KR20200090515A - 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. The compound represented by chemical formula 1 can be used as a material for an organic material layer of the organic light emitting device.

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-layer 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 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 excitons are 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 is O or S,

Q ring is a dibenzofuran group, a benzofuran group, a dibenzothiophene group or a benzothiophene group,

At least one of R ₁ to R ₄ is represented by the following Chemical Formula 2, at least one of R ₁ to R ₄ is represented by the following Chemical Formula 3, and the rest are each independently hydrogen; heavy hydrogen; halogen; Hydroxy; 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; Or substituted or unsubstituted C _1-60 alkenyl,

a, b, c and d are each independently 1 to 4,

[Formula 2]

In Chemical Formula 2,

L ₁ is a direct bond; Or substituted or unsubstituted C _6-60 arylene,

Ar is C _2-60 heteroaryl containing one or more of substituted or unsubstituted O, N, Si and S,

[Formula 3]

In Chemical Formula 3,

L ₂ is a direct bond; Or substituted or unsubstituted C _6-60 arylene.

In addition, the present invention is a first electrode; A second electrode provided to face the first electrode; And 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 an organic light emitting device is provided. do.

The compound represented by Chemical Formula 1 may be used as a material for the organic material layer of the organic light emitting device, and may improve efficiency, low driving voltage, and/or lifespan 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 emission, electron transport, or electron injection 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), electron suppression layer (7), light emitting layer (8), hole blocking layer (9), electron injection and transport layer ( 10) and an example of an organic light-emitting device comprising the cathode 4 is shown.

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

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 this 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 a straight chain or a branched chain, 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, quinazoline 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, 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 example of the 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, heteroarylamine among heteroarylamines may be applied to the description of the aforementioned heterocyclic group. In the present specification, the alkenyl group among the alkenyl groups 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.

Preferably, the formula 1 may be any one selected from compounds represented by the following formulas 1-1 to 1-24.

In Chemical Formulas 1-1 to 1-24,

Y ₁ and Y ₂ are each independently O or S,

The description of R ₁ to R ₄ is as defined above.

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

X is each independently N or CR' ₂ , wherein at least one of X is N,

R'is hydrogen; heavy hydrogen; halogen; Hydroxy; 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 C _1-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S.

Preferably, L ₁ and L ₂ may each independently be a direct bond or any one selected from the group consisting of:

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

The compound represented by Chemical Formula 1 may be prepared by the following Reaction Schemes 1 to 4. The manufacturing method may be more specific in the manufacturing examples to be described later.

[Scheme 1]

[Scheme 2]

[Scheme 3]

[Scheme 4]

In Reaction Schemes 1 to 4, definitions other than X are as defined above, and X is halogen and more preferably bromo or chloro. The reaction is a Suzuki coupling reaction, and is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be modified as known in the art. The manufacturing method may be more specific in the manufacturing examples to be described later.

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 an organic light emitting device is provided. 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 light emitting 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 to this, and may include fewer organic layers.

In addition, the organic material layer may include a hole injection layer, a hole transport layer, a layer that simultaneously performs hole injection and transport, or an electron suppressing layer, and the hole injection layer, a hole transport layer, a layer that simultaneously performs hole injection and transport, or The electron suppressing layer includes a compound represented by Chemical Formula 1 above.

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

In addition, the organic material layer may include an electron transport layer, an electron injection layer, a layer that simultaneously performs electron injection and transport, or a hole blocking layer, and the electron transport layer, an electron injection layer, and a layer that simultaneously performs electron injection and transport, or The hole blocking layer includes a compound represented by Chemical Formula 1 above.

In addition, the organic material layer includes a light emitting layer and an electron injection and transport layer, and the electron injection and 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 (normal type) 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), electron suppression layer (7), light emitting layer (8), hole blocking layer (9), electron injection and transport layer ( 10) and an example of an organic light emitting device composed of the cathode 4 is shown. In such a structure, the compound represented by Chemical Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the electron suppressing layer, the light emitting layer, the hole blocking layer, and the electron injection and transport layer.

The organic light emitting device according to the present invention may be manufactured 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. Further, 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 into 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 such a 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 an 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 substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based substances. Organic materials, anthraquinones, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes from the hole injection layer to the light emitting layer. It is a material that transports holes from the anode or the hole injection layer as a hole transport material and transfers them to the light emitting layer. 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.

The light-emitting material is a material capable of emitting light in the visible light region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole compounds; Poly(p-phenylenevinylene) (PPV)-based 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 pyrene, anthracene, chrysene, periplanene, etc. having an arylamino group, and substituted or unsubstituted as a 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, metal complexes include, but are not limited to, iridium complexes, platinum complexes, and the like.

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 Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used 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 or silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, followed by an aluminum layer or a silver layer in each case.

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, an excellent electron injection effect on a light emitting layer or a light emitting material, and injects holes 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.

The preparation of the compound represented by Chemical Formula 1 and the organic light emitting device including the same will be described in detail in the following Examples. However, the following examples are intended to illustrate the invention, and the scope of the invention is not limited by them.

Manufacturing example 1. Synthesis of Compound E1

The compound 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro [fluoreno[3,4-b]benzofuran-8,9'- Xanthine]-2'-carbonitrile (10.0 g, 17.4 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (5.0 g, 18.8 mmol) in tetrahydrofuran (100 ml) After completely dissolved, potassium carbonate (7.4 g, 53.7 mmol) was dissolved in 43 ml of water and added, and tetrakistriphenyl-phosphine palladium (620 mg, 0.537 mmol) was added, followed by heating and stirring for 5 hours. After lowering the temperature to room temperature and terminating the reaction, the potassium carbonate solution was removed to filter the white solid. The filtered white solid was washed twice each with tetrahydrofuran and ethyl acetate to prepare the compound E1 (9.2 g, yield 78%).

MS[M+H] ⁺ = 678

Manufacturing example 2. Synthesis of Compound E2

Compound 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro [fluoreno[3,4-b]benzofuran-8 in Preparation Example 1] 4-(2'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[benzo[] instead of ,9'-xanthine]-2'-carbonitrile b] Compound E2 was prepared in the same manner as in Preparation Example 1, except that fluoreno[4,3-d]thiophen-8,9'-xanthene]-6-yl)benzonitrile was used.

MS[M+H] ⁺ = 770

Manufacturing example 3. Synthesis of Compound E3

The compound 6-fluoropyro[fureno[3,4-b]benzofuran-8,9'-xanthine]-2'-carbonitrile (10.0g, 21.5mmol) and 2-ethyl-1l2-benzo[ d] Imidazole (3.2 g, 22.1 mmol), cesium carbonate (14.4 g, 44.2 mmol) was added with dimethylacetamide (130 ml), followed by heating and stirring at 120° C. or higher for 12 hours. After lowering the temperature to room temperature and terminating the reaction, water was added to obtain a solid after filtration to prepare the compound E3 (10.4 g, yield 82%).

MS[M+H] ⁺ = 591

Manufacturing example 4. Synthesis of Compound E4

Compound 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro [fluoreno[3,4-b]benzofuran-8 in Preparation Example 1, 4'-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)spiro[fluoreno[3,4] instead of 9'-xanthine]-2'-carbonitrile The compound E4 was prepared in the same manner as in Preparation Example 1, except that -b]benzofuran-8,9'-xanthine]-1-carbonitrile was used.

MS[M+H] ⁺ = 678

Manufacturing example 5. Synthesis of Compound E5

Compound 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro [fluoreno[3,4-b]benzofuran-8 in Preparation Example 1, 10-bromospiro[fluoreno[3,4-b]benzofuran-8,9'-xanthine]-1-carbonitrile, 2-chloro-4, instead of 9'-xanthine]-2'-carbonitrile 2,4-diphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2 instead of 6-diphenyl-1,3,5-triazine The compound E5 was prepared in the same manner as in Preparation Example 1 except that -yl)phenyl)-1,3,5-triazine was used.

MS[M+H] ⁺ = 754

Manufacturing example 6. Synthesis of Compound E6

Compound 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro [fluoreno[3,4-b]benzofuran-8 in Preparation Example 1, 2'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[benzo[b]fluoro instead of 9'-xanthine]-2'-carbonitrile The compound E6 was manufactured by the same method as the preparation example 1 except that leno[4,3-d]thiophen-8,9'-cyoxanthin]-1-carbonitrile was used.

MS[M+H] ⁺ = 710

Manufacturing example 7. Synthesis of Compound E7

6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro [fluoreno[3,4-b]benzofuran-8,9 in Preparation Example 1 2'-(4,4,5,5-tetramethyl-1,3,2-dadioxaborolan-2-yl)spiro[fluoreno[3,4] instead of'-xanthine]-2'-carbonitrile -b] Benzofuran-8,9'-thioxanthin]-1-carbonitrile, except that the compound E7 was prepared in the same manner as in Preparation Example 1.

MS[M+H] ⁺ = 694

Manufacturing example 8. Synthesis of Compound E8

Compound 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro [fluoreno[3,4-b]benzofuran-8 in Preparation Example 1] 4-(8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[fluoreno[, instead of ,9'-xanthine]-2'-carbonitrile The compound E8 was prepared by the same method as Preparation Example 1 except that 3,4-b]furan-6,9'-xanthine]-4-yl)benzonitrile was used.

MS[M+H] ⁺ = 704

Manufacturing example 9. Synthesis of Compound E9

Compound 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro [fluoreno[3,4-b]benzofuran-8 in Preparation Example 1] 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro [fluoreno[3,4] instead of ,9'-xanthine]-2'-carbonitrile The compound E9 was prepared in the same manner as in Preparation Example 1, except that -b]thiophene-6,9'-thioxanthine]-2'-carbonitrile was used.

MS[M+H] ⁺ = 660

Example One

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 에 was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, Fischer (Fischer Co.) was used as the detergent, and distilled water filtered secondarily by a filter of Millipore Co. was used as the distilled water. After washing the ITO for 30 minutes, ultrasonic washing was repeated 10 times with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with a solvent of isopropyl alcohol, acetone, and methanol, followed by drying and transporting to a plasma cleaner. In addition, the substrate was washed for 5 minutes using oxygen plasma, and then transferred to a vacuum evaporator.

A hole injection layer was formed by thermal vacuum deposition of the following compound HI1 and the following compound HI2 to a molar ratio of 98:2 on the ITO transparent electrode, which was the thus prepared anode, to a thickness of 100 Pa. The following compound HT1 was vacuum deposited on the hole injection layer to a thickness of 1150 MPa to form a hole transport layer. Subsequently, an electron suppressing layer was formed by vacuum-depositing the compound EB1 with a thickness of 50 mm 2 on the hole transport layer. Subsequently, the following compound BH and the following compound BD with a thickness of 200 mm 2 were vacuum-deposited on the electron suppressing layer at a weight ratio of 50:1 to form a light emitting layer.

A hole blocking layer was formed by vacuum-depositing the following compound HB1 with a thickness of 50 mm 2 on the light emitting layer. Subsequently, on the hole blocking layer, the compound E1 prepared in Preparation Example 1 and the following compound LiQ were vacuum-deposited at a weight ratio of 1:1 to form an electron injection and transport layer with a thickness of 30 MPa. On the electron injection and transport layer, lithium fluoride (LiF) with a thickness of 12 Å and aluminum with a thickness of 1,000 순차적 were sequentially deposited to form a negative electrode.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7Å/sec, the lithium fluoride of the negative electrode was maintained at a deposition rate of 0.3Å/sec, and the aluminum was maintained at a deposition rate of 2Å/sec, and the vacuum degree during deposition was 2ⅹ10 ^-7 ~ An organic light-emitting device was manufactured by maintaining 5ⅹ10 ^-6 torr.

Example 2 to 5

An organic light emitting diode was manufactured according to the same method as Example 1 except for using the compound shown in Table 1 instead of the compound E1 prepared in Preparation Example 1.

Comparative example 1 to 3

An organic light emitting diode was manufactured according to the same method as Example 1 except for using the compound shown in Table 1 instead of the compound E1 prepared in Preparation Example 1. Compounds ET1, ET2 and ET3 used in Table 1 are as follows.

When 20mA/cm ² current was applied to the organic light emitting devices manufactured by Examples 1 to 5 and Comparative Examples 1 to 3, voltage, efficiency, color coordinates, and lifetime were measured and the results are shown in Table 1 below. T ₉₅ means the time required for the luminance to decrease from the initial luminance (1600 nits) to 95%.

Hole injection and transport layer Voltage (V) Efficiency (cd) Color coordinate (x,y) T ₉₅ (hr) Example 1 Compound E1 4.23 6.21 (0.140, 0.046) 260 Example 2 Compound E3 4.24 6.18 (0.141, 0.046) 245 Example 3 Compound E5 4.12 6.38 (0.142, 0.045) 252 Example 4 Compound E7 4.52 6.15 (0.142, 0.045) 254 Example 5 Compound E8 4.16 6.33 (0.144, 0.044) 245 Comparative Example 1 ET 1 4.48 5.46 (0.143, 0.051) 164 Comparative Example 2 ET 2 4.78 5.32 (0.146, 0.045) 182 Comparative Example 3 ET 3 4.85 5.21 (0.146, 0.053) 187

As shown in Table 1, it was confirmed that the organic light emitting device manufactured by using the compound of the present invention as an electron injection and transport layer exhibits excellent properties in terms of efficiency, driving voltage, and life of the organic light emitting device. Specifically, Examples 1 to 5 exhibited characteristics of low voltage, high efficiency, and long life compared to Comparative Examples using compounds in which cyano groups were not substituted even though the compounds of the present invention and the core were similar.

Although the preferred embodiment (electron injection and transport layer) of the present invention has been described through the above, the present invention is not limited thereto, and can be implemented by various modifications within the scope of the claims and detailed description of the invention. It also falls within the scope of the invention.

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

Claims (6)

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

In Chemical Formula 1,
Y is O or S,
Q ring is a dibenzofuran group, a benzofuran group, a dibenzothiophene group or a benzothiophene group,
At least one of R ₁ to R ₄ is represented by the following Chemical Formula 2, at least one of R ₁ to R ₄ is represented by the following Chemical Formula 3, and the rest are each independently hydrogen; heavy hydrogen; halogen; Hydroxy; 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; Or substituted or unsubstituted C _1-60 alkenyl,
a, b, c and d are each independently 1 to 4,
[Formula 2]

In Chemical Formula 2,
L ₁ is a direct bond; Or substituted or unsubstituted C _6-60 arylene,
Ar is C _2-60 heteroaryl containing one or more of substituted or unsubstituted O, N, Si and S,
[Formula 3]

In Chemical Formula 3,
L ₂ is a direct bond; Or substituted or unsubstituted C _6-60 arylene.
According to claim 1,
Formula 1 is any one selected from compounds represented by the following Formulas 1-1 to 1-24, the compound:

In Chemical Formulas 1-1 to 1-24,
Y ₁ and Y ₂ are each independently O or S,
The description of R ₁ to R ₄ is as defined in claim 1.
According to claim 1,
Ar is any one selected from the group consisting of:

X is each independently N or CR' ₂ , wherein at least one of X is N,
R'is hydrogen; heavy hydrogen; halogen; Hydroxy; 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 C _1-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S.
According to claim 1,
L ₁ and L ₂ are each independently a direct bond or any one 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 5. That is, an organic light emitting device.

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