WO2020185038A1 - Novel compound and organic light emitting device using same - Google Patents

Abstract

The present invention provides: a novel compound represented by chemical formula 1, which is contained in an organic layer of an organic light emitting device and can bring improved efficiency, low driving voltage, and/or improved service life characteristics of the organic light emitting device; and an organic light emitting device comprising same.

Description

Novel compound and organic light emitting device using the same

Cross-reference with related application(s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0029507 filed March 14, 2019 and Korean Patent Application No. 10-2020-0030982 filed March 12, 2020. All contents disclosed in the literature are included as part of this specification.

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

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

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, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of such an 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 layer, and excitons are formed when the injected holes and electrons meet. It glows when it falls back to the ground.

Development of new materials for organic materials used in organic light emitting devices as described above is continuously required.

Prior art literature

Patent Literature

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

The present invention relates to an organic light-emitting device comprising the novel compound.

The present invention provides a compound represented by the following formula 1:

[Formula 1]

In Formula 1,

L is a direct bond, or a substituted or unsubstituted C _6-60 arylene,

A is a substituted or unsubstituted carbazolyl,

X ₁ , X ₂ and X ₃ are each independently N, or CH, provided that at least one of X ₁ , X ₂ , and X ₃ is N,

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _5-60 including at least one hetero atom selected from the group consisting of N, O and S Is heteroaryl.

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 comprises the compound of the present invention.

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

1 shows an example of an organic light emitting device comprising 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 injection layer (5), a hole transport layer (6), an electron suppression layer (7), a light emitting layer (3), an electron transport layer (8), an electron injection layer (9). And an example of an organic light-emitting device including the cathode 4 is shown.

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

(Explanation of terms)

In this specification,

Means a bond connected to another substituent.

In the present specification, the term "substituted or unsubstituted" refers to 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; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O, and S atoms, or substituted or unsubstituted with two or more substituents connected among the above exemplified substituents. . For example, "a substituent to which two or more substituents are connected" 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 connected.

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but it 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 oxygen of the ester group with a straight chain, 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 number of carbon atoms of the imide group is not particularly limited, but it 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 trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.

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

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

In the present specification, the alkyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. 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, cycloheptylmethyl, 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, and the like, but are not limited thereto.

In the present specification, the alkenyl group may be a linear or branched chain, and the number of carbon atoms 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, 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, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but is preferably 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 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, 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 is preferably 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. The aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a 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. When the fluorenyl group is substituted,

Etc. However, it is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group including at least one of O, N, Si and S as a heterogeneous element, and the number of carbons is not particularly limited, but it is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group , Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , Carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl Group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, but are not limited thereto.

In the present specification, the aryl group among the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the example 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 example of the aforementioned alkyl group. In the present specification, for heteroaryl among heteroarylamines, the description of the aforementioned heterocyclic group may be applied. In the present specification, the alkenyl group of the aralkenyl group is the same as the example 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 aforementioned heterocyclic group 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 the cycloalkyl group described above may be applied except that the hydrocarbon ring is formed by bonding of two substituents. In the present specification, the heterocycle is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that two substituents are bonded to each other.

(compound)

The present invention provides a compound represented by the following formula 1:

[Formula 1]

In Formula 1,

L is a direct bond, or a substituted or unsubstituted C _6-60 arylene,

A is a substituted or unsubstituted carbazolyl,

X ₁ , X ₂ , and X ₃ are each independently N, or CH, provided that at least one of X ₁ , X ₂ , and X ₃ is N,

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _5-60 including at least one hetero atom selected from the group consisting of N, O and S Is heteroaryl.

Meanwhile, in Formula 1, L, A, Ar ₁ and Ar ₂ may be substituted or unsubstituted with deuterium.

Meanwhile, in Chemical Formula 1, carbon represented by * means that only hydrogen is substituted and does not include an additional substituent on the carbon.

Preferably, the compound represented by Formula 1 may be a compound represented by Formula 2 or Formula 3:

[Formula 2]

[Formula 3]

In Formula 2 or 3,

L, X ₁ , X ₂ , X ₃ , Ar ₁ , and Ar ₂ are as previously defined,

R ₁ is each independently hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _6-60 aryl, or at least one hetero atom selected from the group consisting of N, O and S It is a substituted or unsubstituted C _5-60 heteroaryl containing,

R ₂ is substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _6-60 aryl,

R ₃ is hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _6-60 aryl, or substituted containing one or more heteroatoms selected from the group consisting of N, O and S Or unsubstituted C _5-60 heteroaryl,

m is an integer from 0 to 8,

n is an integer from 0 to 7.

Meanwhile, in Formula 2 or 3, when R ₁ and R ₃ are not hydrogen or deuterium, they may each independently be substituted or unsubstituted with one or more deuterium, and R ₂ may be substituted or unsubstituted with one or more deuterium. I can.

Preferably, X ₁ , X ₂ and X ₃ may all be N.

Preferably, L may be a direct bond, phenylene or biphenylylene, and each of the phenylene or biphenylylene may be independently substituted or unsubstituted with one or more deuterium.

Preferably, Ar ₁ and Ar ₂ are each independently, phenyl, biphenylyl, terphenylyl, dimethylfluorenyl, naphthyl, phenanthrenyl, triphenylenyl, dibenzofuranyl, dibenzothiophenyl, Carbazol-9-yl, 9-phenyl-9H-carbazolyl, benzoxazolyl, benzothiazolyl, 2-phenylbenzoxazolyl or 2-phenylbenzothiazolyl, each independently substituted with one or more deuterium Or can be unsubstituted.

Preferably, R ₁ may each independently be hydrogen, deuterium, phenyl, dibenzofuranyl, dibenzothiophenyl, or carbazolyl, and the phenyl, dibenzofuranyl, dibenzothiophenyl, or carbazolyl Each of is independently substituted or unsubstituted with one or more deuterium.

When R ₁ is deuterium, preferably m may be 8,

When R ₁ is not deuterium, preferably m may be an integer of 0 to 2.

Preferably, R ₂ may each independently be phenyl substituted or unsubstituted with one or more deuterium.

Preferably, R ₃ may each independently be hydrogen, deuterium, phenyl, dibenzofuranyl, dibenzothiophenyl, or carbazolyl, and the phenyl, dibenzofuranyl, dibenzothiophenyl, or carbazolyl Each of is independently substituted or unsubstituted with one or more deuterium.

When R ₃ is deuterium, preferably n may be 8,

When R ₃ is not deuterium, preferably n may be an integer of 0 to 2.

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

.

The compound represented by Formula 1 according to the present invention has high thermal stability due to the structural characteristics of triphenylene having a high glass transition temperature, and a carbazole-based substituent having hole transport characteristics and a triazine-based substituent having electron transport characteristics (pyripine , Pyrimidine, and triazine) are adjacent to each other in ortho positions, so that intra charge transfer can be easily performed. For this reason, the stability of the molecule is high, and it is advantageous for both hole and electron transport. In addition, since various aryl groups and heterocycles are additionally substituted in Ar ₁ and Ar ₂ of Formula 1 to variously control electron transport properties, it is advantageous to balance charge according to the change of the common layer.

Accordingly, it is applied to the compound organic light-emitting device represented by Formula 1 according to the present invention to have high efficiency, low driving voltage, and long life.

The compound represented by Formula 1 can be prepared through the following Reaction Scheme A-1 or Scheme A-2.

[Scheme A-1]

[Scheme A-2]

In the above Schemes A-1 and A-2, X is halogen, specifically bromo, chloro, iodo. Definitions for other substituents are as described above.

Reaction Schemes A-1 and A-2 include a Suzuki coupling reaction and an amine substitution reaction, and the reaction is preferably carried out in the presence of a palladium catalyst and a base. In addition, the reactor, catalyst, solvent, etc. used for the reaction can be changed to suit the desired product. The method for preparing the compound of Formula 1 may be more specific in Preparation Examples to be described later.

(Organic light emitting device)

The present invention provides an organic light-emitting device including the compound represented by Chemical Formula 1. For 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 a compound represented by 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-emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, an electron suppression layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

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, a hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 above. Including the indicated compound.

In addition, the organic material layer may include an electron suppressing layer, and the electron suppressing layer includes the compound represented by Formula 1 above.

In addition, the organic material layer may include an emission layer, and the emission layer includes the compound represented by Chemical Formula 1.

In addition, the organic material layer may include an electron transport layer, an electron injection layer, or a layer for simultaneous electron transport and electron injection, and the electron transport layer, an electron injection layer, or a layer for simultaneous electron transport and electron injection is represented by the formula It includes the compound represented by 1.

In addition, the organic material layer includes a hole injection layer, a hole transport layer, an electron suppression layer, and an emission layer, and at least one selected from the group consisting of the hole injection layer, the hole transport layer, and the electron suppression layer is a compound represented by Formula 1 It may include.

In addition, the organic light emitting device according to the present invention may be an organic light emitting device having a structure (normal type) 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 inverted type organic light emitting device 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 comprising a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. In such a structure, the compound represented by Formula 1 may be included in the emission layer.

2 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron suppression layer (7), a light emitting layer (3), an electron transport layer (8), an electron injection layer (9). And an example of an organic light-emitting device including the cathode 4 is shown. In such a structure, the compound represented by Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the electron suppression layer, the light-emitting layer, the electron transport layer, and the electron injection layer.

The organic light-emitting device according to the present invention may be manufactured by materials and methods known in the art, except that at least one of the organic material layers includes the compound represented by Chemical Formula 1. 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, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. 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 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 refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

In addition to such a method, an organic light-emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.

For example, the first electrode is an anode, 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 large work function is preferable so that holes can be smoothly injected into the organic material 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); A combination of a metal and an oxide such as ZnO:Al or SNO ₂ :Sb; Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole 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 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 that injects holes from an electrode, and has the ability to transport holes as a hole injection material, so that it has a hole injection effect at the anode, an excellent hole injection effect for a light emitting layer or a light emitting material. A compound that prevents the movement of excitons to the electron injection layer or the electron injection material and has excellent ability to form a thin film is preferable. It is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Organic substances, anthraquinone, 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 holes to the light emitting layer.As a hole transport material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer and having high mobility for holes This is suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer including a conjugated portion and a non-conjugated portion, but are not limited thereto.

The electron-suppression layer is a layer between the hole-transport layer and the light-emitting layer in order to prevent electrons injected from the cathode from passing over to the hole-transport layer without being recombined in the light-emitting layer, and is also called an electron-blocking layer. The electron-suppressing layer is preferably a material having less electron affinity than the electron transport layer.

As the light-emitting material, a material capable of emitting light in a visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency against fluorescence or phosphorescence is preferable. Specific examples of 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole, and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The emission layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group, and the styrylamine compound is substituted or unsubstituted As a compound in which at least one arylvinyl group is substituted on the arylamine, one or two or more substituents selected from the group consisting of an aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are 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 emission layer. As an electron transport material, a material capable of receiving electrons from the cathode and transferring them to the emission layer is suitable. Do. Specific examples include Al complex 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 that have a low work function and are followed by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium, and samarium, and in each case an aluminum layer or a silver layer follows.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer A compound that prevents migration to the layer and has excellent thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, preorenylidene methane, anthrone, etc. Complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include lithium 8-hydroxyquinolinato, 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)( o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is 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-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 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 for illustrating the present invention, and the scope of the present invention is not limited thereto.

[Synthesis Example]

Synthesis Example 1: Synthesis of Compound 1

Step 1) Synthesis of Compound 1-a

In a nitrogen atmosphere, 4-bromo-chloro-2-iodoaniline (50 g, 150.4 mmol) and [1,1'-biphenyl]-2-yl boronic acid (29.8 g, 150.4 mmol) were added to 1000 ml of tetrahydrofuran. Into the mixture was stirred and refluxed. Thereafter, sodium carbonate (47.8 g, 451.3 mmol) was dissolved in 48 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (5.2 g, 4.5 mmol) was added. After 2 hours reaction, the mixture was allowed to cool to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 1079 mL of 20 times chloroform to dissolve it, and after washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and hexane to prepare a brown solid compound 1-a (43.2g, 80%, MS: [M+H]+ = 359.7).

Step 2) Synthesis of Compound 1-b

Compound 1-a (40 g, 111.5 mmol) was added to hydrochloric acid (2 M, 700 mL), stirred at 0° C. for about 15 minutes, and sodium nitrite (8.5 g, 122.6 mmol) was slowly added. After 1 hour, the mixture was heated at 60° C. for 3 hours, cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 800 mL of 20 times chloroform to dissolve it, and after washing twice with an aqueous sodium hydrogen carbonate solution, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and hexane to prepare a dark brown solid compound 1-b (27.4g, 72%, MS: [M+H]+ = 342.0).

Step 3) Synthesis of Compound 1-c

In a nitrogen atmosphere, 1-b (25 g, 73.3 mmol) and bis (pinacolato) diboron (18.6 g, 73.3 mmol) were added to 500 ml of Diox, and stirred and refluxed. Thereafter, tri-potassium phosphate (46.7 g, 219.9 mmol) was added and sufficiently stirred, and then palladium dibenzylidene acetone palladium (1.3 g, 2.2 mmol) and tricyclohexylphosphine (1.2 g, 4.4 mmol) were added. After reaction for 3 hours, the organic layer was allowed to cool to room temperature, and the organic layer was filtered to remove salts, and the filtered organic layer was distilled. This was again added to 285 mL of 10 times chloroform to dissolve it, and after washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethanol to prepare a brown solid compound 1-c (22.8g, 80%, MS: [M+H]+ = 389.7).

Step 4) Synthesis of compound 1-d

In a nitrogen atmosphere, 1-c (20 g, 51.5 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (13.8 g, 51.5 mmol) were added to 400 ml of tetrahydrofuran, stirred and refluxed. I did. Thereafter, sodium carbonate (16.4 g, 154.4 mmol) was dissolved in 16 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (1.8 g, 1.5 mmol) was added. After 1 hour reaction, the mixture was allowed to cool to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 554 mL of 20 times chloroform to dissolve it, and after washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare a yellow solid compound 1-d (19.1g, 69%, MS: [M+H]+ = 539.5).

Step 5) Synthesis of compound 1

In a nitrogen atmosphere, 1-d (18 g, 33.4 mmol) and 9H-carbazole (5.6 g, 33.4 mmol) were added to 360 ml of xylene, followed by stirring and refluxing. Thereafter, sodium tertiary-butoxide (9.6 g, 100.3 mmol) was added and sufficiently stirred, and then bis (tri tertiary-butylphosphine) palladium (0.5 g, 1 mmol) was added. After reacting for 1 hour, the organic layer was allowed to cool to room temperature, and the organic layer was filtered to remove salts, and the filtered organic layer was distilled. This was again added to 10 times 209 mL of chloroform to dissolve it, and after washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through a silica column using chloroform and ethyl acetate to prepare a yellow solid compound compound 1 (13.2g, 63%, MS: [M+H]+ = 625.8).

Synthesis Example 2: Synthesis of Compound 2

In Synthesis Example 1, 9H-carbazole was changed to 9H-carbazole-1,2,3,4,5,6,7,8-d8, except that the same production method as the production method of compound 1 As a result, compound 2 (MS: [M+H]+ = 633.8)) was prepared.

Synthesis Example 3: Synthesis of Compound 3

In Synthesis Example 1, 2-chloro-4,6-diphenyl-1,3,5-triazine was converted to 2-chloro-4-(phenanthren-9-yl)-6-phenyl-1,3,5- Compound 3 (MS[M+H] ⁺ = 725) was prepared in the same manner as in the preparation method of Compound 1, except that it was changed to triazine.

Synthesis Example 4: Synthesis of Compound 4

In Synthesis Example 1, 2-chloro-4,6-diphenyl-1,3,5-triazine to 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine Compound 4 (MS[M+H] ⁺ = 701) was prepared in the same manner as in the preparation method of Compound 1, except that the change was used.

Synthesis Example 5: Synthesis of Compound 5

In Synthesis Example 1, 2-chloro-4,6-diphenyl-1,3,5-triazine was converted to 2-chloro-4-(dibenzo[b,d]thiophen-4-yl)-6-phenyl Compound 5 (MS[M+H] ⁺ = 731) was prepared in the same manner as in the preparation method of Compound 1, except for changing to -1,3,5-triazine and used.

Synthesis Example 6: Synthesis of Compound 6

In Synthesis Example 1, 2-chloro-4,6-diphenyl-1,3,5-triazine and 9H-carbazole were mixed with 2 9-(4-chloro-6-phenyl-1,3,5-triazine. -2-yl)-9H-carbazole and 9H-carbazole-1,2,3,4,5,6,7,8-d8, except that the change was used, the same as the preparation method of compound 1 Compound 6 (MS[M+H] ⁺ = 722) was prepared by the method.

Synthesis Example 7: Synthesis of Compound 7

Step 1) Synthesis of compound 7-d

In Synthesis Example 1, 2-chloro-4,6-diphenyl-1,3,5-triazine to 2-chloro-4-phenyl-6-(phenyl-d5)-1,3,5-triazine Compound 7-d (MS[M+H] ⁺ = 543) was prepared in the same manner as in the preparation method of compound 1-d, except that the change was used.

Step 2) Synthesis of compound 7

In a nitrogen atmosphere, 7-d (15 g, 27.6 mmol) and (9-phenyll-9H-carbazol-3-yl) boronic acid (7.9 g, 27.6 mmol) were added to 300 ml of tetrahydrofuran, followed by stirring and refluxing. Thereafter, sodium carbonate (8.8 g, 82.8 mmol) was dissolved in 9 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (1 g, 0.8 mmol) was added. After 1 hour reaction, the mixture was allowed to cool to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 390 mL of 20 times chloroform to dissolve it, and after washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare a white solid compound 7 (10.9g, 56%, MS: [M+H] ⁺ = 706.9).

Synthesis Example 8: Synthesis of Compound 8

In Synthesis Example 7, 2-chloro-4-phenyl-6-(phenyl-d5)-1,3,5-triazine was converted to 2-chloro-4-(dibenzo[b,d]furan-3-yl)- Compound 8 (MS[M+H] ⁺ = 791) was prepared in the same manner as in the preparation method of Compound 7, except that it was changed to 6-phenyl-1,3,5-triazine.

[Example]

Example 1

A glass substrate coated with a thin film of 1,400 Å of ITO (Indium Tin Oxide) was put in distilled water dissolved in a detergent and washed with ultrasonic waves. In this case, Fischer Co. product was used as a detergent, and distilled water secondarily filtered with a filter made by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

On the thus prepared ITO transparent electrode, the following HT-A compound and the following PD compound were thermally vacuum deposited to a thickness of 100 Å at a weight ratio of 95:5, and then only the following HT-A compound was deposited to a thickness of 1150 Å to form a hole transport layer. Formed. On the hole transport layer, the following HT-B compound was thermally vacuum deposited to a thickness of 450 Å to form an electron blocking layer (electron inhibiting layer). On the electron blocking layer, the compound 1 prepared above and the following GD compound were vacuum-deposited at a weight ratio of 85:15 to a thickness of 400 Å to form a light emitting layer. On the light emitting layer, the following ET-A compound was vacuum deposited to a thickness of 50 Å to form a hole blocking layer. On the hole blocking layer, the following ET-B compound and the following Liq compound were thermally vacuum deposited to a thickness of 250 Å at a weight ratio of 2:1, and then LiF and magnesium were vacuum deposited to a thickness of 30 Å at a weight ratio of 1:1. Thus, an electron transport and injection layer was formed. On the electron injection layer, magnesium and silver were deposited to a thickness of 160 Å in a weight ratio of 1:4 to form a cathode, thereby fabricating an organic light-emitting device.

In the above process, the deposition rate of organic matter was maintained at 0.4~0.7Å/sec, the deposition rate of lithium fluoride at the cathode was 0.3 Å/sec, and the deposition rate of silver and magnesium was 2 Å/sec. An organic light-emitting device was manufactured by maintaining ×10 ^-7 to 5 × 10 ^-6 torr.

Examples 2 to 10 and 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 below was used instead of Compound 1 in Example 1.

For reference, in Examples 9 to 10 and Comparative Examples 3 to 4, an organic light-emitting device was manufactured using the compound shown in Table 1 in place of Compound 1 in a weight ratio of 1:1. For example, in Example 8, instead of Compound 1 in Example 1, Compound 1 and Compound H-2 were used in a weight ratio of 1:1. In Table 1 below, compounds H-2, C1, and C2 are as follows, respectively.

Experimental example

Voltage, efficiency, and lifetime (T95) were measured by applying a current to the organic light-emitting devices manufactured in the above Examples and Comparative Examples, and the results are shown in Table 1 below. At this time, voltage and efficiency were measured by applying a current density of 10 mA/cm ² . In addition, T95 in Table 1 below means the time measured until the initial luminance decreases to 95% at a current density of 20 mA/cm ² .

division	Light-emitting layer compound	Voltage(V)(@10mA/cm 2 )	Efficiency (cd/A)(@10mA/cm 2 )	Luminous color	T95(@20mA/cm 2 )
Example 1	Compound 1	3.01	65.9	green	77
Example 2	Compound 2	3.00	65.8	green	87
Example 3	Compound 3	3.06	66.6	green	75
Example 4	Compound 4	2.97	67.2	green	72
Example 5	Compound 5	3.00	66.3	green	76
Example 6	Compound 6	3.06	66.1	green	99
Example 7	Compound 7	3.02	65.0	green	70
Example 8	Compound 8	2.98	65.9	green	75
Example 9	Compound 1, Compound H-2	3.11	70.0	green	85
Example 10	Compound 8, Compound H-2	3.17	72.5	green	80
Comparative Example 1	Compound C1	3.05	67.1	green	60
Comparative Example 2	Compound C2	3.06	66.0	green	57
Comparative Example 3	Compound C1, Compound H-2	3.12	78.5	green	76
Comparative Example 4	Compound C2, Compound H-2	3.20	79.2	green	70

Examples 1 to 8 and Comparative Examples 1 to 2 are device examples in which a single host is used for the light emitting layer. In the compound of Formula 1, since the carbazole-based substituent having hole transport characteristics and the triazine-based substituent having electron transport characteristics are adjacent to each other at an ortho position, intra charge transfer can be easily performed. For this reason, the stability of the molecule is high, and it is advantageous for both hole and electron transport. In addition, since various aryl groups and heterocycles are additionally substituted in Ar ₁ and Ar ₂ of Formula 1 to variously control electron transport properties, it is advantageous to balance charge according to the change of the common layer.

Examples 9 to 10 are device examples in which two types of hosts are used for the light emitting layer. Even when two types of hosts are used for the light emitting layer, it can be seen that the devices of Examples 9 to 10 using the compound of the present invention have higher efficiency than the devices of Comparative Examples 3 to 4, and in particular, the lifespan characteristics are significantly improved. have.

Therefore, as shown in Table 1, when the compound of Formula 1 is used as a host of an organic light emitting device, it can be seen that the characteristics of low voltage, high efficiency, and long life are exhibited.

Explanation of sign

1: substrate 2: anode

3: light emitting layer 4: cathode

5: hole injection layer 6: hole transport layer

7: electron suppression layer 8: electron transport layer

9: electron injection layer

Claims (10)

1. Compound represented by the following formula 1:

   [Formula 1]

   

   In Formula 1,

   L is a direct bond, or a substituted or unsubstituted C _6-60 arylene,

   A is a substituted or unsubstituted carbazolyl,

   X ₁ , X ₂ and X ₃ are each independently N, or CH, provided that at least one of X ₁ , X ₂ and X ₃ is N,

   Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _5-60 including at least one hetero atom selected from the group consisting of N, O and S Is heteroaryl.
2. The method of claim 1,

   The compound represented by Formula 1 is a compound represented by Formula 2 or 3 below:

   [Formula 2]

   

   [Formula 3]

   

   In Formula 2 or 3,

   L, X ₁ , X ₂ , X ₃ , Ar ₁ , and Ar ₂ are as defined in claim 1,

   R ₁ is each independently hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _6-60 aryl, or at least one hetero atom selected from the group consisting of N, O and S It is a substituted or unsubstituted C _5-60 heteroaryl containing,

   R ₂ is substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _6-60 aryl,

   R ₃ is hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, substituted or unsubstituted C _6-60 aryl, or substituted containing one or more heteroatoms selected from the group consisting of N, O and S Or unsubstituted C _5-60 heteroaryl,

   m is an integer from 0 to 8,

   n is an integer from 0 to 7.
3. The method of claim 1,

   X ₁ , X ₂ and X ₃ are all N, the compound.
4. The method of claim 1,

   L is a direct bond, phenylene or biphenylelene,

   The phenylene or biphenylylene is each independently substituted or unsubstituted with one or more deuterium, a compound.
5. The method of claim 1,

   Ar ₁ and Ar ₂ are each independently, phenyl, biphenylyl, terphenylyl, dimethylfluorenyl, naphthyl, phenanthrenyl, triphenylenyl, dibenzofuranyl, dibenzothiophenyl, carbazole-9 -Yl, 9-phenyl-9H-carbazolyl, benzoxazolyl, benzothiazolyl, 2-phenylbenzoxazolyl or 2-phenylbenzothiazolyl,

   These are each independently substituted or unsubstituted with one or more deuterium, a compound.
6. The method of claim 2,

   Each R ₁ is independently hydrogen, deuterium, phenyl, dibenzofuranyl, dibenzothiophenyl, or carbazolyl,

   The phenyl, dibenzofuranyl, dibenzothiophenyl, or carbazolyl are each independently substituted or unsubstituted with one or more deuterium, a compound.
7. The method of claim 2,

   Each R ₂ is independently, one or more deuterium substituted or unsubstituted phenyl.
8. The method of claim 2,

   Each R ₃ is independently hydrogen, deuterium, phenyl, dibenzofuranyl, dibenzothiophenyl, or carbazolyl,

   The phenyl, dibenzofuranyl, dibenzothiophenyl, or carbazolyl is substituted or unsubstituted with one or more deuterium.
9. The method of claim 1,

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

   

   

   

   

   

   

   

   

   

   

   

   

   

   .
10. 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 9 That is, an organic light-emitting device.

Images