KR102103505B1 - Novel hetero-cyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

Novel hetero-cyclic compound and organic light emitting device comprising the same}

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

In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies have been 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. In order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often formed of a multi-layered structure composed of different materials, for example, 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. When a voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected at the anode, and electrons are injected at the cathode, and an exciton is formed when the injected holes meet the electrons. When it falls to the ground again, it will shine.

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

Korean Patent Publication No. 10-2000-0051826

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

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

[Formula 1]

In Chemical Formula 1,

Y ₁ and Y ₂ are each independently hydrogen; Substituted or unsubstituted C _1-40 alkyl; Substituted or unsubstituted C _6-60 aryl; Or a substituted or unsubstituted C _2-60 heteroaryl containing one or more of O, N, Si and S,

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl; C _2-60 heteroaryl containing one or more of substituted or unsubstituted O, N, Si, and S, or Ar ₁ or Ar ₂ combines with adjacent groups to form a condensed ring,

X ₁ to X ₃ are each independently N or CR ', provided that at least one of them is N,

R 'is hydrogen; Or substituted or unsubstituted C _1-60 alkyl,

L are each independently a direct bond; Substituted or unsubstituted C _6-60 arylene; Or C _2-60 heteroarylene comprising any one or more hetero atoms selected from the group consisting of N, O, S and Si,

R ₁ to R ₃ are each independently halogen; Timing; Cyano, nitrile; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Or a substituted or unsubstituted C _2-60 heteroaryl containing one or more of O, N, Si and S,

m is 0 to 4,

n is 0 to 2,

o is 0 to 3,

z is 1 to 4, except that o + z is 4 or less.

In addition, the present invention is a first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including at least one layer of an organic material provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a compound represented by Chemical Formula 1, and provides an organic light emitting device. do.

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

FIG. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4.
Figure 2 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), hole control layer (7), light emitting layer (8), electron control layer (9), electron transport layer (10) And an example of an organic light-emitting device comprising the cathode 4.

Hereinafter, the present invention will be described in more detail to help understanding.

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

및

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

And

Means a linkage to another substituent.

The term "substituted or unsubstituted" in this specification is deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amino group; Phosphine oxide group; Alkoxy groups; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Aryl sulfoxyl group; Silyl group; Boron group; Alkyl groups; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; An alkenyl group; Alkyl aryl groups; Alkylamine groups; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups containing one or more of N, O and S atoms, or substituted or unsubstituted with two or more substituents among the exemplified substituents above . For example, "a substituent having two or more substituents" 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 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 oxygen of the ester group may be substituted 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 this 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 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 is specifically a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, a phenyl boron group, and the like, 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 straight chain or branched chain, and carbon number 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 are 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, and the like, 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 carbon number of the alkenyl group is 2 to 20. 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, steelbenyl group, styrenyl group, and the like, but are 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 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 is 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 one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number 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 combine with each other to form a spiro structure. When the fluorenyl group is substituted,

It can be back. However, it is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic 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 is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrol group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridil group , Pyridazine group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl 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, isooxazolyl group, tiadiia A sleepy group, a phenothiazinyl group and a dibenzofuranyl group, and the like, but are not limited thereto.

In the present specification, an aryl group in an aralkyl group, an alkenyl group, an alkylaryl group, and an arylamine group is the same as the exemplified aryl group described above. In the present specification, the alkyl group among the aralkyl group, alkylaryl group, and alkylamine group is the same as the above-described alkyl group. In the present specification, the description of the heteroaryl group among heteroarylamines may be applied. In the present specification, the alkenyl group in the alkenyl group is the same as the exemplified alkenyl group. In the present specification, the description of the aryl group described above may be applied, except that the arylene is a divalent group. In the present specification, the description of the heterocyclic group described above may be applied, except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and a description of the aryl group or cycloalkyl group described above may be applied, except that two substituents are formed by bonding. In the present specification, the heterocycle is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied, except that two substituents are formed by bonding.

Meanwhile, in Chemical Formula 1, Y ₁ and Y ₂ may be each independently methyl or phenyl.

In Chemical Formula 1, m, n and o may be 0.

In Chemical Formula 1, z may be 1.

The Chemical Formula 1 may be any one selected from compounds represented by the following Chemical Formulas 1-1 to 1-10.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

In Chemical Formulas 1-1 to 1-10,

L are each independently a direct bond; Substituted or unsubstituted C _6-60 arylene; Or C _2-60 heteroarylene comprising any one or more hetero atoms selected from the group consisting of N, O, S and Si,

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl; C _2-60 heteroaryl including one or more of substituted or unsubstituted O, N, Si, and S, or Ar ₁ or Ar ₂ may combine with adjacent groups to form a condensed ring.

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

Preferably, L may be any one selected from the group consisting of each independently.

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

The compound represented by Chemical Formula 1 may be prepared by, for example, the following Reaction Schemes 1 and 2, respectively. The manufacturing method may be more specific in the manufacturing examples to be described later.

[Scheme 1]

[Scheme 2]

In Reaction Schemes 1 and 2, L, X ₁ , X ₂ , X ₃ , Ar ₁ , and Ar ₂ are as defined above.

In addition, the present invention provides an organic light emitting device comprising the compound represented by the formula (1). In one example, the present invention is a first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including at least one layer of an organic material provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a compound represented by Chemical Formula 1, and provides an organic light emitting device. 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 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 hole control layer, a light emitting layer, an electron control layer, an electron transport layer, an electron injection layer 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 layer is an electron transport layer; Electronic control layer; Electron injection layer; It may include a hole blocking layer or a light emitting layer, the electron transport layer; Electronic control layer; Electron injection layer; The hole blocking layer or the light emitting layer includes a compound represented by Chemical Formula 1 above.

Further, the organic material layer may include a light emitting layer, and the light emitting layer includes a compound represented by Chemical Formula 1.

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

In addition, the electron transport layer, the electron injection layer, or a layer that simultaneously performs electron transport and electron injection includes a compound represented by Chemical Formula 1.

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

Further, the organic light emitting device according to the present invention may be an organic light emitting device having a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. Further, 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 the organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.

FIG. 1 shows an example of an organic light emitting device including a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. In such a structure, the compound represented by Chemical Formula 1 may be included in the light emitting layer.

Figure 2 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), hole control layer (7), light emitting layer (8), electron control layer (9), electron transport layer (10) And an example of an organic light-emitting device comprising the cathode 4. In such a structure, the compound represented by Chemical Formula 1 may be included in one or more of the hole injection layer, hole transport layer, hole control layer, light emitting layer, electron control layer, and electron transport layer.

In addition, the organic light emitting device may further include a hole blocking layer or an electron injection layer, and the compound represented by Formula 1 may be included in the hole blocking layer or 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 layer of the organic material layer 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, a positive electrode is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. Then, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed thereon, and a material that can be used as a cathode is deposited thereon. In addition to this method, an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode 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 application method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, 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 a cathode material from a cathode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.

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

The positive electrode material is preferably a material having a large work function so that hole injection into the organic material layer is smooth. Specific examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of metal and oxide 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 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 is a multilayer structure material such as LiF / Al or LiO ₂ / Al, but is not limited thereto.

The hole injection material is a layer for injecting holes from an electrode, and the hole injection material has the ability to transport holes, and thus has a hole injection effect at an anode, an excellent hole injection effect for a light emitting layer or a light emitting material, and is produced in a light emitting layer A compound that prevents migration of the excited excitons to the electron injection layer or the electron injection 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 positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic matter, hexanitrile hexaazatriphenylene-based organic matter, quinacridone-based organic matter, and perylene-based Organic materials, anthraquinones, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that transports holes from the hole injection layer to the light emitting layer by receiving holes, and is a material that can transport holes to the light emitting layer by receiving holes from the anode or the hole injection layer as a hole transport material and has a high mobility for holes. This is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion, but are not limited thereto.

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

The light emitting layer may include a host material and a dopant material. The host material may be a condensed aromatic ring derivative or a heterocyclic compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic compounds include carbazole derivatives, dibenzofuran derivatives, and ladder types Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material 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 arylamino groups such as pyrene, anthracene, chrysene, periplanten, and the substituted or unsubstituted styrylamine compound. A compound in which at least one arylvinyl group is substituted with the arylamine, a substituent selected from 1 or 2 or more from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group is substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, examples of the metal complex include an iridium complex and a platinum complex, but are not limited thereto.

The electron transporting material is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. As the electron transporting material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer, a material having high mobility for electrons This is suitable. Specific examples include the Al complex of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited to these. 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 those that have a low work function and are followed by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an electron injection effect from a cathode, has an excellent electron injection effect on a light emitting layer or a 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 forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and their derivatives, metal Complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, 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-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, It is not limited to this.

The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a double-sided 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 the organic light emitting device.

Hereinafter, preferred embodiments are presented to help understanding of the invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto.

Manufacturing example  1-1

1) Synthesis of A1-1

(2,3-difluorophenyl) boronic acid (50.0g, 316.6mmol) and methyl-2-bromobenzoate (71.49g, 332.4mmol) were completely dissolved in dioxane (300ml) and then 2M potassium carbonate aqueous solution ( 150 ml) was added, tetrakistriphenyl-phosphino palladium (7.31 g, 2 mol%) was added, followed by stirring for 10 hours. After lowering the temperature to room temperature and terminating the reaction, the potassium carbonate aqueous solution was removed to separate the layers. After removing the solvent, the white solid was recrystallized from hexane to prepare A1-1 (62.87 g, yield 80%).

MS [M + H] ⁺ = 249.23

2) Synthesis of A2-1

A1-1 (30 g, 120.8 mmol), 4-chlorobenzene-1,2-diol (17.91 g, 124.8 mmol), and potassium carbonate (50.08 g, 362.4 mmol) were added to dimethylformamide (300 ml), followed by 3 Stirred for an hour. After lowering the temperature to room temperature and terminating the reaction, water was added, filtered, dissolved in chloroform and extracted, and then column with ethyl acetate and hexane to prepare A2-1 (12.7 g, yield 30%).

MS [M + H] ⁺ = 353.77

3) Synthesis of A2-2

A2-2 was prepared by synthesizing in the same manner as in the synthesis of A2-1.

MS [M + H] ⁺ = 353.77

Manufacturing example  1-2

1) Synthesis of B2-1

B2-1 was synthesized by the same method except that 3-chlorobenzene-1,2-diol was used instead of 4-chlorobenzene-1,2-diol in the synthesis of A2-1.

MS [M + H] ⁺ = 353.77

2) Synthesis of B2-2

B2-2 was prepared by synthesizing in the same manner as in the synthesis of B2-1.

MS [M + H] ⁺ = 353.77

Manufacturing example  2-1

1) Synthesis of A3-1

A2-1 (25 g, 70.86 mmol) was dissolved in tetrahydrofuran (325 mL) under a nitrogen atmosphere, and then stabilized and stirred at -10 ° C. 54 mL of 3.0M methyl magnesium bromide (162.4 mmol in diethyl ether) was slowly added dropwise over 30 minutes, and the reaction solution was heated to room temperature and stirred for 10 hours under a nitrogen atmosphere. After the reaction solution was cooled to 0, an aqueous solution of ammonium chloride (10.4 g, 194.85 mmol) dissolved in 100 mL of distilled water was slowly added thereto. The reaction solution was extracted with distilled water and diethyl ether, and the organic layer solution was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure to prepare A3-1.

2) Synthesis of A4-1

The prepared A3-1 was added to 325 mL of dichloromethane, dissolved, cooled to 0 ° C., and stirred. To this, boron trifluoride diethyl iserate (4 mL, 32.5 mmol) was slowly added for 10 minutes, heated to room temperature, and stirred for 12 hours. When the reaction is completed, an aqueous sodium bicarbonate solution is slowly added at 0 ° C and stirred for 30 minutes. The reaction solution was extracted with dichloromethane and the product was purified by silica column with dichloromethane and hexane to prepare A4-1 (23.72 g, yield 70%).

MS [M + H] ⁺ = 335.80

Manufacturing example  2-2: Synthesis of A3-2 and A4-2

In the synthesis of A3-1, A3-2 was prepared in the same manner, except that phenyl magnesium bromide was used instead of methyl magnesium bromide. In addition, A4-2 was synthesized by the same method except that A3-2 was used instead of A3-1 in the synthesis of A4-1.

MS [M + H] ⁺ = 459.94

Manufacturing example  2-3: Synthesis of A3-3 and A4-3

A3-3 was prepared by the same method except that A2-2 was used instead of A2-1 in the synthesis of A3-1. In addition, A4-2 was synthesized by the same method except that A3-3 was used instead of A3-1 in the synthesis of A4-1.

MS [M + H] ⁺ = 335.80

Manufacturing example  2-4: Synthesis of A3-4 and A4-4

In the synthesis of A3-3, A3-4 was prepared in the same manner, except that phenylmagnesium bromide was used instead of methylmagnesium bromide. In addition, A4-4 was synthesized by the same method except that A3-4 was used instead of A3-3 in the synthesis of A4-3.

MS [M + H] ⁺ = 459.94

Manufacturing example  3-1: Synthesis of A5-1

Compound A4-1 (20 g, 59.73 mmol), bis (pinacolato) diborone (15.92 g, 62.72 mmol), potassium acetate (11.4 g, 119.4 mmol) 1, 4-Dioxane (300 mL) was added, dibenzylidene acetone palladium (686 mg, 0.02 mol%) and tricyclohexylphosphine (645 mg, 0.04 mol%) were added under reflux and stirred for reflux for 12 hours. Upon completion of the reaction, the mixture is cooled to room temperature and filtered through Celite. After concentrating the filtrate under reduced pressure, chloroform was added to the residue, dissolved, washed with water to separate the organic layer, and dried over anhydrous magnesium sulfate. This was distilled under reduced pressure, and recrystallized with ethyl acetate to prepare A5-1 (21.38 g, yield 84%).

MS [M + H] ⁺ = 427.32

Manufacturing example  3-2: Synthesis of A5-2

In the synthesis of A5-1, A5-2 was synthesized by the same method, except that A4-2 was used instead of A4-1.

MS [M + H] ⁺ = 551.46

Manufacturing example  3-3: Synthesis of A5-3

In the synthesis of A5-1, A5-3 was prepared by synthesizing in the same manner, except that A4-3 was used instead of A4-1.

MS [M + H] ⁺ = 427.32

Manufacturing example  3-4: Synthesis of A5-4

In the synthesis of A5-1, A5-4 was synthesized by the same method except that A4-4 was used instead of A4-1.

MS [M + H] ⁺ = 551.46

Manufacturing example  3-5: Synthesis of B5-1

In the synthesis of A5-1, B5-1 was synthesized by the same method except that B4-1 was used instead of A4-1.

MS [M + H] ⁺ = 427.32

Manufacturing example  3-6: Synthesis of B5-2

In the synthesis of B5-1, B5-2 was synthesized by the same method except that B4-2 was used instead of B4-1.

MS [M + H] ⁺ = 551.46

Manufacturing example  3-7: Synthesis of B5-3

B5-3 was synthesized by the same method except that B4-3 was used instead of B4-1 in the synthesis of B5-1.

MS [M + H] ⁺ = 427.32

Manufacturing example  3-8: Synthesis of B5-4

B5-4 was synthesized by the same method except that B4-4 was used instead of B4-1 in the synthesis of B5-1.

MS [M + H] ⁺ = 551.46

Manufacturing example  4-1: Synthesis of Compound 1

The compound A5-1 (10.0g, 23.45mmol) and 2- (3-chlorophenyl) -4,6-diphenylpyrimidine (8.2g, 23.92mmol) were completely dissolved in tetrahydrofuran (300ml) and then 2M potassium. An aqueous carbonate solution (150 ml) was added, and tetrakistriphenyl-phosphino palladium (542 mg, 2 mol%) was added, followed by stirring for 10 hours. After lowering the temperature to room temperature and terminating the reaction, the potassium carbonate aqueous solution was removed to separate the layers. After removal of the solvent, the white solid was recrystallized from tetrahydrofuran and ethyl acetate to prepare the compound 1 (11.09 g, yield 78%).

MS [M + H] ⁺ = 607.73

Manufacturing example  4-2: Synthesis of Compound 2

In the synthesis of Compound 1, A5-2 was substituted for A5-1, and 2- (4-chlorophenyl) -4,6-diphenyl-1 was substituted for 2- (3-chlorophenyl) -4,6-diphenylpyrimidine. Compound 3 was synthesized by the same method except that 3,5-triazine was used.

MS [M + H] ⁺ = 732.86

Manufacturing example  4-3: Synthesis of Compound 3

In the synthesis of Compound 1, A5-2 was used instead of A5-1, and 2-chloro-4,6-diphenylpyrimidine was used instead of 2- (3-chlorophenyl) -4,6-diphenylpyrimidine. Was synthesized in the same manner to prepare compound 3.

MS [M + H] ⁺ = 654.78

Manufacturing example  4-4: Synthesis of Compound 4

1) Synthesis of A6-1

In the synthesis of Compound 1, A5-3 was substituted for A5-1, and 2-chloro-4- (4-chlorophenyl) -6-phenyl- was substituted for 2- (3-chlorophenyl) -4,6-diphenylpyrimidine. A6-1 was synthesized by the same method except that 1,3,5-triazine was used.

MS [M + H] ⁺ = 567.06

2) Synthesis of Compound 4

A6-1 (15 g, 26.4 mmol), 9H-carbazole (15 g, 27.3 mmol), and sodium-t-butoxide (4.56 g, 59.2 mol) were added to xylene, stirred and heated to reflux, and then refluxed [bis (tri -t-butylphosphine)] palladium (269mg. 2mmol%). After lowering the temperature to room temperature and terminating the reaction, it was recrystallized using tetrahydrofuran and ethyl acetate to prepare compound 4 (15.08g, 82%).

MS [M + H] ⁺ = 697.81

Manufacturing example  4-5: Synthesis of Compound 5

In the synthesis of Compound 1, A5-3 was substituted for A5-1, and 2-chloro-4- (9,9-dimethyl-9H-2- was substituted for 2- (3-chlorophenyl) -4,6-diphenylpyrimidine. 1) Compound 6 was synthesized by the same method except that 6-phenyl-1,3,5-triazine was used.

MS [M + H] ⁺ = 724.88

Manufacturing example  4-6: Synthesis of Compound 6

In the synthesis of Compound 1, B5-1 was substituted for A5-1, and 2-chloro-4- (4- (dibenzo [b, d] instead of 2- (3-chlorophenyl) -4,6-diphenylpyrimidine. Compound 6 was prepared by synthesizing in the same manner except that furan-4-yl) phenyl) -6-phenyl-1,3,5-triazine was used.

MS [M + H] ⁺ = 697.81

Manufacturing example  4-7: Synthesis of Compound 7

1) Synthesis of B6-1

In the synthesis of Compound 1, B5-2 was substituted for A5-1, and 2-chloro-4- (3-chlorophenyl) -6-phenyl- was substituted for 2- (3-chlorophenyl) -4,6-diphenylpyrimidine. B6-1 was synthesized by the same method except that 1,3,5-triazine was used.

MS [M + H] ⁺ = 690.21

2) Synthesis of Compound 7

The same method except that B6-1 was used instead of A3-1 in the synthesis of Compound 1, and (3-cyanophenyl) boronic acid was used instead of 2- (3-chlorophenyl) -4,6-diphenylpyrimidine. Compound 7 was synthesized.

MS [M + H] ⁺ = 756.88

Manufacturing example  4-8: Synthesis of Compound 8

In the synthesis of Compound 1, B5-3 was substituted for A5-1, and 2-chloro-4,6-diphenyl-1,3,5- was substituted for 2- (3-chlorophenyl) -4,6-diphenylpyrimidine. Compound 8 was synthesized by the same method except for using triazine.

MS [M + H] ⁺ = 532.62

Manufacturing example  4-9: Synthesis of Compound 9

B5-4 instead of A5-1 in the synthesis of Compound 1, 2-([1,1'-biphenyl] -3-yl instead of 2- (3-chlorophenyl) -4,6-diphenylpyrimidine) Compound 9 was prepared by synthesizing in the same manner except that -4-chloro-6-phenyl-1,3,5-triazine was used.

MS [M + H] ⁺ = 808.95

Manufacturing example  4-10: Synthesis of Compound 10

In the synthesis of Compound 1, B5-4 was substituted for A5-1, and 2-chloro-4- (naphthalen-2-yl) -6-phenyl was substituted for 2- (3-chlorophenyl) -4,6-diphenylpyrimidine. Compound 1 was prepared by synthesizing in the same manner, except that -1,3,5-triazine was used.

MS [M + H] ⁺ = 706.82

Example  One

A glass substrate (corning 7059 glass) coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 Å was put in distilled water in which a dispersing agent was dissolved and washed with ultrasonic waves. As a detergent, a product of Fischer Co. was used, and distilled water was used by Millipore Co. Distilled water filtered secondarily was used as a filter of the product. After washing the ITO for 30 minutes, ultrasonic washing was repeated for 10 minutes by repeating it twice with distilled water. After washing with distilled water, ultrasonic cleaning was performed in the order of isopropyl alcohol, acetone, and methanol, followed by drying.

HAT (hexanitrile hexaazatriphenylene, hexanitrile hexaazatriphenylene) was thermally vacuum-deposited to a thickness of 500 위에 on the prepared ITO transparent electrode to form a hole injection layer. Then, a hole transport layer was formed by vacuum-depositing HT1 (900 kPa), a material for transporting holes, and then vacuum-depositing HT2 on the hole transport layer to a thickness of 50 kV to form a hole control layer. As a light emitting layer, a host H1 and a dopant D1 compound (25: 1) were vacuum deposited to a thickness of 300 Pa. Subsequently, an ETM1 compound (50Å) was formed as an electron control layer on the light-emitting layer, and the electron transport layer with a thickness of 310Å was formed by co-depositing Compound 1 and LiQ (1: 1) synthesized in Preparation Example 4-1 on the electron control layer. Formed. On the electron transport layer, lithium fluoride (LiF) having a thickness of 10 와 and Mg and Ag (10: 1) having a thickness of 150 Å were sequentially deposited and a cathode was formed by depositing aluminum having a thickness of 1,000, to form an organic light emitting device.

In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, lithium fluoride was maintained at 0.2 Å / sec, and aluminum was maintained at a deposition rate of 3 to 7 Å / sec.

Example  2 to 16

An organic light emitting device was manufactured in the same manner as in Example 1, except that the compound shown in Table 1 and LIQ were used in a specific ratio instead of Compound 1 and LIQ (1: 1) as the electron transport layer.

Example  17

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 1 was used instead of ETM1 as the electron control layer and ETM2 was used instead of Compound 1 in the electron transport layer.

Example  18 to 23

The organic light-emitting device in the same manner as in Example 17, except that the compound shown in Table 2 below was used instead of Compound 1 as the electron-regulating layer, and ETM2 and LIQ were used in the electron transport layer at a specific ratio shown in Table 2 below. Was prepared.

Example  24 to 32

Except that in Example 1, the compound shown in Table 3 below was used instead of ETM1 as the electron-regulating layer, and the compound shown in Table 3 below was used as the electron transport layer and LIQ (1: 1) in a specific ratio. The same experiment was conducted.

Comparative example  1 to 13

Except for using the compound shown in Table 3 instead of ETM1 as the electron-regulating layer in Example 1, and using the compound shown in Table 3 below in specific proportions instead of Compound 1 and LIQ (1: 1) as the electron transport layer. Was tested in the same way.

By applying current (20mA / cm ² ) to the organic light emitting devices manufactured in Examples 1 to 32 and Comparative Examples 1 to 13, voltage, efficiency, color coordinates, and life were measured, and the results are shown in Tables 1 to 3, respectively. Shown.

No Electron transport layer: LiQ Voltage (V) Efficiency (Cd / A) Color coordinate (x, y) life span
(T95, h) Example 1 Compound 1: LiQ = 1: 1 3.51 6.71 (0.135, 0.138) 49.0 Example 2 Compound 2: LiQ = 1: 1 3.45 6.63 (0.134, 0.137) 50.2 Example 3 Compound 3: LiQ = 1: 1 3.41 6.58 (0.135, 0.138) 55.2 Example 4 Compound 4: LiQ = 1: 1 3.34 6.82 (0.134, 0.138) 51.2 Example 5 Compound 5: LiQ = 1: 1 3.42 6.72 (0.136, 0.139) 48.9 Example 6 Compound 6: LiQ = 1: 1 3.31 6.52 (0.135, 0.138) 48.5 Example 7 Compound 7: LiQ = 1: 1 3.50 6.69 (0.133, 0.139) 49.1 Example 8 Compound 8: LiQ = 1: 1 3.52 6.81 (0.134, 0.138) 38.2 Example 9 Compound 9: LiQ = 1: 1 3.49 6.78 (0.135, 0.137) 51.0 Example 10 Compound 10: LiQ = 1: 1 3.38 6.66 (0.134, 0.138) 46.8 Example 11 Compound 2: LiQ = 2: 1 3.39 6.78 (0.135, 0.138) 44.2 Example 12 Compound 3: LiQ = 2: 1 3.42 6.59 (0.134, 0.139) 46.5 Example 13 Compound 5: LiQ = 1: 2 3.45 6.66 (0.135, 0.138) 47.1 Example 14 Compound 7: LiQ = 2: 1 3.42 6.59 (0.134, 0.138) 42.5 Example 15 Compound 9: LiQ = 1: 2 3.45 6.66 (0.136, 0.139) 43.0 Example 16 Compound 10: LiQ = 1: 2 3.45 6.66 (0.134, 0.137) 50.8

No Electronic control layer Electron transport layer: LiQ Voltage (V) efficiency
(Cd / A) Color coordinate
(x, y) life span
(T95, h) Example 17 Compound 1 ETM2: LiQ = 1: 1 3.43 7.01 (0.134, 0.139) 46.5 Example 18 Compound 2 ETM2: LiQ = 1: 1 3.32 6.98 (0.135, 0.138) 47.2 Example 19 Compound 3 ETM2: LiQ = 1: 1 3.46 6.66 (0.134, 0.138) 47.2 Example 20 Compound 5 ETM2: LiQ = 1: 2 3.44 6.78 (0.136, 0.139) 49.0 Example 21 Compound 6 ETM2: LiQ = 1: 2 3.45 6.97 (0.134, 0.137) 51.0 Example 22 Compound 9 ETM2: LiQ = 1: 1 3.33 6.89 (0.135, 0.138) 52.0 Example 23 Compound 10 ETM2: LiQ = 2: 1 3.52 6.79 (0.134, 0.138) 48.0

No Electronic control layer Electron transport layer: LiQ Voltage (V) efficiency
(Cd / A) Color coordinate (x, y) life span
(T95, h) Example 24 Compound 1 Compound 2: LiQ = 1: 1 3.44 6.67 (0.134, 0.138) 46.8 Example 25 Compound 4 Compound 8: LiQ = 1: 1 3.45 6.58 (0.137, 0.134) 47.1 Example 26 Compound 7 Compound 10: LiQ = 1: 1 3.52 6.87 (0.138, 0.138) 42.5 Example 27 Compound 9 Compound 1: LiQ = 1: 2 3.38 6.82 (0.135, 0.139) 46.5 Example 28 ETM1 Compound 1 3.39 6.81 (0.135, 0.138) 49.7 Example 29 ETM1 Compound 5 3.51 6.71 (0.135, 0.139) 50.1 Example 30 ETM1 Compound 7 3.45 6.63 (0.134, 0.138) 49.8 Example 31 Compound 1 Compound 7 3.41 6.58 (0.134, 0.138) 47.4 Example 32 Compound 3 Compound 10 3.34 6.82 (0.134, 0.138) 41.5 Comparative Example 1 ETM1 ETM2: LiQ = 1: 1 3.82 5.70 (0.134, 0.139) 28.1 Comparative Example 2 ETM1 ETM2: LiQ = 2: 1 3.94 5.81 (0.135, 0.138) 21.0 Comparative Example 3 ETM1 ET1: LiQ = 1: 1 3.78 5.66 (0.134, 0.138) 33.0 Comparative Example 4 ETM1 ET2: LiQ = 1: 1 3.88 5.82 (0.136, 0.139) 28.0 Comparative Example 5 ETM1 ET4: LiQ = 1: 1 4.01 5.89 (0.134, 0.138) 38.1 Comparative Example 6 ET3 ETM2: LiQ = 1: 1 3.82 5.71 (0.134, 0.138) 33.5 Comparative Example 7 ET5 ETM2: LiQ = 1: 1 3.78 5.89 (0.137, 0.135) 28.2 Comparative Example 8 ET1 ET2: LiQ = 1: 1 3.75 5.91 (0.134, 0.138) 35.1 Comparative Example 9 ET4 ET3: LiQ = 1: 1 3.70 5.84 (0.135, 0.137) 29.4 Comparative Example 10 ET6 ETM2: LiQ = 1: 1 3.80 6.01 (0.135, 0.138) 30.5 Comparative Example 11 ET7 ETM2: LiQ = 1: 1 3.75 5.94 (0.134, 0.138) 31.5 Comparative Example 12 ET8 ETM2: LiQ = 1: 1 3.74 5.88 (0.136, 0.139) 33.5 Comparative Example 13 ET9 ETM2: LiQ = 1: 1 3.81 6.05 (0.134, 0.137) 38.0

According to Tables 1 to 3, it was confirmed that Examples 1 to 32 exhibited characteristics that the voltage was low and the efficiency and lifetime were remarkably superior to those of Comparative Examples 1 to 13.

1: substrate 2: anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: hole control layer 8: light emitting layer
9: electron control layer 10: electron transport layer

Claims (10)

Compound represented by the formula (1):
[Formula 1]

In Chemical Formula 1,
Y ₁ and Y ₂ are each independently hydrogen; Substituted or unsubstituted C _1-40 alkyl; Substituted or unsubstituted C _6-60 aryl; Or a substituted or unsubstituted C _2-60 heteroaryl containing one or more of O, N, Si and S,
Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl; Or a substituted or unsubstituted C _2-60 heteroaryl containing one or more of O, N, Si and S,
X ₁ to X ₃ are each independently N or CR ', provided that at least one of them is N,
R 'is hydrogen; Or substituted or unsubstituted C _1-60 alkyl,
L are each independently a direct bond; Substituted or unsubstituted C _6-60 arylene; Or C _2-60 heteroarylene comprising any one or more hetero atoms selected from the group consisting of N, O, S and Si,
R ₁ to R ₃ are each independently halogen; Timing; Cyano, nitrile; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 thioalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _1-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Or substituted or unsubstituted C _2-60 heteroaryl including one or more of O, N, Si and S,
m is 0 to 4,
n is 0 to 2,
o is 0 to 3,
z is 1 to 4, except that o + z is 4 or less.
According to claim 1,
Y ₁ and Y ₂ are each independently methyl or phenyl.
According to claim 1,
A compound wherein m, n and o are 0.
According to claim 1,
z is 1 compound.
According to claim 1,
Formula 1 is any one selected from compounds represented by the following Formulas 1-1 to 1-10, the compound:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

In Chemical Formulas 1-1 to 1-10,
Description of L, Ar ₁ and Ar ₂ is as defined in claim 1.
According to claim 1,
Ar ₁ and Ar ₂ are Compounds, each independently selected from the group consisting of:

According to claim 1,
Each L is independently a direct bond or a compound selected from the group consisting of:

According to claim 1,
Compound represented by Formula 1 is characterized in that any one selected from the group consisting of the following compounds, compounds:

A first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the compound according to any one of claims 1 to 8. That is, an organic light emitting device.
The method of claim 9,
The organic material layer containing the compound may include an electron transport layer; Electronic control layer; Electron injection layer; Hole blocking layer; Or an organic light-emitting device, characterized in that the light-emitting layer.

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