KR102360902B1 - 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 using 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 in which electric energy is converted 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, fast response time, and excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.

An organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode. The organic layer is often formed 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, 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 the organic light emitting device, when a voltage is applied between the two electrodes, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons When it falls back to the ground state, it lights up.

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

Korean Patent Publication No. 10-2013-073537

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 the following formula (1):

[Formula 1]

In Formula 1,

A is a naphthalene ring,

Y is S, or O;

R ₁ and R ₂ are each independently hydrogen, deuterium, or substituted or unsubstituted C _1-10 alkyl;

X ₁ , X ₂ and X ₃ are each independently N, or CR′, provided that at least two of them are N,

R' is each independently hydrogen, deuterium, substituted or unsubstituted C _1-10 alkyl, substituted or unsubstituted C _6-30 aryl, or one or more heteroatoms selected from the group consisting of N, O and S; a substituted or unsubstituted C _5-60 heteroaryl comprising;

L is a single bond, or a substituted or unsubstituted C _6-30 arylene,

Ar ₁ and Ar ₂ are each independently hydrogen, deuterium, substituted or unsubstituted C _1-10 alkyl, substituted or unsubstituted C _6-30 aryl, or at least one selected from the group consisting of N, O and S substituted or unsubstituted C _5-60 heteroaryl containing a hetero atom,

m and n are each independently an integer from 0 to 4.

In addition, the present invention is a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the above-described polymer of the present invention.

The compound represented by Chemical Formula 1 described above may be used as a material for an organic layer of an 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 the above formula (1) may be used as a material for hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection.

1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a light emitting layer 3 , and a cathode 4 .
2 shows an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8, and a cathode 4 did it

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

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; a phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an arylphosphine group; Or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more, or substituted or unsubstituted, two or more of the above-exemplified substituents are linked. . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the number of carbon atoms in the carbonyl group is not particularly limited, but 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, in the ester group, oxygen of the ester group may be substituted with a linear, 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 from 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 specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. However, the present invention is not limited thereto.

In the present specification, the boron group specifically includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group, and the like.

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

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but are 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 an exemplary embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the carbon number of the alkenyl group is 2 to 10. 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 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 carbon number of the cycloalkyl group is 3 to 20. 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 preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, or a terphenyl group, but 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.

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

etc. can be However, the present invention 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 carbon atoms is not particularly limited, but it is preferably from 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, a triazole group, an 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 group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, but is not limited thereto.

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

Preferably, the compound represented by Formula 1 is a compound represented by the following Formulas 2 to 9:

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

In Formulas 2 to 9,

Y, R ₁ , R ₂ , L, X ₁ , X ₂ , X ₃ , Ar ₁ , Ar ₂ , m and n are as defined above.

Preferably, R ₁ and R ₂ are each independently hydrogen, deuterium, or substituted or unsubstituted C _1-10 alkyl.

Preferably, R' is hydrogen.

Preferably, L is a single bond, phenylene or biphenylylene.

Preferably, Ar ₁ and Ar ₂ are each independently phenyl, methylphenyl, biphenylyl, naphthyl, naphthylphenyl, benzonitrile, benzonitrilephenyl, Ar ₁ and Ar ₂ are each independently phenyl, methylphenyl, biphenylyl, Naphthyl, naphthylphenyl, benzonitrile, benzonitrilephenyl, dibenzofuranyl, dibenzothiophenyl, pyridinyl, phenylpyridinyl, pyridinylphenyl, carbazol-9-yl, 9-phenyl-9H-carbazolyl , or 9H-carbazol-9-yl-N-phenyl.

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

.

.

In the compound represented by Formula 1 according to the present invention, fluorene and xanthene (or thioxanthene) form a spiro bond, so that the electrons of the lone pair of electrons of the central atom (oxygen or sulfur) of xanthene (or thioxanthene) When applied to an organic light emitting device due to the donor effect, an effect of increasing device efficiency can be realized. In particular, by including a naphthalene sphere in which an additional benzene ring is condensed to the benzene ring of xanthene (or thioxanthene), the effect of increasing the lifespan of the organic light emitting device can be realized through the delocalization energy expansion effect. In addition, by including a triazine-based substituent in the other benzene ring in which the naphthalene structure is not formed, the electron-attracting property is strengthened and an effect of increasing the efficiency in the organic light-emitting device can be realized.

The compound represented by Formula 1 may be prepared by a preparation method according to Scheme A below. The manufacturing method may be more specific in Preparation Examples to be described later.

[Scheme A]

In Scheme A, variables other than X are as defined in Formula 1, and X is halogen, preferably Cl or Br. In Scheme A, the reactor, catalyst, solvent, etc. used can be changed as appropriate for the desired product.

In addition, the present invention provides an organic light emitting device comprising the compound represented by Formula 1 above. In one example, the present invention provides a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the compound represented by Formula 1 above. 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, etc. 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 may include a hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes, and the hole injection layer, the hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 The indicated compounds are included.

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

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

In addition, the electron transport layer, the electron injection layer, or the layer that simultaneously injects and transports electrons includes the compound represented by Formula 1 above. In particular, the compound represented by Formula 1 according to the present invention has excellent thermal stability, a deep HOMO level of 6.0 eV or more, a high triplet energy (ET), and hole stability. In addition, when the compound represented by Formula 1 is used in an organic layer capable of simultaneously performing electron injection and electron transport, an n-type dopant used in the art may be mixed and used.

In addition, the organic light emitting device according to the present invention may be a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting device according to the present invention may be an 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 the organic light emitting diode 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 including 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 light emitting layer.

2 shows an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8, and a cathode 4 did it In such a structure, the compound represented by Formula 1 may be included in at least one of the hole injection layer, the hole transport layer, the light emitting layer, and the electron transport layer.

The organic light emitting device according to the present invention may be manufactured using materials and methods known in the art, except that at least one layer of the organic material layer includes the compound represented by Formula 1 above. Also, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic light emitting diode according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode And, after forming an organic 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 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 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 this 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.

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.

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

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

The hole injection layer is a layer for injecting holes from the electrode, and as a hole injection material, it has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and is produced in the light emitting layer A compound which prevents the movement of excitons to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the 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 material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light emitting layer. As a hole transport material, a material capable of transporting holes from the anode or hole injection layer to the light emitting layer and transferring them to the light emitting layer. This is suitable. Specific examples include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.

The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene, rubrene, and the like, but is not limited thereto.

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

Examples of the dopant material include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periflanthene, and the like, having an arylamino group. As the styrylamine compound, a substituted or unsubstituted It is a compound in which at least one arylvinyl group is substituted in the arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but is not limited thereto. In addition, examples of the metal complex include, but are not limited to, an iridium complex and a platinum complex.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports them to the light emitting layer. 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 may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.

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 with respect to the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer. A compound which prevents movement to a layer and is excellent in the ability to form a thin film is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc., derivatives thereof, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.

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

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

Synthesis of intermediate compounds

(1) Synthesis of intermediate compound la

[Scheme 1-1]

The compound 2-bromo-1,1'-biphenyl (50.0 g, 214.5 mmol) was dissolved in tetrahydrofuran (500 ml) at -78 ° C., and 2.5M n-butyllithium solution (86 ml, 214.5 mmol) was added dropwise. do. After that, 9-bromo-7H-benzo [c] xanthene-7-one (1P, 69 g, 214.5 mmol) was added and the temperature of the solution was raised to room temperature. After completion of the reaction by adding water, tetrahydrofuran is extracted, the solution is all distilled, and the solution is dissolved in 500 ml of an acetic acid solution, followed by reflux and heating. After the reaction was terminated by lowering the temperature to room temperature, a white solid was filtered out by filtration. The filtered white solid was washed twice with water and ethanol, respectively, to prepare a compound of Formula 1a-P (59.4 g, yield 60%).

MS[M+H] ⁺ = 461

The compound represented by the formula 1a-P (20.0 g, 43.4 mmol) and the compound 1a-sm (11.0 g, 43.4 mmol) were completely dissolved in Dioxane (200 mL), and potassium acetate (12.7 g, 130.1 mmol) was added thereto. was added, heated and stirred. After the reaction was terminated by lowering the temperature to room temperature, potassium acetate was removed by filtration. The filtered solution was solidified with ethanol and filtered. The white solid was washed twice with ethanol, respectively, to prepare a compound represented by Formula 1a (17.6 g, yield 80).

MS [M+H] ⁺ = 509

(2) Synthesis of intermediate compound 2a

[Scheme 2-1]

In Scheme 1-1, an intermediate compound 2a was synthesized in the same manner except that compound 2P was used instead of compound 1P.

MS [M+H] ⁺ = 509

(3) Synthesis of intermediate compound 3a

[Scheme 3-1]

In Scheme 1-1, an intermediate compound 3a was synthesized in the same manner except that compound 3P was used instead of compound 1P.

MS [M+H] ⁺ = 509

(4) Synthesis of intermediate compound 4a

[Scheme 4-1]

In Scheme 1-1, an intermediate compound 4a was synthesized in the same manner except that compound 4P was used instead of compound 1P.

MS [M+H] ⁺ = 509

(5) Synthesis of intermediate compound 5a

[Scheme 5-1]

In Scheme 1-1, an intermediate compound 5a was synthesized in the same manner except that compound 5P was used instead of compound 1P.

MS [M+H] ⁺ = 509

(6) Synthesis of intermediate compound 6a

[Scheme 6-1]

In Scheme 1-1, an intermediate compound 6a was synthesized in the same manner except that compound 6P was used instead of compound 1P.

MS [M+H] ⁺ = 509

(7) Synthesis of intermediate compound 7a

[Scheme 7-1]

In Scheme 1-1, an intermediate compound 7a was synthesized in the same manner except that compound 7P was used instead of compound 1P.

MS [M+H] ⁺ = 525

(8) Synthesis of intermediate compound 8a

[Scheme 8-1]

In Scheme 1-1, an intermediate compound 8a was synthesized in the same manner except that compound 8P was used instead of compound 1P.

MS [M+H] ⁺ = 525

(9) Synthesis of intermediate compound 9a

[Scheme 9-1]

In Scheme 1-1, an intermediate compound 9a was synthesized in the same manner except that compound 9P was used instead of compound 1P.

MS [M+H] ⁺ = 525

(10) Synthesis of intermediate compound 10a

[Scheme 10-1]

In Scheme 1-1, an intermediate compound 10a was synthesized in the same manner except that compound 10P was used instead of compound 1P.

MS [M+H] ⁺ = 525

(11) Synthesis of intermediate compound 11a

[Scheme 11-1]

In Scheme 1-1, an intermediate compound 11a was synthesized in the same manner except that compound 11P was used instead of compound 1P.

MS [M+H] ⁺ = 525

(12) Synthesis of intermediate compound 12a

[Scheme 12-1]

In Scheme 1-1, an intermediate compound 12a was synthesized in the same manner except that compound 12P was used instead of compound 1P.

MS [M+H] ⁺ = 525

Example 1. Synthesis of Formula E1

(1) Synthesis of compound E1

[Scheme 1]

The compound 4,4,5,5-tetramethyl-2-(spiro[benzo[c]xanthene-7,9'-fluorene]-9yl)-1,3,2-dioxaborolane ( la, 10.0 g, 19.7 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (1b, 5.3 g, 19.7 mmol) were completely dissolved in tetrahydrofuran (100 ml) and potassium carbonate (8.2 g, 59.0 mmol) was dissolved in 50 ml of water, and tetrakistriphenyl-phosphinopalladium (682 mg, 0.59 mmol) was added, followed by heating and stirring for 8 hours. After the reaction was terminated by lowering the temperature to room temperature, the potassium carbonate solution was removed and the above white solid was filtered. The filtered white solid was washed twice with tetrahydrofuran and ethyl acetate, respectively, to prepare a compound of Formula E1 (10.9 g, yield 90%).

MS[M+H] ⁺ = 614

Example 2. Synthesis of Formula E2

[Scheme 2]

In Example 1, instead of compound la (19.7 mmol), 2a (19.7 mmol) of Scheme 2 was used, and instead of compound lb (19.7 mmol), 2b (19.7 mmol) of Scheme 2 was used, except that, A compound represented by Formula E2 was prepared in the same manner as in the preparation method of E1 of Example 1.

MS [M+H] ⁺ = 765

Example 3. Synthesis of Formula E3

[Scheme 3]

In Example 1, instead of compound la (19.7 mmol), 3a (19.7 mmol) of Scheme 3 was used, and instead of compound lb (19.7 mmol), 3b (19.7 mmol) of Scheme 3 was used, except that A compound represented by Formula E3 was prepared in the same manner as in the preparation method of E1 of Example 1.

MS [M+H] ⁺ = 739

Example 4. Synthesis of Formula E4

[Scheme 4]

In Example 1, instead of compound la (19.7 mmol), 4a (19.7 mmol) of Scheme 4 was used, and instead of compound lb (19.7 mmol), 4b (19.7 mmol) of Scheme 4 was used, except that A compound represented by Formula E4 was prepared in the same manner as in the preparation method of E1 of Example 1.

MS [M+H] ⁺ = 690

Example 5. Synthesis of Formula E5

[Scheme 5]

In Example 1, instead of compound la (19.7 mmol), 5a (19.7 mmol) of Scheme 5 was used, and 5b (19.7 mmol) of Scheme 5 was used instead of compound lb (19.7 mmol). A compound represented by Formula E5 was prepared in the same manner as in the preparation method of E1 of Example 1.

MS [M+H] ⁺ = 715

Example 6. Synthesis of Formula E6

[Scheme 6]

In Example 1, instead of compound la (19.7 mmol), 6a (19.7 mmol) of Scheme 6 was used, and instead of compound lb (19.7 mmol), 6b (19.7 mmol) of Scheme 6 was used, except that, A compound represented by Formula E6 was prepared in the same manner as in the preparation method of E1 of Example 1.

MS [M+H] ⁺ = 715

Example 7. Synthesis of Formula E7

[Scheme 7]

In Example 1, instead of compound la (19.7 mmol), 7a (19.7 mmol) of Scheme 7 was used, and instead of compound lb (19.7 mmol), 7b (19.7 mmol) of Scheme 7 was used, except that A compound represented by Formula E7 was prepared in the same manner as in the preparation method of E1 of Example 1.

MS [M+H] ⁺ = 782

Example 8. Synthesis of Formula E8

[Scheme 8]

In Example 1, instead of compound la (19.7 mmol), 8a (19.7 mmol) of Scheme 8 was used, and instead of compound lb (19.7 mmol), 8b (19.7 mmol) of Scheme 8 was used, except that, A compound represented by Formula E8 was prepared in the same manner as in the preparation method of E1 of Example 1.

MS [M+H] ⁺ = 657

Example 9. Synthesis of Formula E9

[Scheme 9]

In Example 1, instead of compound la (19.7 mmol), 9a (19.7 mmol) of Scheme 9 was used, and instead of compound lb (19.7 mmol), 9b (19.7 mmol) of Scheme 9 was used, except that A compound represented by Formula E9 was prepared in the same manner as in the preparation method of E1 of Example 1.

MS [M+H] ⁺ = 755

Example 10. Synthesis of Formula E10

[Scheme 10]

In Example 1, instead of compound la (19.7 mmol), 10a (19.7 mmol) of Scheme 10 was used, and instead of compound lb (19.7 mmol), 10b (19.7 mmol) of Scheme 10 was used, except that A compound represented by Formula E10 was prepared in the same manner as in the preparation method of E1 of Example 1.

MS [M+H] ⁺ = 629

Example 11. Synthesis of Formula E11

[Scheme 11]

In Example 1, instead of compound la (19.7 mmol), 11a (19.7 mmol) of Scheme 11 was used, and instead of compound lb (19.7 mmol), 11b (19.7 mmol) of Scheme 11 was used, except that A compound represented by Formula E11 was prepared in the same manner as in the preparation method of E1 of Example 1.

MS [M+H] ⁺ = 706

Example 12. Synthesis of Formula E12

[Scheme 12]

In Example 1, instead of compound la (19.7 mmol), 12a (19.7 mmol) of Scheme 12 was used, and instead of compound lb (19.7 mmol), 12b (19.7 mmol) of Scheme 12 was used, except that A compound represented by Formula E12 was prepared in the same manner as in the preparation method of E1 of Example 1.

MS [M+H] ⁺ = 629

Example 13. Synthesis of Formula E13

[Scheme 13]

In Example 1, the compound represented by Formula E13 was prepared in the same manner as in the preparation method of E1 of Example 1, except that 13b (19.7 mmol) of Scheme 13 was used instead of compound lb (19.7 mmol). did

MS [M+H] ⁺ = 778

[Experimental Example 1]

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing the ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, and after drying, it was 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 HI-A compound was thermally vacuum deposited to a thickness of 600 Å to form a hole injection layer. A hole transport layer was formed by sequentially vacuum-depositing 50 Å of the HAT compound and 60 Å of the HT-A compound on the hole injection layer.

Subsequently, the following BH compound and BD compound were vacuum-deposited in a weight ratio of 25:1 to a thickness of 20 nm on the hole transport layer to form a light emitting layer.

On the light emitting layer, the compound (E1) of Example 1 and the following LiQ compound were vacuum-deposited at a weight ratio of 1:1 to form an electron injection and transport layer to a thickness of 350 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 10 Å and aluminum to a thickness of 1000 Å on the electron injection and transport layer.

In the above process, the deposition rate of organic material was maintained at 0.4 to 0.9 Å/sec, the deposition rate of lithium fluoride of the negative electrode was maintained at 0.3 Å/sec, and the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was 1×10 ^- By maintaining ⁷ to 5 × 10 ^-5 torr, an organic light emitting device was manufactured.

Experimental Examples 2 to 12

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1, except that the compounds (E2 to E12) of Examples 2 to 12 were used instead of the compound (E1) of Example 1.

Comparative Examples 1 to 12

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1, except that the following compounds (ET-1-A to ET-1-L) were used instead of the compound (E1) of Example 1.

The driving voltage and luminous efficiency were measured at a current density of 10 mA/cm ² for the organic light-emitting devices prepared in the Experimental Examples and Comparative Examples, and the time at which the luminance becomes 90% compared to the initial luminance at a current density of 20 mA/cm ² (T90) was measured. The results are shown in Table 1 below.

division compound Voltage
(V@10 mA/cm ² ) efficiency
(cd/A@10 mA/cm ² ) color coordinates
(x, y) Life (h)
T90 at 20 mA/cm ² ) Experimental Example 1 compound E1 4.01 4.88 (0.142, 0.096) 300 Experimental Example 2 compound E2 4.15 5.08 (0.142, 0.097) 201 Experimental Example 3 compound E3 4.20 4.80 (0.142, 0.096) 280 Experimental Example 4 compound E4 4.03 4.82 (0.142, 0.096) 318 Experimental Example 5 compound E5 4.14 4.76 (0.142, 0.096) 394 Experimental Example 6 compound E6 4.13 4.81 (0.142, 0.097) 379 Experimental Example 7 compound E7 4.12 5.02 (0.142, 0.096) 245 Experimental Example 8 compound E8 4.19 4.79 (0.142, 0.099) 260 Experimental Example 9 compound E9 4.13 4.90 (0.142, 0.096) 230 Experimental Example 10 compound E10 4.18 4.81 (0.142, 0.099) 222 Experimental Example 11 compound E11 4.08 4.92 (0.142, 0.096) 281 Experimental Example 12 compound E12 3.98 5.00 (0.142, 0.097) 219 Experimental Example 13 compound E13 4.05 4.80 (0.142, 0.097) 256 Comparative Example 1 Compound ET-1-A 6.00 2.10 (0.142, 0.096) 11 Comparative Example 2 Compound ET-1-B 5.89 2.21 (0.142, 0.096) 22 Comparative Example 3 Compound ET-1-C 4.02 4.80 (0.142, 0.096) 100 Comparative Example 4 Compound ET-1-D 4.44 4.70 (0.142, 0.096) 88 Comparative Example 5 Compound ET-1-E 4.31 4.22 (0.142, 0.096) 77 Comparative Example 6 Compound ET-1-F 4.67 4.25 (0.142, 0.096) 60 Comparative Example 7 Compound ET-1-G 4.20 4.78 (0.142, 0.097) 61 Comparative Example 8 Compound ET-1-H 4.20 5.00 (0.142, 0.097) 52 Comparative Example 9 Compound ET-1-I 4.33 4.75 (0.142, 0.097) 81 Comparative Example 10 Compound ET-1-J 4.10 4.66 (0.142, 0.097) 111 Comparative Example 11 Compound ET-1-K 4.11 4.54 (0.142, 0.097) 72 Comparative Example 12 Compound ET-1-L 4.23 4.34 (0.142, 0.097) 61

As shown in Table 1, the compound represented by Formula 1 according to the present invention may be used in an organic material layer capable of simultaneously performing electron injection and electron transport of the organic light emitting device.

Comparing Experimental Examples 1 to 12 in Table 1, both compounds having two cores of xanthene or thioxanthene show significantly superior characteristics in terms of driving voltage, efficiency, and lifespan of the organic light emitting diode. was able to confirm

Comparing the experimental examples of Table 1 and Comparative Examples 1 and 2, the compound in which triazine or pyrimidine is substituted for xanthene or thioxanthene as shown in Formula 1 according to the present invention is xanthene or thioxanthene and tri It was confirmed that azine or pyrimidine showed significantly superior properties in terms of efficiency and lifespan of the organic light emitting diode compared to the unsubstituted compound.

Comparing the Experimental Example of Table 1 with Comparative Examples 3, 4, and 7, the compound in which a naphthalene ring is formed in xanthene or thioxanthene as shown in Formula 1 according to the present invention has a longer lifespan of the organic light emitting diode compared to the other compounds. It was confirmed that it showed remarkably excellent characteristics in terms of

Comparing the experimental examples of Table 1 and Comparative Examples 5 to 6, the compound in which a naphthalene ring is formed in xanthene or thioxanthene as shown in Formula 1 according to the present invention, compared to the compound in which the naphthalene ring is not, the efficiency and lifespan of the organic light emitting diode It was confirmed that it showed remarkably excellent characteristics in terms of

Comparing the experimental examples in Table 1 and Comparative Examples 8 to 9, the compound in which a naphthalene ring is formed in xanthene or thioxanthene as shown in Formula 1 according to the present invention is more organic than the compound in which a six-membered heterocyclic group is formed in fluorene It was confirmed that the light emitting device exhibits remarkably excellent characteristics in terms of lifetime.

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

Claims (10)

A compound represented by the following formula (1):
[Formula 1]

In Formula 1,
A is a naphthalene ring,
Y is S, or O;
R ₁ and R ₂ are each independently hydrogen, deuterium, or substituted or unsubstituted C _1-10 alkyl;
X ₁ , X ₂ and X ₃ are each independently N, or CR′, provided that at least two of them are N,
R' is each independently hydrogen, deuterium, substituted or unsubstituted C _1-10 alkyl, substituted or unsubstituted C _6-30 aryl, or one or more heteroatoms selected from the group consisting of N, O and S; substituted or unsubstituted C _5-60 heteroaryl comprising;
L is a single bond, or a substituted or unsubstituted C _6-30 arylene,
Ar ₁ and Ar ₂ are each independently hydrogen, deuterium, substituted or unsubstituted C _1-10 alkyl, substituted or unsubstituted C _6-30 aryl, or at least one selected from the group consisting of N, O and S substituted or unsubstituted C _5-60 heteroaryl containing a hetero atom,
m and n are each independently an integer from 0 to 4.
According to claim 1,
The compound represented by Formula 1 is a compound represented by the following Formulas 2 to 9, a compound:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

In Formulas 2 to 9,
Y, R ₁ , R ₂ , L, X ₁ , X ₂ , X ₃ , Ar ₁ , Ar ₂ , m and n are as defined in claim 1.
According to claim 1,
R ₁ and R ₂ are each independently hydrogen, deuterium, or substituted or unsubstituted C _1-10 alkyl.
According to claim 1,
R' is hydrogen.
According to claim 1,
L is a single bond, phenylene or biphenylylene.
According to claim 1,
Ar ₁ and Ar ₂ are each independently phenyl, methylphenyl, biphenylyl, naphthyl, naphthylphenyl, benzonitrile, benzonitrilephenyl, dibenzofuranyl, dibenzothiophenyl, pyridinyl, phenylpyridinyl, pyridinyl phenyl, carbazol-9-yl, 9-phenyl-9H-carbazolyl, or 9H-carbazol-9-yl-N-phenyl.
According to claim 1,
m and n are each independently 0 or 1.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of:

.
a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers contains the compound according to any one of claims 1 to 8 which is an organic light emitting device.
10. The method of claim 9,
The organic material layer is a hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes, an organic light emitting device.

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