KR20210020843A - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention relates to a novel compound represented by chemical formula 1 and to an organic light emitting device comprising the same. The compound is capable of improving efficiency, having low driving voltage, and/or improving service life properties 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 using organic materials. An organic light-emitting device using the organic light-emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.

The organic light emitting device generally has a structure including an anode and a cathode, and an organic material layer between the anode and the cathode. The organic material layer is often made of a multi-layered structure 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. It glows when it falls back to the ground.

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

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 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,

L is substituted or unsubstituted dibenzofuran-diyl, or substituted or unsubstituted dibenzothiophene-diyl,

X ₁ to X ₃ are each independently CR _a or N, but at least one of _{X 1} to X _{3 is N,}

Each R _a is 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,

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,

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

n3 is an integer from 0 to 4.

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, wherein the organic light-emitting device comprises: to provide.

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

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 the understanding of the present invention.

및

는 다른 치환기에 연결되는 결합을 의미한다.In this specification,

And

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 it is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the ester group may be substituted with an oxygen of the ester group with a straight chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

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

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

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

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

In the present specification, the alkyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cycloheptylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

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

In the present specification, the cycloalkyl group is not particularly limited, but is preferably 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

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

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 carbons is not particularly limited, but 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, the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, arylamine group, and 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, for heteroaryl among heteroarylamines, the above-described description of heteroaryl may be applied. In the present specification, the alkenyl group of the aralkenyl group is the same as the example of the alkenyl group described above. In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group. In the present specification, the description of the 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 the cycloalkyl group described above may be applied except that the hydrocarbon ring is formed by bonding of two substituents. In the present specification, the 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 any one selected from the group consisting of:

In the above equations,

Y is O or S,

R _b and R _c are each independently hydrogen; heavy hydrogen; Or substituted or unsubstituted C _6-60 aryl; and,

p1 is an integer from 0 to 2,

p2 is an integer from 0 to 4,

p3 and p4 are each independently an integer of 0 to 3.

Preferably, _{both R b} and R _c are hydrogen. At this time, preferably, all of p1 to p4 are 0.

Preferably _{, at least one of R b} and R _c may be deuterium, and the rest may be hydrogen.

Preferably, _{both R b} and R _c are deuterium, wherein preferably p1 is an integer of 2, p2 is an integer of 4, and p3 and p4 are both integers of 3.

Preferably _{, one of R b} and R _c is phenyl, and the other is hydrogen.

In addition, in Formula 1, preferably, one or two of _{X 1} to X _{3 are CR a} , and the remainder is N. At this time, preferably, _{all of R a} are hydrogen.

Preferably, all of X ₁ to X ₃ are N.

Preferably, Ar ₁ and Ar ₂ are each independently phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, dibenzofuranyl, or dibenzothiophenyl, and Ar ₁ and Ar ₂ Each is independently unsubstituted or substituted with one or more deuterium. Alternatively _{, at least one of Ar 1} and Ar ₂ may be all substituted with deuterium.

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

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

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

.

.

Meanwhile, the present invention provides a method of preparing the compound represented by Formula 1 using an amine substitution reaction or a Suzuki coupling reaction.

For example, the compound represented by Formula 1 may be prepared by an amine substitution reaction of compound (i) and compound (ii) as in Scheme 1:

[Scheme 1]

In Reaction Scheme 1, Ar ₁ , Ar ₂ , L, X ₁ to X ₃ , R ₁ to R ₄ , n ₁ to n ₄ are as previously defined, and Z ₁ is a halogen group such as chloro or boromo.

The amine substitution half may be performed in the presence of a palladium-based catalyst and a base.

As the palladium catalyst, bis(tri-tert-butylphosphine)palladium(0) (bis(tri-tert-butylphosphine)palladium(0); Pd(P-tBu ₃ ) ₂ ), tetrakis-(triphenylphosphine) Pin) palladium (tetrakis(triphenylphosphine)palladium(0), Pd(PPh ₃ ) ₄ ), tris(dibenzylideneacetone)dipalladium (Tris(dibenzylideneacetone)dipalladium, Pd ₂ (dba) ₃ )), bis(triphenyl Phosphine) palladium chloride (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 (Palladium(II) chloride, PdCl ₂ ), and the like, Any one or a mixture of two or more of these may be used.

In addition, as the base, sodium tert-butoxide, potassium tert-butoxide, sodium tert-pentoxide, sodium ethoxide, Inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, sodium 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.

In addition, the reaction of the compound (i) and the compound (ii) may be carried out in an organic solvent. As the organic solvent, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol diethyl ether, dimethoxyethane, bis (2-methoxyethyl) ether, diethylene glycol diethyl ether, tetrahydrofuran Or an ether solvent such as 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.

Further, the compounds (i) and (ii) may be directly prepared by using a conventional chemical reaction, or may be obtained and used commercially. In the case of direct manufacturing, the manufacturing method will be described in detail in Synthesis Examples below.

As another example, the compound represented by Formula 1 may be prepared by a Suzuki coupling reaction of compound (iii) and compound (iv) as shown in Scheme 2 below:

[Scheme 2]

In Reaction Scheme 2, Ar ₁ , Ar ₂ , L, X ₁ to X ₃ , R ₁ to R ₄ , n ₁ to n ₄ are as previously defined, Z ₂ is a halogen group such as chloro or boromo, and W Is a boron-containing organic group such as a boronic acid group, a boronic acid ester group, or a boronic acid pinacol ester group.

The Suzuki coupling reaction may be carried out in the presence of a base and a palladium catalyst, wherein the base and palladium catalyst usable are the same as described in the amine substitution reaction.

In addition, the Suzuki coupling reaction may be carried out in water as a solvent.

Further, the compound (iii) and the compound (iv) may be directly prepared using a conventional chemical reaction, or may be obtained and used commercially. In the case of direct manufacturing, the manufacturing method will be described in detail in Synthesis Examples below.

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

For example, the present invention provides a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers 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 organic light emitting device of an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of 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.

The organic light emitting device according to the present invention can be manufactured using 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 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); A combination of a metal and an oxide 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 multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

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

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

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

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the emission layer. As an electron transport material, a material capable of injecting electrons from the cathode and transferring them to the emission layer, and a material having high mobility for electrons is suitable. Do. Specific examples include Al complex of 8-hydroxyquinoline; Complexes containing Alq _3; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials that have a low work function and are followed by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium, and samarium, and in each case an aluminum layer or a silver layer follows.

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

Examples of the metal complex compound include lithium 8-hydroxyquinolinato, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is not limited to this.

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

In addition, the compound 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 fabrication of the organic light emitting device according to the present invention described above will be described in detail in the following examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

[Synthesis Example]

Synthesis Example 1: Synthesis of Compound 1

Step 1) Synthesis of Compound 1-1

In a nitrogen atmosphere, 1-bromo-3-chlorodibenzo[b,d]furan (15.0g, 53.3mmol) and bis(pinacolato)diboron (14.9g, 58.6mmol) were stirred in 300ml of 1,4-dioxane while refluxing. After that, potassium acetate (KOAc) (7.8g, 79.9mmol) was added, stirred sufficiently, and then bis(dibenzylideneacetone)palladium(0) (Pd(dba) ₂ ) (0.9g, 1.6mmol) and tricyclohexylphosphine (PCy ₃ ) (0.9 g, 3.2mmol) was added. After reacting for 6 hours, cooling to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.0 g of compound 1-1. (Yield 74%, MS: [M+H]+= 330)

Step 2) Synthesis of Compound 1-2

In a nitrogen atmosphere, compound 1-1 (15.0g, 45.6mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (13.4g, 50.2mmol) were added to Tetrahydrofuran (THF) 300ml and stirred and refluxed. I did. After that, potassium carbonate (K ₂ CO ₃ ) (25.2g, 182.6mmol) was dissolved in 76ml of water, added, stirred thoroughly, and then tetrakis(triphenylphosphine)palladium(0) (Pd(PPh ₃ ) ₄ ) (1.6g, 1.4mmol ) Was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.1 g of compound 1-2. (Yield 76%, MS: [M+H]+= 435)

Step 3) Synthesis of Compound 1

In a nitrogen atmosphere, compound 1-2 (15.0g, 34.6mmol) and 3H-3-azadibenzo[g,ij]naphtho[2,1,8-cde]azulene (11.1g, 38.0mmol) were added to 300ml of toluene and stirred. Refluxed. After that, sodium tert-butoxide (NaOtBu) (5.0g, 51.9mmol), bis(tri-tert-butylphosphine)palladium(0) (Pd(P-tBu ₃ ) ₂ ) (0.5g, 1mmol) were added. After the reaction for 12 hours, the mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 11.4 g of compound 1 was prepared through sublimation purification. (Yield 48%, MS: [M+H]+= 690)

Synthesis Example 2: Synthesis of Compound 2

In Synthesis Example 1, 1-bromo-3-chlorodibenzo[b,d]furan was converted to 1-bromo-4-chlorodibenzo[b,d]furan, and 2-chloro-4,6-diphenyl-1,3,5- Compound 2 was prepared by the same method as the method for preparing compound 1, except that triazine was changed to 2-chloro-4-(naphthalen-1-yl)-6-phenyl-1,3,5-triazine. I did. (MS[M+H] ⁺ = 740)

Synthesis Example 3: Synthesis of Compound 3

Step 1) Synthesis of compound 3-1

In a nitrogen atmosphere, 1-chloro-7-fluorodibenzo[b,d]furan (15.0g, 68.0mmol) and bis(pinacolato)diboron (19.0g, 74.8mmol) were stirred in 300ml of 1,4-dioxane while refluxing. After that, potassium acetate (10.0g, 102.0mmol) was added and sufficiently stirred, and then bis(dibenzylideneacetone)palladium(0) (1.2g, 2.0mmol) and tricyclohexylphosphine (1.1g, 4.1mmol) were added. After reacting for 9 hours, cooling to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8 g of compound 3-1. (Yield 65%, MS: [M+H]+= 313)

Step 2) Synthesis of compound 3-2

Compound 3-1 (15.0g, 48.1mmol) and 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6-phenyl-1,3,5-triazine (18.9g, 52.9mmol) was added to 300ml of THF and stirred and refluxed. After that, potassium carbonate (26.6g, 192.2mmol) was dissolved in 80ml of water, and after sufficiently stirring, tetrakis(triphenylphosphine)palladium(0) (1.7g, 1.4mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.8 g of compound 3-2. (Yield 77%, MS: [M+H]+= 509)

Step 3) Synthesis of compound 3

In a nitrogen atmosphere, compound 3-2 (20.0g, 39.4mmol) and 3H-3-azadibenzo[g,ij]naphtho[2,1,8-cde]azulene (12.6g, 43.3mmol) were added to DMF 400ml and refluxed. Stirred. After that, cesium carbonate (38.5g, 118.2mmol) was added and stirred. After 10 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 12.6 g of compound 3 was prepared through sublimation purification. (Yield 41%, MS: [M+H]+= 780)

Synthesis Example 4: Synthesis of Compound 4

In Synthesis Example 3, 1-chloro-7-fluorodibenzo[b,d]furan was converted to 3-chloro-6-fluorodibenzo[b,d]furan, and 2-chloro-4-(dibenzo[b,d]furan-1 Except that -yl)-6-phenyl-1,3,5-triazine was changed to 2-chloro-4-(naphthalen-2-yl)-6-phenyl-1,3,5-triazine and used, Compound 4 was prepared by the same method as the method for preparing compound 3. (MS[M+H] ⁺ = 740)

Synthesis Example 5: Synthesis of Compound 5

Step 1) Synthesis of compound 5-1

2-bromo-7-chlorodibenzo[b,d]furan (15.0g, 53.3mmol) and 3H-3-azadibenzo[g,ij]naphtho[2,1,8-cde]azulene (17.1g, 58.6) in nitrogen atmosphere mmol) was added to 300ml of toluene and stirred and refluxed. After this, sodium tert-butoxide (7.7g, 79.9mmol) and bis (tri-tert-butylphosphine) palladium(0) (0.8g, 1.6mmol) were added. After the reaction for 9 hours, it was cooled to room temperature, and the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.0 g of compound 5-1. (Yield 80%, MS: [M+H]+= 493)

Step 2) Synthesis of compound 5-2

In a nitrogen atmosphere, compound 5-1 (15.0g, 30.5mmol) and bis(pinacolato)diboron (8.5g, 33.5mmol) were stirred under reflux in 300ml of 1,4-dioxane. After that, potassium acetate (4.5g, 45.7mmol) was added and sufficiently stirred, and then bis(dibenzylideneacetone)palladium(0) (0.5g, 0.9mmol) and tricyclohexylphosphine (0.5g, 1.8mmol) were added. After reacting for 7 hours, cooling to room temperature, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound 5-2. (Yield 72%, MS: [M+H]+= 584)

Step 3) Synthesis of compound 5

In a nitrogen atmosphere, compound 5-2 (15.0g, 25.7mmol) and 4-chloro-2,6-diphenylpyrimidine (7.5g, 28.3mmol) were added to 300ml of THF and stirred and refluxed. After that, potassium carbonate (14.2g, 102.8mmol) was dissolved in 43ml of water and stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (0.9g, 0.8mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 8.3 g of compound 5 was prepared through sublimation purification. (Yield 47%, MS: [M+H]+= 689)

Synthesis Example 6: Synthesis of Compound 6

Step 1) Synthesis of compound 6-1

In a nitrogen atmosphere, dibenzo[b,d]thiophen-4-ylboronic acid (15.0g, 65.8mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (19.4g, 72.3mmol) were added to THF 300ml. Put in, and stirred and refluxed. Thereafter, potassium carbonate (36.4g, 263.1mmol) was dissolved in 109ml of water and stirred sufficiently, and then tetrakis(triphenylphosphine)palladium(0) (2.3g, 2mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.5 g of compound 6-1. (Yield 75%, MS: [M+H]+= 417)

Step 2) Synthesis of compound 6-2

Compound 6-1 (20.0g, 48.1mmol) and N-bromosuccinimide (NBS) (9.0g, 50.5mmol) were added to 400ml of dimethylformamide (DMF) and stirred at room temperature in a nitrogen atmosphere. After the reaction for 5 hours, the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.1 g of compound 6-2. (Yield 72%, MS: [M+H]+= 495)

Step 3) Synthesis of compound 6

In a nitrogen atmosphere, compound 6-2 (15.0g, 30.3mmol) and 3H-3-azadibenzo[g,ij]naphtho[2,1,8-cde]azulene (9.7g, 33.4mmol) were added to 300ml of toluene and stirred. Refluxed. After that, sodium tert-butoxide (4.4g, 45.5mmol) and bis (tri-tert-butylphosphine) palladium(0) (0.5g, 0.9mmol) were added. After the reaction for 6 hours, it was cooled to room temperature, and the organic layer was separated using chloroform and water, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. After the concentrated compound was purified by silica gel column chromatography, 7.3g of compound 6 was prepared through sublimation purification. (Yield 34%, MS: [M+H]+= 706)

[Device example]

Example 1

A glass substrate coated with a thin film of ITO (Indium Tin Oxide) to a thickness of 1,400Å was put in distilled water dissolved in a detergent and washed with ultrasonic waves. In this case, Fischer Co. product was used as a detergent, and distilled water secondarily filtered with a filter made by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, 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 and hexanitril 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 as a hole transport layer was vacuum-deposited to a thickness of 800 Å, and then EB-A as an electron blocking layer was thermally vacuum deposited to a thickness of 600 Å.

Subsequently, the compound 1 prepared in Synthesis Example 1 and 2wt% of the dopant RD were vacuum deposited as a light emitting layer to a thickness of 400Å.

Subsequently, as an electron transport layer, the following ET-A and Liq were thermally vacuum deposited to a thickness of 360 Å at a ratio of 1:1, and Liq was vacuum deposited to a thickness of 5 Å thereon to form an electron injection layer.

An organic light emitting diode was manufactured by sequentially depositing magnesium and silver on the electron injection layer to a thickness of 220 Å at a ratio of 10:1 and aluminum to a thickness of 1000 Å to form a cathode.

Examples 2 to 6

The organic light-emitting devices of Examples 2 to 6 were each prepared in the same manner as in Example 1, except that the host compound of the emission layer in Example 1 was changed to the compounds shown in Table 1 instead of Compound 1. Was produced.

The compounds used in the examples of Table 1 are as follows.

Comparative Examples 1 to 3

The organic light emitting devices of Comparative Examples 1 to 3 were manufactured using the same method as in Example 1, except that the host compound of the emission layer in Example 1 was changed to the compounds shown in Table 1 instead of Compound 1 I did. The compounds of RH-A, RH-B and RH-C used in Comparative Examples of Table 1 are as follows.

Experimental Example 1

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

Host @ 10 mA / cm ² @ 20 mA / cm ² Voltage
(V) efficiency
(cd/A) LT97 (hr) Example 1 Compound 1 4.86 21.6 106 Example 2 Compound 2 4.89 21.3 97 Example 3 Compound 3 4.86 21.7 107 Example 4 Compound 4 4.95 20.2 104 Example 5 Compound 5 5.03 19.9 93 Example 6 Compound 6 5.16 19.4 97 Comparative Example 1 RH-A 6.42 16.3 65 Comparative Example 2 RH-B 6.31 12.1 52 Comparative Example 3 RH-C 7.52 8.2 23

As a result of the experiment, the organic light-emitting device of the example in which the compounds having the structure of Formula 1 were used as the host of the red emission layer of the organic electroluminescent device was compared with the organic light-emitting device of the comparative example using the compounds not having the structure of Formula 1 as a host, It can be seen that it exhibits the characteristics of low voltage, high efficiency, and long life.

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 (12)

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

In Formula 1,
L is substituted or unsubstituted dibenzofuran-diyl, or substituted or unsubstituted dibenzothiophene-diyl,
X ₁ to X ₃ are each independently CR _a or N, but at least one of _{X 1} to X _{3 is N,}
Each R _a is 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,
Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,
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 and n4 are each independently an integer of 0 to 3,
n3 is an integer from 0 to 4.
The method of claim 1,
The L is any one selected from the group consisting of,
compound:

In the above equations,
Y is O or S,
R _b and R _c are each independently hydrogen; heavy hydrogen; Or substituted or unsubstituted C _6-60 aryl; and,
p1 is an integer from 0 to 2,
p2 is an integer from 0 to 4,
p3 and p4 are each independently an integer of 0 to 3.
The method of claim 2,
Wherein both R _b and R _c are hydrogen, or
Wherein R _b and R _c are both deuterium,
compound.
The method of claim 2,
One of R _b and R _c is phenyl, and the other is hydrogen,
compound.
The method of claim 1,
Any one or two of X ₁ to X _{3 are CR a} , and the rest are N,
Wherein R _a is all hydrogen,
compound.
The method of claim 1,
Wherein X ₁ to X ₃ are all N,
compound.
The method of claim 1,
Ar ₁ and Ar ₂ are each independently phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, dibenzofuranyl, or dibenzothiophenyl,
The Ar ₁ and Ar ₂ are each independently unsubstituted or substituted with one or more deuterium,
compound.
The method of claim 1,
Wherein 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, and the rest 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, and the rest are all hydrogen; or
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, and one of the other is phenyl, and the others are all hydrogen,
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 includes the compound according to any one of claims 1 to 11 That is, an organic light emitting device.

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