KR20210022493A - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel compound and an organic light emitting device using the same. The present invention provides a compound represented by chemical formula 1. The compound represented by chemical formula 1 described above can be used as a material for an organic layer of the organic light emitting device, and can improve efficiency, low driving voltage, and/or lifespan characteristics in the organic light emitting device.

Description

Novel compound and organic light emitting device comprising the same

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

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

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 material layer is often made of a multi-layered structure made of different materials in order to increase the efficiency and stability of the organic light emitting device.For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of such an organic light emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. When it falls back to the ground, it glows.

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

Accordingly, the present invention provides a material for a novel organic light-emitting device that can be used in an organic light-emitting device and at the same time, which can be used in a solution process.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to a novel 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,

X is O, or S,

L is a single bond; Substituted or unsubstituted C _6-60 arylene; _{C 2-60} heteroarylene containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S; and,

R ₁ , R ₂ , R ₃ , and R ₄ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _2-60 alkynyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _6-60 aryl; _{C 2-60} heteroaryl including any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O, and S; Substituted or unsubstituted tri(C _1-60 alkyl)silyl; Or a substituted or unsubstituted tri(C _6-60 aryl)silyl, or two adjacent substituents are bonded to form a C _6-60 aromatic ring,

n1 is an integer from 0 to 2,

n2 to n4 are each independently an integer of 0 to 3,

Ar ₁ is represented by the following formula (2),

[Formula 2]

In Chemical Formula 2,

Ar ₂ is substituted or unsubstituted C _6-60 aryl; _{Or C 2-60} heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S; and,

V ₁ to V ₄ are each independently CR _a or N,

W ₁ and W ₂ are each independently a single bond, CR _b , O or S,

R _a and R _b are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _6-60 aryl; _{Or C 2-60} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S; Or, or two adjacent R _a , or two adjacent R _b are bonded to each other to C _{6- 60} to form an aromatic ring,

p is an integer of 0 or 1.

In addition, the present invention, the first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises a compound represented by Formula 1 to provide.

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

1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.
2 is an example of an organic light-emitting device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron injection and transport layer 8, and a cathode 4 Is shown.

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

또는

는 다른 치환기에 연결되는 결합을 의미한다.In this specification,

or

Means a bond connected to another substituent.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Cyano group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means substituted or unsubstituted with one or more substituents selected from the group consisting of heteroaryl containing one or more of N, O, and S atoms, or substituted or unsubstituted with two or more substituents connected among the above exemplified substituents. . For example, "a substituent to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, or may be interpreted as a substituent to which two phenyl groups are connected.

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the ester group may be substituted with a C1-C25 linear, branched or cyclic alkyl group or an aryl group having 6 to 25 carbon atoms in the oxygen of the ester group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.

In the present specification, the boron group specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, 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 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 alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cycloheptylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present specification, the alkenyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but 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 are not limited thereto.

In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a 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 phenanthrenyl 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,

Can be, etc. However, it is not limited thereto.

In the present specification, heteroaryl is a heteroaryl containing 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 2 to 60 carbon atoms. Examples of heteroaryl include xanthene, thioxanthen, thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, Pyrimidyl group, triazine group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino Pyrazinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group ( phenanthroline), isoxazolyl group, thiadiazolyl group, phenothiazinyl group, and dibenzofuranyl group, but are not limited thereto.

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

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

In Formula 1, preferably L is a single bond.

Preferably, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen. At this time, preferably, n1 to n4 are 0.

Preferably, one of R ₁ , R ₂ , R ₃ and R ₄ is phenyl or pyridinyl and the other is hydrogen. At this time, preferably, one of n1 to n4 is 1, and the other is 0.

Preferably, two adjacent R ₁ , two adjacent R ₂ , two adjacent R ₃ , or two adjacent R ₄ are bonded to each other to form a benzene ring, and the remaining R ₁ to R ₄ are hydrogen.

In addition, in Formula 1, Ar ₁ is preferably any one selected from the group consisting of the following Formulas 2-1 to 2-3:

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In Formulas 2-1 to 2-3,

Ar ₂ is as defined in Chemical Formula 1,

R _a1 , R _a2 and R _a3 are each independently hydrogen or deuterium; Or two adjacent R _a1 , two adjacent R _a2 , or two adjacent R _a3 bonded to each other to form a benzene ring, and the rest is hydrogen,

Each R _b1 is independently hydrogen or deuterium,

W ₃ and W ₄ are each independently O or S,

p is an integer of 0 or 1.

More preferably, Ar ₁ is any one selected from the group consisting of:

In the above formulas,

Ar ₂ is as defined in Chemical Formula 1,

W ₃ and W ₄ are each independently O or S.

Preferably, Ar ₂ is phenylyl, biphenylyl, terphenylyl, naphthyl, anthracenyl, phenanthrenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, dibenzopyu Ranyl, dibenzothiophenyl, carbazol-9-yl, or 9-phenyl-carbazolyl, and Ar ₂ is unsubstituted or substituted with one or more deuterium.

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

Meanwhile, the present invention provides a method for preparing a compound represented by Formula 1, such as the following Scheme 1 as an example:

[Scheme 1]

In Reaction Scheme 1, X, L, and Ar ₂ are as defined in Formula 1, Y ₁ and Y ₂ are each independently a halogen group such as chloro or boromo, and Z is a boronic acid group, a boronic acid ester group, or It is a boron-containing organic group such as a boronic acid pinacol ester group, and Ar ₁ ′ is a substituent having the following structure,

In the above structure, V ₁ to V ₄ , W ₁ and W ₂ are as defined in Formula 1.

Specifically, compound (1) of Formula 1 is a palladium-catalyzed coupling reaction between a compound (i) having a parental structure and a compound (ii) including an electron acceptor substituent bonded to the parental structure, and compound (iii) Manufacturing a; And it can be prepared by a production method comprising the step of subjecting the compound (iii) to a Suzuki coupling reaction in the presence of the compound (iv) containing the above-described boron-containing organic group, and a base and a palladium catalyst.

As a palladium-based catalyst usable in the palladium-catalyzed coupling reaction and Suzuki coupling reaction, bis(tri-tert-butylphosphine)palladium (bis(tri-tert-butylphosphine)palladium(0), Pd(P)) -tBu ₃ ) ₂ ), tetrakis (triphenylphosphine) palladium (tetrakis (triphenylphosphine) palladium (0), Pd (PPh ₃ ) ₄ ), tris (dibenzylideneacetone) dipalladium (Tris (dibenzylideneacetone) dipalladium) , Pd ₂ (dba) ₃ )), bis (triphenylphosphine) palladium chloride, Pd (PPh ₃ ) ₂ Cl ₂ ), bis (acetonitrile) palladium chloride (Bis (acetonitrile) palladium (II) chloride, Pd(CH ₃ CN) ₂ Cl ₂ ), palladium(II) acetate, Pd(OAc) ₂ ), palladium(II) acetylacetonate, Pd (acac) ₂ ], Allylpalladium(II) chloride dimer (Allylpalladium(II) chloride dimer, Pd(allyl)Cl) ₂ ), Palladium on carbon (Pd/C), or palladium(II) chloride (II) chloride, PdCl ₂ ), and the like, and any one or a mixture of two or more of them may be used.

In addition, the palladium-catalyzed coupling reaction and the Suzuki coupling reaction may be performed in the presence of a base, and in this case, the base is sodium tert-butoxide, potassium tert-butoxide. -butoxide), sodium tert-pentoxide, sodium ethoxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydride hydride), lithium hydride or potassium hydride; Organic bases such as tetraethylammonium hydroxide ((Et ₄ NOH), bis(tetraethylammonium) carbonate, triethylamine; inorganic salts such as cesium fluoride, and any one or a mixture of two or more of them may be used. I can.

The palladium catalyzed coupling reaction may be performed in an organic solvent, and the Suzuki coupling reaction may be performed in water as a solvent.

As the organic solvent, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol diethyl ether, dimethoxyethane, bis(2-methoxyethyl) ether, diethylene glycol diethyl ether, tetrahydro Ether solvents such as furan or anisole; Aromatic hydrocarbon-based solvents such as benzene, toluene or xylene; Halogenated aromatic solvents such as chlorobenzene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylimidazolidone or acetonitrile; Or a sulfoxide-based solvent such as dimethyl sulfoxide (DMSO), and any one or a mixture of two or more of them may be used.

In addition, the reactants used in the preparation of compound (1) of Formula 1 may be prepared using a conventional organic reaction, or may be obtained and used commercially.

For example, the compound (i) having the parental structure may be prepared in the same manner as in Scheme 2 below. Scheme 2 below is only an example for explaining the present invention, but the present invention is not limited thereto.

[Scheme 2]

In Scheme 2, X is O or S, and Y is a halogen group such as bromo.

Specific examples of the method for preparing the compound of Formula 1 are presented in more detail in the following Preparation Examples.

In addition, the present invention provides an organic light-emitting device including the compound represented by Formula 1 above.

For example, the present invention provides a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers contains the compound according to the present invention. .

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 an organic light-emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.

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

2 is an example of an organic light-emitting device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron injection and transport layer 8, and a cathode 4 Is shown. In such a structure, the compound represented by Formula 1 may be included in the hole injection layer, the hole transport layer, or the emission layer. In the above structure, an electron blocking layer (not shown) may be further included between the hole transport layer and the emission layer, and a hole blocking layer (not shown) may be further included between the emission layer and the electron injection and transport layer.

The organic light-emitting device according to the present invention can be manufactured by materials and methods known in the art, except for using the compound according to the present invention.

For example, the organic light emitting device according to the present invention may be manufactured by sequentially laminating an anode, an organic material layer, and a cathode on a substrate. At this time, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. And, after forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron injection and transport layer thereon, it can be prepared by depositing a material that can be used as a cathode thereon.

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

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

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

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

It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; There are multilayered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

The hole injection layer is a layer that injects holes from the electrode, and has the ability to transport holes as a hole injection material, so that it has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and is generated from the light emitting layer. A compound that prevents the movement of excitons to the electron injection layer or the electron injection material and has excellent ability to form a thin film is preferable. It is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Organic substances, anthraquinone, polyaniline, and polythiophene-based conductive compounds, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the emission layer.The hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the emission layer, and has high mobility for holes. The material is suitable. Specific examples include an arylamine-based organic material, a conductive compound, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

Meanwhile, the organic light-emitting device according to an embodiment may further include an electron blocking layer selectively on the hole transport layer. The electron blocking layer is formed on the hole transport layer and is preferably provided in contact with the light emitting layer to control hole mobility and prevent excessive movement of electrons to increase the probability of hole-electron coupling, thereby increasing the efficiency of the organic light-emitting device. It refers to the layer that plays a role in improving the value. The electron blocking layer includes an electron blocking material, and an arylamine-based organic material may be used as an example of the electron blocking material, but is not limited thereto.

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

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

Meanwhile, the organic light-emitting device according to an embodiment may further include a hole blocking layer selectively on the emission layer. The hole blocking layer is formed on the emission layer and is preferably provided in contact with the emission layer to improve the efficiency of the organic light emitting device by increasing the probability of hole-electron bonding by controlling electron mobility and preventing excessive movement of holes. It means the layer that plays a role. The hole-blocking layer includes a hole-blocking material, and examples of the hole-blocking material include: a subazine derivative including triazine; Triazole derivatives; Oxadiazole derivatives; Phenanthroline derivatives; A compound into which an electron withdrawing group is introduced, such as a phosphine oxide derivative, may be used, but is not limited thereto.

An electron transport layer is formed on the emission layer or on the hole blocking layer. The electron transport layer is a layer that receives electrons from the cathode or an electron injection layer to be described later and transports electrons to the emission layer. As an electron transport material, the electron transport material is a material capable of receiving electrons from the cathode and transferring them to the emission layer. Larger materials are suitable. Specific examples include pyridine derivatives; Pyrimidine derivatives; Triazole derivatives; Al complex of 8-hydroxyquinoline; Complexes containing Alq _3; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.

Meanwhile, the electron injection layer is a layer located between the electron transport layer and the cathode to inject electrons from the cathode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect for the light emitting layer or the light emitting material. It is preferable to have a compound that prevents the movement of excitons generated in the light emitting layer to the hole injection layer and has excellent thin film formation ability. Specifically, LiF, NaCl, CsF, Li ₂ O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, pre Orenylidene methane, anthrone, and their derivatives, metal 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-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is not limited to this.

Meanwhile, the electron transport layer and the electron injection layer may be provided in the form of an electron transport layer and an electron injection and transport layer that simultaneously serve as an electron transport layer and an electron injection layer for transporting received electrons to the emission layer.

The organic light-emitting device according to the present invention may be a top emission type, a bottom emission type, or a double-sided emission type depending on the material used.

In addition, the compound according to the present invention 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 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 for illustrating the present invention, and the scope of the present invention is not limited thereto.

[Synthesis Example]

Synthesis Example A: Synthesis of Intermediate A

Step 1) Synthesis of Intermediate A-1

Dibenzo[b,d]furan-1-ylboronic acid (25.0g, 117.9mmol) and 1-bromo-2-nitronaphthalene (32.7g, 129.7mmol) were dissolved in Tetrahydrofuran (THF) 255ml, and in the resulting mixed solution, A solution in which potassium carbonate (65.2 g, 471.7 mmol) _{was dissolved in 125 ml of H 2} O was added. Here, tetrakis(triphenylphosphine)palladium(0) (Pd(PPh ₃ ) ₄ , 6.8g, 5.9mmol) was added and stirred for 8 hours under reflux conditions in an argon atmosphere. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was transferred to a separatory funnel, and extracted with ethyl acetate. The extract _{was dried over MgSO 4} , filtered and concentrated, and the sample was purified by silica gel column chromatography to obtain 28.8 g of Intermediate A-1. (Yield 72%, MS[M+H]+= 339)

Step 2) Synthesis of Intermediate A-2

Intermediate A-1 (25.0g, 73.7mmol) prepared in step 1, triphenylphosphine (PPh ₃ , 15.3g, 110.5mmol), and 250ml of o-dichlorobenzene (o-DCB) were added to a reactor and under reflux conditions for 24 hours. Stirred. When the reaction was completed, the mixture was cooled to room temperature, distilled under reduced pressure to remove the solvent, and extracted with _{CH 2} Cl _2. The extract _{was dried over MgSO 4} , filtered and concentrated, and the sample was purified by silica gel column chromatography to obtain 15.4 g of Intermediate A-2. (Yield 68%, MS[M+H]+= 307)

Step 3) Synthesis of Intermediate A

Intermediate A-2 prepared in step 2 (15.0g, 48.8mmol), sodium chloride (48.5g, 829.7mmol), aluminum chloride (AlCl ₃ , 247.3g, 1854.6mmol) and 450ml of benzene were added thereto at 0℃ for 16 hours. While stirring. When the reaction was completed, the mixture was washed _{with water and an aqueous NaHCO 3 solution, dried over MgSO 4} , filtered and concentrated, and the sample was purified by silica gel column chromatography to obtain 5.4 g of Intermediate A. (Yield 36%, MS[M+H]+= 305)

Synthesis Example B: Synthesis of Intermediate B

In Synthesis Example A, an intermediate in the same manner as in the preparation method of Intermediate A, except that dibenzo[b,d]furan-1-ylboronic acid was changed to dibenzo[b,d]thiophen-1-ylboronic acid. Prepared B. (MS[M+H] ⁺ = 382)

Synthesis example C: Synthesis of Intermediate C

In Synthesis Example A, Intermediate C was prepared in the same manner as in Intermediate A, except that 1-bromo-2-nitronaphthalene was changed to 1-bromo-2-nitro-6-phenylnaphthalene. (MS[M+H] ⁺ = 381)

Synthesis example D: Synthesis of Intermediate D

In Synthesis Example A, the same manufacturing method as that of Intermediate A, except that dibenzo[b,d]furan-1-ylboronic acid was changed to naphtho[1,2-b]benzofuran-7-ylboronic acid. To prepare Intermediate D. (MS[M+H] ⁺ = 355)

Synthesis Example 1: Synthesis of Compound 1

Step 1) Synthesis of Compound 1-1

Intermediate A (10.0g, 32.8mmol), 2,3-dichloroquinoxaline (7.2g, 36.0mmol) is dissolved in 300ml of toluene, sodium tert-butoxide (NaOtBu, 4.7g, 49.1mmol), bis(tri-tert-butylphosphine)palladium (0) (Pd(P-tBu ₃ ) ₂ , 0.3g, 0.7mmol) was added, followed by stirring for 6 hours under reflux conditions in an argon atmosphere. When the reaction was completed, after cooling to room temperature, H ₂ O was added and the reaction solution was transferred to a separatory funnel for extraction. The extract _{was dried over MgSO 4} , concentrated, and the sample was purified by silica gel column chromatography to obtain 11.5 g of compound 1-1. (Yield 75%, MS[M+H]+= 467)

Step 2) Synthesis of Compound 1

Compound 1-1 (10.0g, 21.4mmol) and phenylboronic acid (2.9g, 23.5mmol) were dissolved in 150ml of THF, and potassium carbonate (11.8g, 85.5mmol) was dissolved in 50ml of _{H 2 O.} Here, tetrakis(triphenylphosphine)palladium(0) (1.2g, 1.1mmol) was added, and the mixture was stirred for 8 hours under reflux conditions in an argon atmosphere. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was transferred to a separatory funnel, and extracted with ethyl acetate. The extract _{was dried over MgSO 4} , filtered and concentrated, and the sample was purified by silica gel column chromatography, and then 3.5 g of compound 1 was obtained through sublimation purification. (Yield 32%, MS[M+H]+= 509)

Synthesis Example 2: Synthesis of Compound 2

In Synthesis Example 1, except that phenylboronic acid was changed to naphthalen-2-ylboronic acid and used, compound 2 was prepared in the same manner as in the preparation method of compound 1. (MS[M+H] ⁺ = 559)

Synthesis Example 3: Synthesis of Compound 3

In Synthesis Example 1, 2,3-dichloroquinoxaline was changed to 2,3-dichlorobenzo[f]quinoxaline, except that the compound 3 was prepared in the same manner as the preparation method of Compound 1. (MS[M+H] ⁺ = 559)

Synthesis Example 4: Synthesis of Compound 4

In Synthesis Example 1, 2,3-dichloroquinoxaline was used as 2,3-dichlorobenzo[f]quinoxaline, and phenylboronic acid was used as 2-(dibenzo[b,d]furan-2-yl)-4,4,5,5-tetramethyl. Except for changing to -1,3,2-dioxaborolane and used, compound 4 was prepared in the same manner as in the preparation method of compound 1. (MS[M+H] ⁺ = 649)

Synthesis Example 5: Synthesis of Compound 5

In Synthesis Example 1, except that 2,3-dichloroquinoxaline was changed to 2,3-dichlorobenzo[4,5]thieno[2,3-b]pyrazine, and phenylboronic acid was changed to naphthalen-1-ylboronic acid, Compound 5 was prepared in the same manner as in the preparation method of compound 1. (MS[M+H] ⁺ = 615)

Synthesis Example 6: Synthesis of Compound 6

In Synthesis Example 1, 2,3-dichloroquinoxaline was used as 2,3-dichlorobenzo[4,5]thieno[2,3-b]pyrazine, and phenylboronic acid was used as 2-(9,9-dimethyl-9H-fluoren-2- Compound 6 was prepared in the same manner as in the preparation method of Compound 1, except that yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was used. (MS[M+H] ⁺ = 681)

Synthesis Example 7: Synthesis of Compound 7

In Synthesis Example 1, except that 2,3-dichloroquinoxaline was changed to 2,3-dichlorobenzofuro[2,3-b]pyrazine, and phenylboronic acid to (phenyl-d5)boronic acid was used. Compound 7 was prepared by the same method as described above. (MS[M+H] ⁺ = 554)

Synthesis Example 8: Synthesis of Compound 8

In Synthesis Example 1, compound 8 was prepared in the same manner as in the preparation method of compound 1, except that intermediate A was changed to intermediate B and used. (MS[M+H] ⁺ = 525)

Synthesis Example 9: Synthesis of Compound 9

In Synthesis Example 1, compound 9 was prepared in the same manner as in the preparation method of Compound 1, except that intermediate A was changed to intermediate B and phenylboronic acid was changed to [1,1'-biphenyl]-3-ylboronic acid. Was prepared. (MS[M+H] ⁺ = 601)

Synthesis Example 10: Synthesis of Compound 10

In Synthesis Example 1, intermediate A was used as intermediate B, 2,3-dichloroquinoxaline was used as 2,3-dichlorodibenzo[f,h]quinoxaline, and phenylboronic acid was used as 9-phenyl-2-(4,4,5,5-tetramethyl). Compound 10 was prepared in the same manner as in the preparation method of Compound 1, except for changing to -1,3,2-dioxaborolan-2-yl)-9H-carbazole. (MS[M+H] ⁺ = 790)

Synthesis example 11: Synthesis of compound 11

In Synthesis Example 1, compound 11 was prepared in the same manner as in the preparation method of compound 1, except that intermediate A was changed to intermediate C and phenylboronic acid was changed to (phenyl-d5) boronic acid. (MS[M+H] ⁺ = 591)

Synthesis example 12: Synthesis of compound 12

In Synthesis Example 1, compound 12 was prepared in the same manner as in the preparation method of compound 1, except that intermediate A was changed to intermediate D and phenylboronic acid was changed to dibenzo[b,d]furan-4-ylboronic acid. I did. (MS[M+H] ⁺ = 650)

[Device example]

Comparative Example 1

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

On the prepared ITO transparent electrode, the following HI-A and hexaazatriphenylene (HAT-CN) were sequentially thermally vacuum deposited to a thickness of 800 Å and 50 Å, respectively, to form a hole injection layer. The following HT-A was vacuum-deposited to a thickness of 800 Å as a hole transport layer, and EB-A was thermally vacuum deposited to a thickness of 600 Å as an electron blocking layer thereon. Subsequently, on the electron blocking layer, the following host RH-A and dopant RD were mixed at a weight ratio of 98:2 and then vacuum deposited to a thickness of 400 Å to form a light emitting layer. Subsequently, as an electron transport layer, the following ET-A and Liq were mixed at a weight ratio of 1:1 and thermally vacuum deposited to a thickness of 360 Å, and Liq was vacuum deposited thereon to a thickness of 5 Å to form an electron injection layer.

On the electron injection layer, magnesium and silver were sequentially mixed at a weight ratio of 10:1 and deposited to a thickness of 220 Å, and aluminum was deposited thereon to a thickness of 1000 Å to form a cathode, thereby manufacturing an organic light-emitting device.

Comparative Examples 2 and 3, and Examples 1 to 12

Organic light emission of Comparative Examples 2 and 3, and Examples 1 to 12 using the same method as in Comparative Example 1, except that the compound shown in Table 1 was used instead of RH-A in Comparative Example 1 Each device was fabricated.

By applying a current to the organic light emitting device fabricated in the above Examples and Comparative Examples, driving voltage, current efficiency, and lifetime (LT97) were measured, and the results are shown in Table 1 below. At this time, voltage and efficiency were measured by applying a current density ^{of 10mA/cm 2.} In addition, LT97 refers to the time until the initial luminance decreases to 97% at the current density of 20 mA/cm ^2.

Host @ 10mA / cm ² @20mA/cm ² Driving voltage
(V) Current efficiency
(cd/A) LT97 (hr) Example 1 Compound 1 4.54 22.5 110 Example 2 Compound 2 4.53 22.3 121 Example 3 Compound 3 4.56 22.0 123 Example 4 Compound 4 4.61 22.8 111 Example 5 Compound 5 4.58 22.1 108 Example 6 Compound 6 4.53 21.3 97 Example 7 Compound 7 4.56 22.6 101 Example 8 Compound 8 4.76 23.1 106 Example 9 Compound 9 4.71 23.0 104 Example 10 Compound 10 4.73 23.3 108 Example 11 Compound 11 4.58 22.1 132 Example 12 Compound 12 4.65 22.9 95 Comparative Example 1 RH-A 5.10 18.3 65 Comparative Example 2 RH-B 5.15 20.9 83 Comparative Example 3 RH-C 5.81 12.3 46

The compounds RH-B and RH-C used in Comparative Examples 2 and 3 are compounds having the following structures, respectively.

The compound represented by Formula 1 is composed of a structure in which the structure of Formula 2 serves as an electron acceptor and a parental structure that serves as an electron donor are connected. In addition, since the two units of completely different properties are directly bonded, they have a small band gap by exchanging charges inside the molecule, which is advantageous for energy transfer to the red dopant and is suitable for use as a host of the red light emitting layer. In addition, the parental structure serving as an electron donor exhibits high stability by condensing both benzocarbazole and benzofuran or benzothiophene to form a ring. In particular, the structure in which the unit serving as an electron acceptor has two nitrogen atoms facing each other in the form of pyrazine, as in the structure of Formula 2, has a stronger electron pulling property than the quinazoline structure applied in the comparative example. Show.

As a result, when the compounds having the structure of Formula 1 are applied as a host of the red emission layer of an organic electroluminescent device, the characteristics of low voltage, high efficiency, and long life can be obtained, thereby obtaining an optimum device.

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

Claims (10)

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

In Formula 1,
X is O, or S,
L is a single bond; Substituted or unsubstituted C _6-60 arylene; _{C 2-60} heteroarylene containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S; and,
R ₁ , R ₂ , R ₃ , and R ₄ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _2-60 alkynyl; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _6-60 aryl; _{C 2-60} heteroaryl including any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O, and S; Substituted or unsubstituted tri(C _1-60 alkyl)silyl; Or a substituted or unsubstituted tri(C _6-60 aryl)silyl, or two adjacent substituents are bonded to form a C _6-60 aromatic ring,
n1 is an integer from 0 to 2,
n2 to n4 are each independently an integer of 0 to 3,
Ar ₁ is represented by the following formula (2),
[Formula 2]

In Chemical Formula 2,
Ar ₂ is substituted or unsubstituted C _6-60 aryl; _{Or C 2-60} heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S; and,
V ₁ to V ₄ are each independently CR _a or N,
W ₁ and W ₂ are each independently a single bond, CR _b , O or S,
R _a and R _b are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _6-60 aryl; _{Or C 2-60} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S; Or, or two adjacent R _a , or two adjacent R _b are bonded to each other to C _{6- 60} to form an aromatic ring,
p is an integer of 0 or 1.
The method of claim 1,
L is a single bond,
compound.
The method of claim 1,
R ₁ , R ₂ , R ₃ and R ₄ are all hydrogen,
compound.
The method of claim 1,
One of R ₁ , R ₂ , R ₃ and R ₄ is phenyl or pyridinyl, and the other is hydrogen,
compound.
The method of claim 1,
Two adjacent R ₁ , two adjacent R ₂ , two adjacent R ₃ , or two adjacent R ₄ bonded to each other to form a benzene ring, the rest being hydrogen,
compound.
The method of claim 1,
The Ar ₁ is any one selected from the group consisting of the following Chemical Formulas 2-1 to 2-3,
compound:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In Formulas 2-1 to 2-3,
Ar ₂ is as defined in claim 1,
R _a1 , R _a2 and R _a3 are each independently hydrogen or deuterium; Or two adjacent R _a1 , two adjacent R _a2 , or two adjacent R _a3 bonded to each other to form a benzene ring, and the rest is hydrogen,
Each R _b1 is independently hydrogen or deuterium,
W ₃ and W ₄ are each independently O or S,
p is an integer of 0 or 1.
The method of claim 1,
The Ar ₁ is any one selected from the group consisting of,
compound:

In the above formulas,
Ar ₂ is as defined in claim 1,
W ₃ and W ₄ are each independently O or S.
The method of claim 1,
Ar ₂ is phenylyl, biphenylyl, terphenylyl, naphthyl, anthracenyl, phenanthrenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, dibenzofuranyl, di Benzothiophenyl, carbazol-9-yl, or 9-phenyl-carbazolyl,
Ar ₂ is unsubstituted or substituted with one or more deuterium,
compound.
The method of claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of,
compound:

A first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers contains the compound according to any one of claims 1 to 9 That is, an organic light emitting device.

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