KR102469105B1 - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

Novel compound and organic light emitting device comprising the same {Novel compound and organic light emitting device comprising the same}

The present invention relates to a novel 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. The organic material layer is often composed of a multi-layer 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 layer, an electron suppression layer, a light emitting layer, a hole blocking layer, an electron transport layer, It may consist of an injection layer or the like. 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 organic light emitting material 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 is O, S, or SO ₂ ;

Ar ₁ is phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, dimethylfluorenyl, naphthyl phenyl, or phenanthrenyl phenyl;

Ar ₂ is a substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,

L ₁ and L ₂ are each independently a single bond; Or a substituted or unsubstituted C _6-60 arylene.

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. .

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, electron suppression, light emission, hole blocking, electron transport, or electron injection.

1 shows an example of an organic light emitting device composed of a substrate 1, an anode 2, an electron suppression layer 3, a light emitting layer 4, and a cathode 5.
2 shows a substrate (1), an anode (2), a hole injection layer (6), a hole transport layer (7), an electron blocking layer (3), a light emitting layer (4), a hole blocking layer (8), an electron injection and transport layer ( 9) and an example of an organic light emitting element composed of a cathode 5 is shown.

Hereinafter, in order to aid understanding of the present invention, it will be described in more detail. However, the following examples are merely illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

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.

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

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 group; 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 heteroaryl 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 heteroaryl group is a heteroaryl group containing one or more 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. According to one embodiment, the heteroaryl group has 6 to 30 carbon atoms. According to one embodiment, the carbon number of the heteroaryl group is 6 to 20. Examples of the heteroaryl 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 heteroaryl 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 heteroaryl group described above may be applied except that 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, heteroaryl is not a monovalent group, and the description of the above-described heteroaryl group may be applied, except that it is formed by combining two substituents.

Preferably, Chemical Formula 1 may be represented by the following Chemical Formulas 1-1 to 1-4:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formula 1-1 to Formula 1-4,

X, Ar ₁ , Ar ₂ , L ₁ and L ₂ are described as defined in Chemical Formula 1 above.

Preferably, Ar ₁ may be any one selected from the group consisting of:

.

.

Preferably, Ar ₂ may be a substituted or unsubstituted C _6-20 aryl;

More preferably, Ar ₂ can be phenyl, biphenylyl, or naphthyl.

Preferably, L ₁ is a single bond; Or it may be a substituted or unsubstituted C _6-20 arylene,

More preferably, L ₁ may be a single bond, phenylene, or biphenylylene;

Most preferably, L ₁ can be a single bond or phenylene.

Preferably, L ₂ is a single bond; Or it may be a substituted or unsubstituted C _6-20 arylene,

More preferably, L ₂ can be a single bond, phenylene, or biphenylylene;

Most preferably, L ₂ can be phenylene.

Preferably, at least one of L ₁ and L ₂ may be phenylene;

More preferably, L ₂ may be phenylene.

Representative examples of the compound represented by Formula 1 are as follows:

The compound represented by Formula 1 can be prepared by, for example, a manufacturing method such as the following Reaction Scheme 1, and other compounds can be prepared similarly.

[Scheme 1]

In Reaction Scheme 1, X, Ar ₁ , Ar ₂ , L ₁ and L ₂ are as defined in Formula 1, X ₁ is halogen, and preferably X ₁ is chloro or bromo.

Reaction Scheme 1 is an amine substitution reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the amine substitution 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 blocking layer, an electron transport layer, an electron injection layer, and the like as organic layers. However, the structure of the organic light emitting diode is not limited thereto and may include a smaller number of organic material layers.

In addition, the organic material layer may include an electron suppression layer or a light emitting layer, and the electron suppression layer or the light emitting layer may include the compound represented by Chemical Formula 1. Preferably, the compound represented by Chemical Formula 1 may be included as a material of the electron blocking layer.

In addition, the organic material layer may include a hole transport layer, a hole injection layer, or a layer that simultaneously transports and injects holes, and the hole transport layer, the hole injection layer, or the layer for simultaneously transporting and injecting holes is The compound represented by 1 may be included.

In addition, the organic material layer may include an electron transport layer, an electron injection layer, or an electron injection and transport layer, and the electron transport layer, electron injection layer, or electron injection and transport layer may include the compound represented by 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, an electron suppression layer 3, a light emitting layer 4, and a cathode 5. In this structure, the compound represented by Chemical Formula 1 may be included in the electron blocking layer.

2 shows a substrate (1), an anode (2), a hole injection layer (6), a hole transport layer (7), an electron blocking layer (3), a light emitting layer (4), a hole blocking layer (8), an electron injection and transport layer ( 9) and an example of an organic light emitting element composed of a cathode 5 is shown. In such a structure, the compound represented by Formula 1 may be included in at least one layer of the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, and the electron injection and transport 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 And, after forming 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, 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 layer 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 generated in the light emitting layer A compound that prevents migration of excitons to the electron injecting layer or electron injecting material and has excellent thin film formation ability is preferred. 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 electron blocking layer is a layer placed between the hole transport layer and the light emitting layer in order to prevent electrons injected from the cathode from being recombined in the light emitting layer and passing to the hole transport layer, and is also called an electron blocking layer or an electron blocking layer. . A material having a smaller electron affinity than the electron transport layer is preferable for the electron blocking layer. Preferably, the compound represented by Chemical Formula 1 may be included as a material of the electron blocking layer.

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 hole blocking layer is a layer placed between the electron transport layer and the light emitting layer to prevent holes injected from the anode from being recombinated in the light emitting layer and passing to the electron transport layer, and is also called a hole blocking layer. A material having high ionization energy is preferred for the hole-blocking layer.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable. do. 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.

On the other hand, in the present invention, the "electron injection and transport layer" is a layer that performs both the roles of the electron injection layer and the electron transport layer, and materials that play the role of each layer may be used alone or in combination, but are limited thereto. It doesn't work.

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, in order to aid understanding of the present invention, it will be described in more detail. However, the following examples are merely illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

Preparation Example 1

After completely dissolving compound 2-(4-bromophenyl)-5-phenylfuran (8.51 g, 28.46 mmol) and compound a1 (11.24 g, 28.46 mmol) in Xylene (280 mL) in a 500 mL round bottom flask under a nitrogen atmosphere, NaOtBu ( 4.10 g, 42.69 mmol) was added, and Bis(tri- tert -butylphosphine) palladium(0) (0.15 g, 0.28 mmol) was added, followed by heating and stirring for 6 hours. After lowering the temperature to room temperature and filtering to remove the base, Xylene was concentrated under reduced pressure and recrystallized with ethyl acetate (270 mL) to prepare Compound 1 (9.85 g, yield: 50%).

MS[M+H] ⁺ = 690

Preparation Example 2

Compound 2-(4-bromophenyl)-5-(naphthalen-1-yl)furan (7.11 g, 20.37 mmol) and compound a2 (8.45 g, 21.39 mmol) were mixed in Xylene (240 mL) in a 500 mL round bottom flask under a nitrogen atmosphere. ), NaOtBu (2.94 g, 30.56 mmol) was added, Bis(tri- tert -butylphosphine) palladium(0) (0.10 g, 0.20 mmol) was added, and the mixture was heated and stirred for 5 hours. After lowering the temperature to room temperature and filtering to remove the base, Xylene was concentrated under reduced pressure and recrystallized with ethyl acetate (260 mL) to prepare Compound 2 (7.83 g, yield: 58%).

MS[M+H] ⁺ = 664

Preparation Example 3

Compound 2-([1,1'-biphenyl]-2-yl)-5-(4-bromophenyl)furan (9.34 g, 24.91 mmol) and compound a3 (8.34 g, 26.15 mmol) in Xylene (240 mL), NaOtBu (3.59 g, 37.36 mmol) was added, and Bis(tri- tert -butylphosphine) palladium(0) (0.13 g, 0.25 mmol) was added and heated for 4 hours. Stir. After lowering the temperature to room temperature and filtering to remove the base, Xylene was concentrated under reduced pressure and recrystallized with ethyl acetate (290 mL) to prepare compound 3 (9.37 g, yield: 61%).

MS[M+H] ⁺ = 614

Production Example 4

Compound 2-([1,1'-biphenyl]-3-yl)-5-(4-bromophenyl)furan (7.86 g, 20.96 mmol) and compound a4 (9.82 g, 22.01 mmol) in Xylene (230 mL), NaOtBu (3.02 g, 31.44 mmol) was added, and Bis(tri- tert -butylphosphine) palladium(0) (0.11 g, 0.21 mmol) was added and heated for 4 hours. Stir. After lowering the temperature to room temperature and filtering to remove the base, Xylene was concentrated under reduced pressure and recrystallized with ethyl acetate (310 mL) to prepare compound 4 (7.62 g, yield: 55%).

MS[M+H] ⁺ = 740

Preparation Example 5

Compound 2-([1,1'-biphenyl]-4-yl)-5-(4-bromophenyl)furan (6.95 g, 18.53 mmol) and compound a5 (9.63 g, 19.46 mmol) in Xylene (260 mL), NaOtBu (2.67 g, 27.80 mmol) was added, and Bis(tri- tert -butylphosphine) palladium(0) (0.09 g, 0.19 mmol) was added and heated for 6 hours. Stir. After lowering the temperature to room temperature and filtering to remove the base, Xylene was concentrated under reduced pressure and recrystallized with ethyl acetate (260 mL) to prepare Compound 5 (8.82 g, yield: 67%).

MS[M+H] ⁺ = 790

Preparation Example 6

After completely dissolving compound 4-(4-bromophenyl)-2-phenylfuran (8.11 g, 27.21 mmol) and compound a6 (12.30 g, 29.94 mmol) in Xylene (240 mL) in a 500 mL round bottom flask under a nitrogen atmosphere, NaOtBu ( 3.92 g, 40.82 mmol) was added, and Bis(tri- tert -butylphosphine) palladium(0) (0.28 g, 0.54 mmol) was added, followed by heating and stirring for 4 hours. After lowering the temperature to room temperature and filtering to remove the base, Xylene was concentrated under reduced pressure and recrystallized with ethyl acetate (210 mL) to prepare compound 6 (10.04 g, yield: 59%).

MS[M+H] ⁺ = 628

Preparation Example 7

Compound 2-(4-bromophenyl)-5-(naphthalen-1-yl)thiophene (6.88 g, 18.90 mmol) and compound a7 (9.09 g, 20.79 mmol) were mixed in Xylene (260 mL) in a 500 mL round bottom flask under a nitrogen atmosphere. ), NaOtBu (2.72 g, 28.35 mmol) was added, Bis(tri- tert -butylphosphine) palladium(0) (0.19 g, 0.38 mmol) was added, and the mixture was heated and stirred for 4 hours. After lowering the temperature to room temperature and filtering to remove the base, Xylene was concentrated under reduced pressure and recrystallized with ethyl acetate (230 mL) to prepare compound 7 (8.64 g, yield: 68%).

MS[M+H] ⁺ = 710

Preparation Example 8

Compound 2-([1,1'-biphenyl]-3-yl)-5-(4-bromophenyl)thiophene (9.22 g, 23.64 mmol) and compound a8 (10.80 g, 24.82 mmol) in Xylene (250 mL), NaOtBu (3.41 g, 35.46 mmol) was added, and Bis(tri- tert -butylphosphine) palladium(0) (0.12 g, 0.24 mmol) was added and heated for 5 hours. Stir. After lowering the temperature to room temperature and filtering to remove the base, Xylene was concentrated under reduced pressure and recrystallized with ethyl acetate (310 mL) to prepare Compound 8 (11.19 g, yield: 63%).

MS[M+H] ⁺ = 746

Preparation Example 9

Compound 2-([1,1'-biphenyl]-3-yl)-5-(4-bromophenyl)thiophene 1,1-dioxide (8.82 g, 20.90 mmol) and compound a9 were added to a 500 mL round bottom flask under a nitrogen atmosphere. (9.20 g, 21.95 mmol) was completely dissolved in Xylene (230 mL), NaOtBu (3.01 g, 31.35 mmol) was added, and Bis ( tritert -butylphosphine) palladium (0) (0.11 g, 0.21 mmol) was added. After heating and stirring for 4 hours. After lowering the temperature to room temperature and filtering to remove the base, Xylene was concentrated under reduced pressure and recrystallized with tetrahydrofuran (250 mL) to prepare compound 9 (9.64 g, yield: 61%).

MS[M+H] ⁺ = 762

Example 1

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1,000 Å was put in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a Fischer Co. product was used as the detergent, and distilled water filtered through a second filter of a Millipore Co. product was used as the 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.

A mixture of compound HI1 and compound HI2 was thermally vacuum deposited to a thickness of 100 Å in a ratio of 98:2 (molar ratio) on the ITO transparent electrode prepared as described above to form a hole injection layer. A hole transport layer was formed by vacuum depositing a compound (1150 Å) represented by Chemical Formula HT1 on the hole injection layer. Subsequently, an electron blocking layer was formed by vacuum depositing Compound 1 prepared in Preparation Example 1 to a film thickness of 50 Å on the hole transport layer. Subsequently, the following compound BH and the following compound BD were vacuum-deposited in a weight ratio of 25:1 to a film thickness of 200 Å on the electron blocking layer to form a light emitting layer. A hole blocking layer was formed by vacuum depositing the following compound HB1 to a film thickness of 50 Å on the light emitting layer. Subsequently, the following compound ET1 and the following compound LiQ were vacuum deposited at a weight ratio of 1:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 310 Å. A negative electrode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7 Å / sec, the deposition rate of lithium fluoride on the cathode was 0.3 Å / sec, and the deposition rate of aluminum was 2 Å / sec, and the vacuum degree during deposition was 2 × 10 ^-7 Maintaining ~ 5ⅹ10 ^-6 torr, an organic light emitting device was manufactured.

Examples 2 to 9

An organic light emitting device was manufactured in the same manner as in Example 1, except that the compound shown in Table 1 was used instead of Compound 1 of Preparation Example 1.

Comparative Examples 1 to 4

An organic light emitting device was manufactured in the same manner as in Example 1, except that the compound shown in Table 1 was used instead of Compound 1 of Preparation Example 1. Compounds EB2, EB3, EB4 and EB5 used in Table 1 are as follows.

Experimental example

When a current of 10 mA/cm ² was applied to the organic light emitting devices prepared in Examples and Comparative Examples, voltage, efficiency, color coordinates, and lifetime were measured, and the results are shown in Table 1 below. T95 means the time required for the luminance to decrease from the initial luminance (1600 nit) to 95%.

compound
(electron suppression layer) Voltage
(V@10mA/cm ² ) efficiency
(cd/A@10mA/cm ² ) color coordinates
(x,y) T95
(hr@10mA/cm ² ) Example 1 compound 1 4.21 6.85 (0.146, 0.046) 275 Example 2 compound 2 4.23 6.76 (0.146, 0.045) 260 Example 3 compound 3 4.22 6.77 (0.147, 0.047) 285 Example 4 compound 4 4.24 6.89 (0.146, 0.046) 260 Example 5 compound 5 4.26 6.71 (0.145, 0.045) 275 Example 6 compound 6 4.38 6.83 (0.145, 0.045) 255 Example 7 compound 7 4.39 6.44 (0.147, 0.044) 240 Example 8 compound 8 4.37 6.46 (0.147, 0.045) 245 Example 9 compound 9 4.52 6.55 (0.146, 0.045) 230 Comparative Example 1 Compound EB2 4.90 6.13 (0.147, 0.046) 175 Comparative Example 2 Compound EB3 4.85 6.29 (0.146, 0.045) 185 Comparative Example 3 Compound EB4 5.46 5.81 (0.145, 0.046) 75 Comparative Example 4 Compound EB5 5.51 5.95 (0.147, 0.045) 90

As shown in Table 1, the organic light emitting device using the compound of the present invention as an electron blocking layer exhibited excellent characteristics in terms of efficiency, driving voltage and stability of the organic light emitting device.

In Examples 1 to 9, it was found that low voltage, high efficiency, and long lifespan were exhibited when a material in which an amine containing thiophene and furan substituted with an aryl group was connected to position 2 of the triphenylene core was used as an electron blocking layer.

Comparative Examples 1 and 2 use materials of EB2 and EB3 in which spirobifluorenyl-substituted amine is connected to position 2 of the Triphenylene Core in the electron suppression layer, thereby demonstrating one embodiment of the present invention in terms of driving voltage, efficiency and lifetime. showed inferior characteristics than the example.

In Comparative Examples 3 and 4, materials of EB4 and EB5 containing two triphenylenyls as amine substituents were used in the electron blocking layer, and the charge balance collapsed, resulting in a voltage increase, a decrease in efficiency, and especially stability than the compounds of the present invention. showed poor characteristics.

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

Claims (8)

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

In Formula 1,
X is O, S, or SO ₂ ;
Ar ₁ is phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, dimethylfluorenyl, naphthyl phenyl, or phenanthrenyl phenyl;
Ar ₂ is a substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,
L ₁ and L ₂ are each independently a single bond; Or a substituted or unsubstituted C _6-60 arylene.
According to claim 1,
Formula 1 is represented by any one of the following Formulas 1-1 to 1-4,
compound:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formula 1-1 to Formula 1-4,
Descriptions of X, Ar ₁ , Ar ₂ , L ₁ and L ₂ are as defined in claim 1.
According to claim 1,
Ar ₁ is any one selected from the group consisting of
compound:

.
According to claim 1,
Ar ₂ is phenyl, biphenylyl, or naphthyl;
compound.
According to claim 1,
L ₁ is a single bond, phenylene, or biphenylylene;
compound.
According to claim 1,
L ₂ is a single bond, phenylene, or biphenylylene;
compound.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
compound:

.
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 according to any one of claims 1 to 7. doing,
organic light emitting device.

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