermediate a and intermediate B was used instead of intermediate A. (MS: MS[M+H] ⁺ = 766)

Example 3: Preparation of Compound 3

Compound 3 was prepared in the same manner as in Example 1, except that Intermediate c was used instead of Intermediate a and Intermediate C was used instead of Intermediate A. (MS: MS[M+H] ⁺ = 837)

Example 4: Preparation of Compound 4

Compound 4 was prepared in the same manner as in the preparation method of Compound 1 in Example 1, except that Intermediate b was used instead of Intermediate a. (MS: MS[M+H] ⁺ = 867)

Example 5: Preparation of Compound 5

Compound 5 was prepared in the same manner as in Example 1, except that intermediate b was used instead of intermediate a and intermediate D was used instead of intermediate A. (MS: MS[M+H] ⁺ = 761)

Example 6: Preparation of Compound 6

Compound 6 was prepared in the same manner as in Example 1 for preparing compound 1, except that intermediate c was used instead of intermediate a and intermediate E was used instead of intermediate A. (MS: MS[M+H] ⁺ = 837)

Example 7: Preparation of Compound 7

Compound 7 was prepared in the same manner as in Example 1 for preparing compound 1, except that intermediate d was used instead of intermediate a and intermediate F was used instead of intermediate A. (MS: MS[M+H] ⁺ = 837)

Example 8: Preparation of Compound 8

11,12-dihydroindolo[2,3-a]carbazole-1,3,4,7,8,10-d6 instead of 11,12-dihydroindolo[2,3-a]carbazole Compound 8 was prepared in the same manner as in Example 1 for preparing Compound 1, except that Intermediate F was used instead of Intermediate A. (MS: MS[M+H] ⁺ = 767)

<Experimental Example 1>

A glass substrate coated with ITO (Indium Tin Oxide) to a thickness of 1,400 Å was put in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product of Fischer Co. was used as a detergent, and distilled water filtered through a second filter of a product of Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was performed twice with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with solvents such as isopropyl alcohol, acetone, and methanol, dried, and transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transferred to a vacuum deposition machine.

The following HT-A and 5% by weight of PD were thermally vacuum deposited to a thickness of 100 Å on the prepared ITO transparent electrode, and then only the HT-A material was deposited to a thickness of 1150 Å to form a hole transport layer. The following HT-B was thermally vacuum deposited thereon to a thickness of 450 Å as an electron blocking layer. Subsequently, Compound 1 prepared in Example 1 was used as a host and 15% by weight of GD as a dopant was vacuum deposited to a thickness of 400 Å to form a light emitting layer. Subsequently, ET-A below was vacuum deposited to a thickness of 50 Å as a hole blocking layer. Subsequently, as an electron transport and injection layer, ET-B and Liq were thermally vacuum deposited to a thickness of 250 Å at a ratio of 2:1, followed by vacuum deposition of LiF and magnesium at a ratio of 1:1 to a thickness of 30 Å. An organic light emitting device was manufactured by depositing magnesium and silver to a thickness of 160 Å at a ratio of 1:4 on the electron injection layer to form a cathode.

<Experimental Examples 2 to 12 and Comparative Experimental Examples 1 to 5>

Experimental Examples 2 to 12 and Comparative Experimental Examples 1 to 5 were each manufactured in the same manner as in Experimental Example 1, except that the host material was changed as shown in Table 1 below. At this time, when a mixture of two types of compounds is used as the host, the weight ratio between the host compounds is indicated in parentheses.

The organic light emitting devices manufactured in Experimental Examples 2 to 12 and Comparative Experimental Examples 1 to 5 were heat-treated in an oven at 100 ° C. for 30 minutes, then taken out, and current was applied to measure voltage, efficiency, and lifetime (T ₉₅ ), and the results It is shown in Table 1 below. At this time, the voltage and efficiency were measured by applying a current density of 10 mA/cm ² , and T ₉₅ refers to the time until the initial luminance decreases to 95% at a current density of 20 mA/cm ² .

host substance Voltage (V) Efficiency (cd/A) Life (T ₉₅ , hr) Experimental Example 1 compound 1 4.57 53.3 83 Experimental Example 2 compound 2 4.56 54.2 98 Experimental Example 3 compound 3 4.53 53.6 81 Experimental Example 4 compound 4 4.55 54.4 80 Experimental Example 5 compound 5 4.62 55.8 82 Experimental Example 6 compound 6 4.63 55.7 78 Experimental Example 7 compound 7 4.71 51.3 80 Experimental Example 8 compound 8 4.73 52.1 97 Experimental Example 9 PGH-1:Compound 1 = (60:40) 4.36 60.4 122 Experimental Example 10 PGH-2:Compound 3 = (60:40) 4.32 61.1 120 Experimental Example 11 PGH-2:Compound 5 = (60:40) 4.33 62.0 121 Experimental Example 12 PGH-2:compound 6 = (60:40) 4.38 58.1 118 Comparative Experimental Example 1 GH-A 4.81 48.2 57 Comparative Experimental Example 2 GH-B 4.75 41.8 61 Comparative Experimental Example 3 GH-C 5.16 38.0 53 Comparative Experimental Example 4 PGH-1:GH-A = (60:40) 4.67 40.5 81 Comparative Experimental Example 5 PGH-2:GH-C = (60:40) 4.73 43.1 70

As can be seen from Table 1, it was confirmed that the organic light emitting device including the compound having the structure of Formula 1 exhibits characteristics of low voltage, high efficiency, and long life compared to the organic light emitting device not including the compound having the structure of Formula 1. did. In particular, when the compound of Formula 1 was mixed with the compound of Formula 4, it was confirmed that exciplex was formed and the effect was greater.

As a result, when the compound of Formula 1 is used as a host for the light emitting layer of an organic electroluminescent device, a device with low voltage, high efficiency, and long lifespan can be obtained.

1: substrate 2: anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: light emitting layer 8: electron transport layer

Claims (11)

A compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
X ₁ to X ₃ are all N;
Ar ₁ and Ar ₂ are each independently substituted or unsubstituted aryl having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms including at least one of O, N, Si and S, wherein at least one of Ar ₁ and Ar ₂ is represented by Formula 2 or Formula 3 below,
R ₁ , R ₂ and R' are each independently hydrogen; heavy hydrogen; halogen; hydroxy; nitrile; nitro; amino; substituted or unsubstituted alkyl having 2 to 60 carbon atoms; 2 to 60 substituted or unsubstituted alkoxy; Substituted or unsubstituted 2 to 60 alkenyl; 6 to 60 substituted or unsubstituted aryl; Or a substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms including one or more of O, N, Si and S,
a is an integer from 1 to 7;
b is an integer from 1 to 10;
[Formula 2]

[Formula 3]

In Formulas 2 and 3,
R ₃ is hydrogen; heavy hydrogen; halogen; hydroxy; nitrile; nitro; amino; substituted or unsubstituted alkyl having 2 to 60 carbon atoms; 2 to 60 substituted or unsubstituted alkoxy; Substituted or unsubstituted 2 to 60 alkenyl; 6 to 60 substituted or unsubstituted aryl; Or a substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms including one or more of O, N, Si and S,
c is an integer from 1 to 7;
According to claim 1,
Formula 1 is any one selected from compounds represented by Formulas 1-1 to 1-8, a compound:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

In Formulas 1-1 to 1-8,
Descriptions of X ₁ , X ₂ , X ₃ , Ar ₁ , Ar ₂ , R ₁ to R ₃ , a, b and c are as defined in claim 1.
delete According to claim 1,
A compound wherein Ar ₁ and Ar ₂ are each independently any one selected from the group consisting of:

.
According to claim 1,
R ₁ to R ₃ are each independently hydrogen or deuterium. compound.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of the following compounds:

.
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 at least one organic material layer is any one of claims 1, 2, and 4 to 6. An organic light emitting device comprising the compound according to one claim.
According to claim 7,
The organic material layer containing the compound is a light emitting layer, an organic light emitting device.
According to claim 8,
The light emitting layer further comprises a compound represented by Formula 4, an organic light emitting device:
[Formula 4]

In Formula 4,
Ar ₃ and Ar ₄ are each independently substituted or unsubstituted aryl having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms including one or more of O, N, Si and S,
R ₄ and R ₅ are each independently hydrogen; heavy hydrogen; halogen; cyano; nitro; amino; substituted or unsubstituted alkyl having 1 to 60 carbon atoms; Substituted or unsubstituted 3 to 60 cycloalkyl; Substituted or unsubstituted 2 to 60 alkenyl; 6 to 60 substituted or unsubstituted aryl; Or a substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms including one or more of O, N, Si and S,
p and q are each independently an integer of 0 to 7;
According to claim 9,
Ar ₃ and Ar ₄ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, dibenzofuranyl, dibenzothiophenyl or dimethylfluorenyl, the organic light emitting device.
According to claim 9,
The compound represented by Formula 4 is any one selected from the group consisting of:

.

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