KR102455462B1 - 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 comprising the same.

Description

Novel compound and organic light emitting device using the same

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

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

An organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode. The organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, it may be made of an electron injection layer, etc. When a voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons It lights up when it falls back to the ground state.

The 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 can be used in a solution process at the same time.

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; Substituted or unsubstituted C _2-60 heteroarylene 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 combine to form a C _6-60 aromatic ring,

n1 and n4 are each independently an integer of 0 to 2,

n2 and n3 are each independently an integer of 0 to 3,

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

[Formula 2]

In Formula 2,

Ar ₂ is 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;

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 including any one or more heteroatoms selected from the group consisting of N, O and S; Or, two adjacent R _a , or two adjacent R _b are bonded to each other to C _{6- 60} forming 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 at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the compound represented by Formula 1 above; to provide.

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

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

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

또는

는 다른 치환기에 연결되는 결합을 의미한다.In this specification,

or

means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; cyano group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an aryl phosphine group; or N, O, and S atoms, which is substituted or unsubstituted with one or more substituents selected from the group consisting of heteroaryl containing one or more . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in 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 from 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

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

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

In the present specification, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. However, the present invention is not limited thereto.

In the present specification, the boron group specifically includes a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron 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 number of carbon atoms in the alkyl group is 1 to 20. 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, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but are not limited thereto.

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

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

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a monocyclic aryl group such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a chrysenyl group, or a fluorenyl group, but is not limited thereto.

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

etc. can be However, the present invention is not limited thereto.

In the present specification, 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 is preferably from 2 to 60 carbon atoms. Examples of heteroaryl include xanthene, thioxanthen, thiophene, furan, pyrrole, imidazole, thiazole, oxazole, oxadiazole, triazole, pyridyl, bipyridyl, Pyrimidyl group, triazine group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyridopyrazinyl 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), an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

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

The present invention provides a compound represented by the above formula (1).

In Formula 1, preferably L is a single bond.

Preferably, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen. In this case, 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. In this case, 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 combine with 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 Formula 1 above,

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 combine with each other to form a benzene ring, the remainder being hydrogen,

R _b1 is each 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 Formula 1 above,

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, dibenzofu Ranyl, dibenzothiophenyl, carbazol-9-yl, or 9-phenyl-carbazolyl, wherein Ar ₂ is unsubstituted or substituted with one or more deuterium.

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

On the other hand, the present invention provides a method for preparing a compound represented by the formula (1), as shown in Scheme 1 below as an example:

[Scheme 1]

In 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 Boronic acid pinacol ester (boronic acid pinacol ester), such as a boron-containing organic group, Ar ₁ ' is a substituent having the following structure,

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

Specifically, the compound (1) of Formula 1 is a compound (iii) by reacting a compound (i) having a parent nucleus structure and a compound (ii) containing an electron accepting substituent bonded to the parent nucleus structure through a palladium-catalyzed coupling reaction. preparing a; and Suzuki coupling reaction of the compound (iii) with the compound (iv) containing the above-described boron-containing organic group, in the presence of a base and a palladium catalyst.

As a palladium-based catalyst usable for the palladium-catalyzed coupling reaction and the Suzuki coupling reaction, 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 (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 (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 thereof may be used.

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

Examples of the organic solvent include diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol diethyl ether, dimethoxyethane, bis(2-methoxyethyl)ether, diethylene glycol diethyl ether, tetrahydro etheric 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 thereof 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 commercially obtained and used.

For example, the compound (i) having the parent nucleus structure may be prepared by the same method as in Scheme 2 below. Scheme 2 below is only an example for explaining the present invention, and 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 Preparation Examples below.

In addition, the present invention provides an organic light emitting device including the compound represented by the formula (1).

In one example, the present invention provides a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound according to the present invention. .

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

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

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

The organic light emitting device according to the present invention may 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 stacking an anode, an organic material layer, and a cathode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode. and 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, and then depositing a material that can be used as a cathode thereon.

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

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

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

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

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

The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer. material is suitable. Specific examples include, but are not limited to, an arylamine-based organic material, a conductive compound, and a block copolymer having a conjugated portion and a non-conjugated portion together.

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

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

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

On the other hand, the organic light emitting device according to an embodiment may further selectively include a hole blocking layer on the light emitting layer. The hole blocking layer is formed on the light emitting layer, preferably provided in contact with the light emitting layer, to improve the efficiency of the organic light emitting device by controlling electron mobility and preventing excessive movement of holes to increase the hole-electron coupling probability layer that plays a role. The hole blocking layer includes a hole blocking material, and examples of the hole blocking material include azine derivatives 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 the present invention is not limited thereto.

An electron transport layer is formed on the light emitting 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 them to the light emitting 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.

On the other hand, the electron injection layer is located between the electron transport layer and the cathode and injects electrons from the cathode, has the ability to transport electrons, and 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 use a compound that has excellent properties, prevents movement of excitons generated in the light emitting layer to the hole injection layer, and is excellent in 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 the like, derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.

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

On the other hand, the electron transport layer and the electron injection layer can be provided in the form of an electron injection and transport layer that simultaneously performs the roles of the electron transport layer and the electron injection layer for transporting the received electrons to the light emitting layer.

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

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

[Synthesis 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 255ml of Tetrahydrofuran (THF), and in the resulting mixed solution, A solution of potassium carbonate (65.2 g, 471.7 mmol) dissolved in H ₂ O 125 ml was added. Here, tetrakis(triphenylphosphine)palladium(0) (Pd(PPh ₃ ) ₄ , 6.8 g, 5.9 mmol) was added, and the mixture was stirred for 8 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, after cooling to room temperature, the reaction solution was transferred to a separatory funnel, and extracted with ethyl acetate. After drying the extract with MgSO ₄ , filtration and concentration, 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), triphenylphosphine (PPh ₃ , 15.3g, 110.5mmol), and 250ml of o-dichlorobenzene (o-DCB) prepared in step 1 were put into a reactor and refluxed for 24 hours. stirred. Upon completion of the reaction, 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 (15.0g, 48.8mmol), sodium chloride (48.5g, 829.7mmol), aluminum chloride (AlCl ₃ , 247.3g, 1854.6mmol) and 450ml of benzene prepared in step 2 were added, and 16 hours at 0°C. stirred for a while. When the reaction was completed, it was washed with water and an aqueous NaHCO ₃ solution, dried over MgSO ₄ , filtered and concentrated, and then 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, except that dibenzo[b,d]furan-1-ylboronic acid was changed to dibenzo[b,d]thiophen-1-ylboronic acid and used, the intermediate was prepared in the same manner as in the preparation method of Intermediate A. B was prepared. (MS[M+H] ⁺ = 382)

Synthesis example C: Synthesis of Intermediate C

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

Synthesis example D: Synthesis of intermediate D

In Synthesis Example A, except that dibenzo[b,d]furan-1-ylboronic acid was changed to naphtho[1,2-b]benzofuran-7-ylboronic acid and used, the same preparation method as the preparation method of Intermediate A Intermediate D was prepared. (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) was dissolved in 300ml of toluene, and sodium tert-butoxide (NaOtBu, 4.7g, 49.1mmol), bis(tri-tert-butylphosphine)palladium (0) (Pd(P-tBu ₃ ) ₂ , 0.3 g, 0.7 mmol) was added, and the mixture was stirred for 6 hours under reflux conditions in an argon atmosphere. Upon completion of the reaction, 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 (10.0 g, 21.4 mmol) and phenylboronic acid (2.9 g, 23.5 mmol) were dissolved in 150 ml of THF, and potassium carbonate (11.8 g, 85.5 mmol) was dissolved in H ₂ O 50 ml. 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. Upon completion of the reaction, after cooling to room temperature, the reaction solution was transferred to a separatory funnel, and extracted with ethyl acetate. After drying the extract with MgSO ₄ , filtration and concentration, 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, compound 2 was prepared in the same manner as in the preparation method of compound 1, except that phenylboronic acid was changed to naphthalen-2-ylboronic acid and used. (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, and compound 3 was prepared in the same manner as in the preparation method of compound 1, except that it was used. (MS[M+H] ⁺ = 559)

Synthesis Example 4: Synthesis of compound 4

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

Synthesis Example 5: Synthesis of compound 5

In Synthesis Example 1, 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 by the same preparation method as that of compound 1. (MS[M+H] ⁺ = 615)

Synthesis Example 6: Synthesis of compound 6

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

Synthesis Example 7: Synthesis of compound 7

In Synthesis Example 1, 2,3-dichloroquinoxaline was changed to 2,3-dichlorobenzofuro[2,3-b]pyrazine, and phenylboronic acid was changed to (phenyl-d5)boronic acid. Compound 7 was prepared in the same manner 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 used as Intermediate B and phenylboronic acid was changed to [1,1'-biphenyl]-3-ylboronic acid. prepared. (MS[M+H] ⁺ = 601)

Synthesis Example 10: Synthesis of compound 10

In Synthesis Example 1, intermediate A to intermediate B, 2,3-dichloroquinoxaline to 2,3-dichlorodibenzo[f,h]quinoxaline, phenylboronic acid to 9-phenyl-2-(4,4,5,5-tetramethyl -1,3,2-dioxaborolan-2-yl)-9H-carbazole was used, except that compound 10 was prepared in the same manner as in the preparation method of compound 1. (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. did. (MS[M+H] ⁺ = 650)

[Element example]

Comparative Example 1

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

On the thus prepared ITO transparent electrode, the following HI-A and hexanitrile 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 thereon, and EB-A below as an electron blocking layer was thermally vacuum-deposited thereon to a thickness of 600 Å. Then, on the electron blocking layer, the following host RH-A and dopant RD were mixed in a weight ratio of 98:2 and vacuum deposited to a thickness of 400 Å to form a light emitting layer. Then, as an electron transport layer, the following ET-A and Liq were mixed in a weight ratio of 1:1 and thermally vacuum-deposited to a thickness of 360 Å, and then Liq was again vacuum-deposited to a thickness of 5 Å to form an electron injection layer.

On the electron injection layer, magnesium and silver were sequentially mixed in 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 diodes manufactured in 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 means the time until the initial luminance decreases to 97% at a current density of 20 mA/cm ² .

host @10mA/cm ² @20mA/cm ² drive 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

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 serving as an electron acceptor and a parent nucleus structure serving as an electron donor are connected. In addition, since two units with 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 for the red light emitting layer. In addition, the parent nucleus 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 acting as an electron acceptor has two nitrogen atoms facing each other in the form of pyrazine, such as the structure of Formula 2, has a stronger electron-attracting property than the quinazoline structure applied in Comparative Example, and exhibits low voltage characteristics when applied as a host. indicates.

As a result, when the compounds having the structure of Formula 1 are applied as the host of the red light emitting layer of the organic electroluminescent device, it is possible to obtain an optimal device by showing 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 (10)

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

In Formula 1,
X is O, or S;
L is a single bond,
R ₁ , R ₂ , R ₃ , and R ₄ are each independently hydrogen; heavy hydrogen; or phenyl, or two adjacent substituents combine to form a benzene ring,
n1 and n4 are each independently an integer of 0 to 2,
n2 and n3 are each independently an integer of 0 to 3,
Ar ₁ is any one selected from the group consisting of

In the above formulas,
Ar ₂ is phenylyl, biphenylyl, terphenylyl, naphthyl, anthracenyl, phenanthrenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, dibenzofuranyl, dibenzo thiophenyl, carbazol-9-yl, or 9-phenyl-carbazolyl;
Wherein Ar ₂ is unsubstituted, or substituted with one or more deuterium,
W ₃ and W ₄ are each independently O or S.
delete 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 and the other is hydrogen;
compound.
According to claim 1,
two adjacent R ₁ , two adjacent R ₂ , two adjacent R ₃ , or two adjacent R ₄ combine with each other to form a benzene ring, the remainder being hydrogen;
compound.
delete delete delete According to 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 at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers is one of claims 1, 3 to 5, and 9 Any one comprising the compound according to claim 1, an organic light emitting device.

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